Leigh Canham (Eds.) - Handbook of Porous Silicon-Springer International Publishing (2014)

Leigh Canham
Editor
Handbook of
Porous Silicon
1 3Reference
Handbook of Porous Silicon
Leigh Canham
Editor
Handbook of
Porous Silicon
With 247 Figures and 139 Tables
Editor
Leigh Canham
pSiMedica Ltd
Malvern, UK
ISBN 978-3-319-05743-9
ISBN 978-3-319-05744-6 (eBook)
ISBN 978-3-319-05745-3 (print and electronic bundle)
DOI 10.1007/978-3-319-05744-6
Springer Zug Heidelberg New York Dordrecht London
Library of Congress Control Number: 2014954093
# Springer International Publishing Switzerland 2014
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Preface
The semiconductor silicon has often been referred to as the most studied and most
influential material made by mankind. The stone, bronze, and iron ages became
the silicon age with the emergence of integrated circuits. Micromachining it
enabled complex microdevices with moving parts to be realized. Nanostructuring
it via porosification has yielded some amazing phenomena, most of which are
covered in this handbook.
Scientific interest in porous silicon has grown significantly over the last 25 years
fundamentally because it is a form of silicon that has both highly tunable and
remarkable properties. These properties can be dramatically different from those of
solid silicon and have enabled opportunities to arise in diverse fields that started in
electronics but now include microsystems, optoelectronics, optics, acoustics,
energy conversion, diagnostics, nutrition, medical therapy and, cosmetics.
By having almost 100 complementary reviews, this handbook strives to be the
most comprehensive textbook on the material ever published. I hope it will be
useful to my many friends and research colleagues already very active with porous
silicon research but also to those new to the field.
The expertise required to create this handbook represents the combined intellect
of more than 80 scientists from more than 30 countries whose pioneering work
has shaped this multidisciplinary scientific field of endeavor. The handbook is
organized into five parts that cover fabrication, properties, characterization,
processing, and applications. Each part has an introductory review where I have
tried to show the important links with more focused reviews elsewhere and to
highlight and provide references to important topics that did not receive dedicated
reviews. Nonetheless, I apologize in advance for the many omissions of important
work that fell through the cracks. Within each part, the reviews are also grouped
and ordered by complementary topics. For example, the first part on fabrication
starts with the various techniques but then progresses to fabrication of different
types of porosity with the given technique(s) and then the different physical forms
of porous silicon. In a similar manner, the properties part of the handbook groups
together complementary reviews on specific optical, magnetic, emissive, and
chemical properties and so on.
There are many people to thank for such a bold enterprise. It has taken years of
both planning and execution, so first and foremost, I would like to thank both the
v
vi
Preface
contributors and the publisher, Springer, for their patience! I would like to thank
Karin Bartsch, Coordinating Editor at Springer, for her tireless efforts at dealing
with so many authors, myself in particular. Rasidha Sulthana also did a great job in
managing the reformatting, type-setting, and checking of proofs for 94 review
articles. I would like to thank Sonia Ojo and Lydia Mueller, Senior Editors at
Springer, for their continued faith and support of this lengthy project. Finally, thank
you, the reader, for your interest in this material. I hope this book facilitates your
research in the future and perhaps stimulates you to join our vibrant and expanding
porous silicon community. The old dog of semiconductors continues to exhibit
new tricks.
Malvern
August 2014
L. Canham
Contents
Part I Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
........................
Porous Silicon Formation by Anodization . . . . . . . . . . . . . . . . . . . . . . .

Armando Loni
11
..................
23
Porous Silicon Formation by Stain Etching . . . . . . . . . . . . . . . . . . . . . .

Kurt W. Kolasinski
35
Routes of Formation for Porous Silicon

Leigh Canham
Porous Silicon Formation by Galvanic Etching

Kurt W. Kolasinski
Porous Silicon Formation by Metal Nanoparticle-Assisted

Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Claude Levy-Clement
49
Porous Silicon Formation by Photoetching . . . . . . . . . . . . . . . . . . . . . .

Sadao Adachi
67
Porous Silicon Formation by HNO3/HF Vapor Etching . . . . . . . . . . . .

Brahim Bessas
75
Porous Silicon Formation by Porous Silica Reduction . . . . . . . . . . . . .

Leigh Canham
85
.................
93
Macroporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Noureddine Gabouze and Francois Ozanam
103
Mesoporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alexey Khokhlov and Rustem Valiullin
115
Microporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Leigh Canham
129
Porous Silicon Formation by Mechanical Means

Jaroslaw Jakubowicz
vii
viii
Contents
Pore Volume (Porosity) in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . .

Leigh Canham
135
Ultrathin Porous Silicon Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Brahim Bessas
143
Porous Silicon Multilayers and Superlattices . . . . . . . . . . . . . . . . . . . .

Vivechana Agarwal
153
Porous Silicon Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Leigh Canham
163
MACE Silicon Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Ciro Chiappini
171
..........................
187
Polymer - Porous Silicon Composites

Ester Segal and Maksym A. Krepker
Part II
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
199
..........................
201
Thermal Properties of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . .

Nobuyoshi Koshida
207
Mechanical Properties of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . .

Leigh Canham
213
Mesopore Diffusion Within Porous Silicon . . . . . . . . . . . . . . . . . . . . . .

Jorg Karger and Rustem Valiullin
221
Refractive Index of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Honglae Sohn
231
........................
245
.....................................
255
.........................
263
Diamagnetic Behavior of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . .

Klemens Rumpf and Petra Granitzer
281
Ferromagnetism and Ferromagnetic Silicon Nanocomposites . . . . . . .

Petra Granitzer and Klemens Rumpf
287
Tunable Properties of Porous Silicon

Leigh Canham
Optical Birefringence of Porous Silicon

Minoru Fujii and Joachim Diener
Color of Porous Silicon
Leigh Canham
Electrical Transport in Porous Silicon

Sanjay K. Ram
Paramagnetic and Superparamagnetic Silicon

Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
297
Contents
ix
Photoluminescence of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . .

Bernard Gelloz
307
.........................
321
Thermoluminescence of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . .

Valeriy Skryshevsky
335
Optical Gain in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Katerina Herynkov and Ivan Pelant
345
Electroluminescence of Porous Silicon

Bernard Gelloz
Chemical Reactivity and Surface Chemistry of

Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Michael J. Sailor
355
Biocompatibility of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Suet P. Low and Nicolas H. Voelcker
381
Biodegradability of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Qurrat Shabir
395
Part III
403
Characterization
.................................
Characterization Challenges with Porous Silicon . . . . . . . . . . . . . . . . .

Leigh Canham
405
Microscopy of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Raul J. Martn-Palma and Vicente Torres-Costa
413
...........................
423
Gas Adsorption Analysis of Porous Silicon . . . . . . . . . . . . . . . . . . . . . .

Armando Loni
431
X-Ray Diffraction in Porous Silicon

Jeffery L. Coffer
NMR Cryoporometry and Estimation of Pore Sizes in

Mesoporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rustem Valiullin
439
...............
449
Magnetic Characterization Methods for Porous Silicon . . . . . . . . . . . .

455
Chemical Characterization of Porous Silicon . . . . . . . . . . . . . . . . . . . .

Mihaela Kusko and Iuliana Mihalache
463
Characterization of Porous Silicon by Infrared Spectroscopy . . . . . . .

Yukio H. Ogata
473
Characterization of Porous Silicon by Calorimetry

Jarno Salonen
Contents
Cell Culture on Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Nicolas H. Voelcker and Suet P. Low
481
Electronic Band Structure in Porous Silicon . . . . . . . . . . . . . . . . . . . . .

Julia Tag
uena-Martnez and Chumin Wang
497
........................
505
Effects of Irradiation on Porous Silicon

Roberto Koropecki and Roberto Arce
Part IV
Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
521
Typical Processing Steps with Porous Silicon . . . . . . . . . . . . . . . . . . . .

Leigh Canham
523
...........................
531
Colloidal Lithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Luca Boarino and Michele Laus
541
Imprinting Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Judson D. Ryckman and Sharon M. Weiss
551
Drying Techniques Applied to Porous Silicon . . . . . . . . . . . . . . . . . . . .

Leigh Canham
559
Homoepitaxy on Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Barbara Terheiden
567
Heteroepitaxy on Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Reza Sabet Dariani
581
Oxidation of Macroporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Ekaterina V. Astrova
589
Sintering of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Izabela Kuzma-Filipek
599
Photolithography on Porous Silicon

Adrian Keating
Porous Silicon and Conductive Polymer Nanostructures

Via Templating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Farid A. Harraz
611
Melt Intrusion in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Armando Loni
623
..................
629
Gas and Liquid Doping of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . .

Riccardo Rurali
639
Functional Coatings of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . .

Frederique Cunin
647
Porous Silicon and Electrochemical Deposition

Yukio H. Ogata and Kazuhiro Fukami
Contents
xi
Electroencapsulation of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . .

Matti Murtomaa and Jarno Salonen
665
Photoluminescent Nanoparticle Derivatization

Via Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Benjamin R. Horrocks
671
...............
683
Milling of Porous Silicon Microparticles . . . . . . . . . . . . . . . . . . . . . . . .

Armando Loni
695
Ohmic and Rectifying Contacts to Porous Silicon . . . . . . . . . . . . . . . . .

Jayita Kanungo and Sukumar Basu
705
Processing of Macroporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . .

715
Part V
731
Silicon-Carbon Bond Formation on Porous Silicon

Lawrence A. Huck and Jillian M. Buriak
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Application Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Leigh Canham
733
RF Electrical Isolation with Porous Silicon . . . . . . . . . . . . . . . . . . . . . .

Gael Gautier
741
.........................
753
Porous Silicon Gettering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Izabela Kuzma-Filipek and Hariharsudan Sivaramakrishnan Radhakrishnan
767
Porous Silicon Micromachining Technology . . . . . . . . . . . . . . . . . . . . .

Giuseppe Barillaro
779
Porous Silicon Functionalities for BioMEMS . . . . . . . . . . . . . . . . . . . .

Julien Schweicher and Tejal A. Desai
787
...............
797
Porous Silicon Photonic Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

J. Octavio Estevez and Vivechana Agarwal
805
Porous Silicon Optical Waveguides . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Sharon M. Weiss and Xing Wei
815
Porous Silicon Diffraction Gratings . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Adrian Keating
823
.............................
835
Thermal Isolation with Porous Silicon

Androula G. Nassiopoulou
Porous Silicon for Microdevices and Microsystems

Luca De Stefano and Ilaria Rea
Porous Silicon Phononic Crystals

Paul Snow
xii
Contents
..................................
845
Porous Silicon Optical Biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Giorgi Shtenberg and Ester Segal
857
Porous Silicon-Based Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . .

Yannick Coffinier and Rabah Boukherroub
869
Porous Silicon Immunoaffinity Microarrays . . . . . . . . . . . . . . . . . . . . .

Belinda Adler, Hong Yan, Simon Ekstrom, and Thomas Laurell
887
Porous Silicon in Brachytherapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Leigh Canham and Drew Ferguson
901
Drug Delivery with Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Jarno Salonen
909
Porous Silicon and Tissue Engineering Scaffolds . . . . . . . . . . . . . . . . .

Jeffery L. Coffer
921
Porous Silicon in Photodynamic and Photothermal Therapy . . . . . . . .

Victor Yu Timoshenko
929
Porous Silicon in Immunoisolation and Bio-filtration . . . . . . . . . . . . . .

937
Porous Silicon and Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Tayyar Dzhafarov
945
Porous Silicon and Micro-Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . .

Gael Gautier
957
Porous Silicon and Li-Ion Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Nae-Lih Wu
965
Energetics with Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Monuko duPlessis
975
Porous Silicon and Functional Foods . . . . . . . . . . . . . . . . . . . . . . . . . . .

Leigh Canham
985
Porous Silicon for Oral Hygiene and Cosmetics . . . . . . . . . . . . . . . . . .

Leigh Canham
999
Porous Silicon Gas Sensing

Giuseppe Barillaro
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1009
Contributors
Sadao Adachi Division of Electronics and Informatics, Faculty of Science and

Technology, Gunma University, Gunma, Kiryu-shi, Japan
Belinda Adler Faculty of Engineering, Department of Biomedical Engineering,
Lund University, Lund, Sweden
Vivechana Agarwal Centro de Investigacion en Ingenieria y Ciencias Aplicadads,
Universidad Autonoma del Estado de Morelos, Col. Chamilpa, Cuernavaca,
Mexico
Roberto Arce Grupo de Semiconductores Nanoestructurados, Instituto de Fsica
del Litoral, IFIS Litoral (UNL-CONICET), Santa Fe, Argentina
Ekaterina V. Astrova Ioffe Physical Technical Institute, St. Petersburg, Russia
Giuseppe Barillaro Dipartimento di Ingegneria dellInformazione, Universit di
Pisa, Pisa, Italy
Sukumar Basu IC Design & Fabrication Center, Department of Electronics &
Telecommunication Engineering, Jadavpur University, Kolkata, India
Brahim Bessas Research and Technology Centre of Energy, Borj-Cedria
Technopark, Hammam-Lif, Tunisia
Luca Boarino Nanofacility Piemonte, Istituto Nazionale di Ricerca Metrologica,
Torino, Italy
Rabah Boukherroub Parc de la Haute Borne, Institut de Recherche Interdisciplinaire (IRI), Groupe NanoBiointerfaces, Villeneuve dAscq Cedex, France
Jillian M. Buriak Department of Chemistry, University of Alberta, Edmonton,
AB, Canada
Leigh Canham pSiMedica Ltd., Malvern Hills Science Park, Malvern, Worcester,
UK
Ciro Chiappini Department of Materials, Imperial College London, Faculty of
Engineering, London, UK
xiii
xiv
Contributors
Jeffery L. Coffer Department of Chemistry, Texas Christian University, Fort

Worth, TX, USA
Yannick Coffinier Parc de la Haute Borne, Institut de Recherche Interdisciplinaire (IRI), Groupe NanoBiointerfaces, Villeneuve dAscq Cedex, France
Frederique Cunin Institut Charles Gerhardt Montpellier, Montpellier, France
Reza Sabet Dariani Department of Physics, Alzahra University, Tehran, Iran
Tejal A. Desai Department of Bioengineering and Therapeutic Sciences,
University of California, San Francisco, CA, USA
Luca De Stefano IMM-CNR Institute for Microelectronics and Microsystems
Unit of Naples, National Research Council, Naples, Italy
Joachim Diener Physik-Department, Technische Universitat Munchen, Garching,
Germany
Monuko duPlessis Carl and Emily Fuchs Institute for Microelectronics, Department of Electrical, Electronic and Computer Engineering, University of Pretoria,
Pretoria, South Africa
Tayyar Dzhafarov Department of Solar and Hydrogen Energy Converters,
Institute of Physics, Azerbaijan National Academy of Sciences, Baku, Azerbaijan
Simon Ekstrom Faculty of Engineering, Department of Biomedical Engineering,
J. Octavio Estevez CIICAp-UAEM, Av. Universidad, Col. Chamilpa, Cuernavaca,
Morelos, Mexico
Drew Ferguson OncoSil Medical Ltd, Malvern Hills Science Park, Malvern,
Worcestershire, UK
Minoru Fujii Department of Electrical and Electronic Engineering, Graduate
School of Engineering, Kobe University, Kobe, Japan
Kazuhiro Fukami Department of Materials Science and Engineering, Kyoto
University, Kyoto, Japan
Noureddine Gabouze Centre de Recherche sur la Technologie des Semiconducteurs et lEnergie (CRTSE), Algiers, Algeria
Gael Gautier Universite de Tours, GREMAN, Tours, France
Bernard Gelloz School of Engineering, Nagoya University, Nagoya, Japan
Petra Granitzer Institute of Physics, Karl-Franzens-University Graz, Graz,
Austria
Contributors
xv
Farid A. Harraz Nanostructured Materials and Nanotechnology Division, Central

Metallurgical Research and Development Institute (CMRDI), Cairo, Egypt
Promising Centre for Sensors and Electronic Devices (PCSED), Advanced Materials and NanoResearch Centre, Najran University, Najran, Saudi Arabia
Katerina Herynkov Institute of Physics, Academy of Sciences of the Czech
Republic, Prague 6, Czech Republic
Benjamin R. Horrocks School of Chemistry, Newcastle University, Newcastle
upon Tyne, UK
Lawrence A. Huck Department of Chemistry, University of Alberta, Edmonton,
AB, Canada
Jaroslaw Jakubowicz Poznan University of Technology, Institute of Materials
Science and Engineering, Poznan, Poland
Jayita Kanungo IC Design & Fabrication Center, Department of Electronics &
Jorg K
arger Faculty of Physics and Earth Sciences, University of Leipzig,
Leipzig, Germany
Adrian Keating The Microelectronics Research Group, School of Mechanical
and Chemical Engineering, The University of Western Australia, Crawley, WA,
Australia
Alexey Khokhlov Faculty of Physics and Earth Sciences, University of Leipzig,
Leipzig, Germany
Kurt W. Kolasinski Department of Chemistry, West Chester University, West
Chester, PA, USA
Roberto Koropecki Grupo de Semiconductores Nanoestructurados, Instituto de
Fsica del Litoral, IFIS Litoral (UNL-CONICET), Santa Fe, Argentina
Nobuyoshi Koshida Tokyo University of Agriculture and Technology, Tokyo,
Japan
Maksym A. Krepker Department of Biotechnology and Food Engineering,
Technion Israel Institute of Technology, Haifa, Israel
Mihaela Kusko Laboratory of Nanobiotechnology, National Institute for
Research and Development in Microtechnologies (IMT Bucharest), Bucharest,
Romania
Izabela Kuzma-Filipek IMEC, Heverlee, Belgium
Thomas Laurell Faculty of Engineering, Department of Biomedical Engineering,
xvi
Contributors
Michele Laus Dipartimento di Scienze e Innovazione Tecnologica (DISIT),

Universit del Piemonte Orientale A. Avogadro, INSTM, UdR Alessandria,
Alessandria, Italy
Claude Levy-Clement Institut de Chimie et des Materiaux Paris-Est, CNRS,
Thiais, France
Armando Loni pSiMedica Ltd, Malvern, Worcestershire, UK
Suet P. Low Mawson Institute, University of South Australia, Adelaide, SA,
Australia
Raul J. Martn-Palma Departamento de Fsica Aplicada, Universidad Autonoma
de Madrid, Cantoblanco, Madrid, Spain
Iuliana Mihalache Laboratory of Nanobiotechnology, National Institute for
Research and Development in Microtechnologies (IMT Bucharest), Bucharest,
Romania
Matti Murtomaa Department of Physics and Astronomy, University of Turku,
Turku, Finland
Androula G. Nassiopoulou NCSR Demokritos, Institute of Nanoscience and
Nanotechnology (INN), Terma Patriarchou Grigoriou, Athens, Greece
Yukio H. Ogata Institute of Advanced Energy, Kyoto University, Uji, Kyoto,
Japan
Francois Ozanam Physique de
polytechnique, Palaiseau, France
la
Matie`re
Condensee,
CNRS-Ecole
Ivan Pelant Institute of Physics, Academy of Sciences of the Czech Republic,

Prague 6, Czech Republic
Hariharsudan Sivaramakrishnan Radhakrishnan IMEC, Heverlee, Belgium
Sanjay K. Ram Department of Physics and Astronomy, Aarhus University,
Aarhus C, Denmark
Interdisciplinary Nanoscience Center iNANO, Aarhus University, Aarhus C,
Denmark
Ilaria Rea IMM-CNR Institute for Microelectronics and Microsystems Unit of
Naples, National Research Council, Naples, Italy
Klemens Rumpf Institute of Physics, Karl-Franzens-University Graz, Graz,
Austria
Riccardo Rurali Institut de Cie`ncia de Materials de Barcelona (ICMAB-CSIC),
Campus de Bellaterra, Bellaterra, Spain
Contributors
xvii
Judson D. Ryckman Department of Electrical Engineering and Computer

Science, Vanderbilt University, Nashville, TN, USA
Michael J. Sailor Department of Chemistry and Biochemistry, University of
California, San Diego, La Jolla, CA, USA
Jarno Salonen Department of Physics and Astronomy, Laboratory of Industrial
Physics, University of Turku, Turku, Finland
Julien Schweicher Department of Chemistry, Universite Libre de Bruxelles,
Bruxelles, Belgium
Ester Segal Department of Biotechnology and Food Engineering, The Russell
Berrie Nanotechnology Institute, Technion Israel Institute of Technology, Haifa,
Israel
Qurrat Shabir pSiMedica Ltd, Malvern, Worcester, UK
Giorgi Shtenberg The interdepartmental Program of Biotechnology, Department
of Biotechnology and Food Engineering, Technion Israel Institute of Technology,
Haifa, Israel
Valeriy Skryshevsky Institute of High Technologies, Taras Shevchenko National
University of Kyiv, Kyiv, Ukraine
Paul Snow Department of Physics, University of Bath, Bath, UK
Honglae Sohn Department of Chemistry, Chosun University, Gwangju, Republic
of Korea
Julia Tag
uena-Martnez Instituto de Energas Renovables, Universidad Nacional
Autonoma de Mexico, Temixco, Morelos, Mexico
Barbara Terheiden Department of Physics, University of Konstanz, Constance,
Germany
Victor Yu Timoshenko Physics Department, M.V. Lomonosov Moscow State
University, Moscow, Russia
Vicente Torres-Costa Departamento de Fsica Aplicada, Universidad Autonoma
de Madrid, Cantoblanco, Madrid, Spain
Rustem Valiullin Faculty of Physics and Earth Sciences, University of Leipzig,
Leipzig, Germany
Nicolas H. Voelcker Mawson Institute, University of South Australia, Adelaide,
SA, Australia
Chumin Wang Instituto de Investigaciones en Materiales, Universidad Nacional
Autonoma de Mexico, Mexico, Mexico
xviii
Contributors
Xing Wei Department of Electrical Engineering and Computer Science, Vanderbilt University, Nashville, TN, USA
Sharon M. Weiss Department of Electrical Engineering and Computer Science,
Vanderbilt University, Nashville, TN, USA
Nae-Lih Wu Department of Chemical Engineering, National Taiwan University,
Taipei, Taiwan
Hong Yan Faculty of Engineering, Department of Biomedical Engineering,
Part I
Fabrication

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Schematic Route Map . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Specific Fabrication Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3
4
5
8
Abstract
Porous silicon has been fabricated by both top-down techniques from solid
silicon and bottom-up routes from silicon atoms and silicon-based molecules.
Over the last 50 years, electrochemical etching has been the most investigated
approach for chip-based applications and has been utilized to create highly
directional mesoporosity and macroporosity. Chemical conversion of porous or
solid silica is now receiving increasing attention for applications that require
inexpensive mesoporous silicon in powder form. Very few techniques are
currently available for creating wholly microporous silicon with pore size below
2 nm. This review summarizes, from a chronological perspective, how more
than 30 fabrication routes have now been developed to create different types of
porous silicon.
Introduction
Porous silicon, solid silicon with voids therein, can be generated by diverse means.
Although top-down techniques utilizing electrochemical etching techniques have
dominated the academic literature over the last 50 years, from 1960 to 2010, there
L. Canham (*)
pSiMedica Ltd., Malvern Hills Science Park, Malvern, Worcester, UK
e-mail: lcanham@psivida.com
L. Canham (ed.), Handbook of Porous Silicon,
DOI 10.1007/978-3-319-05744-6_1
L. Canham
have since been many other routes demonstrated: both top-down routes from solid
silicon and bottom-up routes from silicon atoms and silicon-based molecules.
The purpose of this review is to capture for the reader, in one brief document, all
those fabrication techniques the author is aware of and highlight their potential
applicability, depending on desired structures, targeted application area, and
acceptable levels of cost. In the following chapters of this handbook, eight of
these are then chosen to be reviewed in detail.
Schematic Route Map

Figure 1 illustrates the traditional route whereby porous silicon is created from solid
silicon, which itself is derived from solid silica. A number of techniques such as
anodization (see handbook chapter Porous Silicon Formation by Anodization),
vapor etching ( Porous Silicon Formation by HNO3/HF Vapor Etching),
glancing angle deposition, lithographic etching, and photoetching ( Porous
Silicon Formation by Photoetching) are suitable for Si wafer-based processing.
Others can be used on both wafer and powder silicon feedstocks, such as stain
etching (handbook chapter Porous Silicon Formation by Stain Etching),
galvanic etching ( Porous Silicon Formation by Galvanic Etching), and
MACE ( Porous Silicon Formation by Metal Nanoparticle-Assisted Etchingand
MACE Silicon Nanostructures). Most of these techniques create highly
directional porosity and therefore properties that can be highly anisotropic (see
handbook chapters Electrical Transport in Porous Silicon; Mechanical
Properties of Porous Silicon and Optical Birefringence of Porous Silicon).
Until quite recently, etching of highly porous structures from solid silicon was
reliant on acidic fluoride chemistry; however, alkali-based etches have now been
shown to be at least capable of macropore generation under restricted conditions.
Porosifying controlled areas of a silicon wafer enables porous silicon to be
integrated with silicon circuitry or MEMS devices within chip-based products.
Although porous silicon particles (microparticles and nanoparticles) can be
derived from anodized wafers (see handbook chapters Milling of Porous Silicon
Microparticles and Photoluminescent Nanoparticle Derivatization Via Porous
Silicon), this route is only viable for low-volume high-value product areas, as in
some medical therapy applications (see handbook chapter Drug Delivery with
Porous Silicon).
If highly porous structures are required at high volumes, etching techniques will
typically have to remove large quantities of solid silicon as waste, unless recycled.
For lower-value, high-volume porous silicon products that are not silicon
chip-based (see handbook chapters Porous Silicon and Functional Foods and
Porous Silicon for Oral Hygiene and Cosmetics), there is therefore increasing
interest in fabrication routes that utilize existing highly porous feedstocks or
silicon-based molecules that are themselves waste products from solid silicon
manufacturing. These increasingly use chemical conversion of, for example, silica,
silane, or silicon tetrachloride (see Fig. 2). The chemical conversion can be
Fig. 1 Routes to porous silicon via solid silicon
Fig. 2 Routes to porous silicon using chemical conversion
promoted thermally, mechanically, or electrochemically. Here the morphology of

porosity can reflect that of the starting solid feedstocks (see handbook chapter
Porous Silicon Formation by Porous Silica Reduction) or how the silicon
nanoparticles are assembled into a porous body via sintering (see handbook chapter
Porous Silicon Formation by Mechanical Means).
Specific Fabrication Techniques

Table 1 illustrates the variety of processes (currently more than 30) now available
to create porous silicon, arranged in approximately the chronological order they have
been introduced. Historically, it was high levels of mesopores (see handbook chapter
on Mesoporous Silicon) that were created first via anodization (1) and stain
L. Canham
Table 1 A multitude of routes to form porous silicon. The techniques highlighted in black are
reviewed in detail in the handbook. Also highlighted in black are those techniques reported to
generate macroporous and microporous silicon. The literature has to date been dominated by
mesoporous silicon fabrication
Fabrication technique
Anodization
Stain etching
Anodization
Class of
technique
Etching (wet)
Etching (wet)
Etching (wet)
Class of
porosity
Mesoporous
Mesoporous
Macroporous
Anodization
Etching (wet)
Microporous
Spark erosion
Etching (dry)
Mesoporous
Photoetching
Etching (wet)
Mesoporous
Laser ablation
Hydrothermal etching
Metal ion-assisted
chemical etching
(MACE)
Galvanic etching
Plasma deposition
Vapor etching
Laser-induced plasma
Thermal
Etching (wet)
Etching (wet)
Mesoporous
Mesoporous
Mesoporous
Etching (wet)
Deposition
Etching (wet)
Etching (dry)
Mesoporous
Mesoporous
Mesoporous
Macroporous
Glancing angle
deposition
Melt gasification
Deposition
Mesoporous
Thermal
Macroporous
Plasma hydrogenation
Dealloying
Laser-induced silane
decomposition
Magnesiothermic
reduction of silica
Deposition
Etching (wet)
Deposition
Mesoporous
Mesoporous
Mesoporous
Conversion
reaction
Mechanochemical
reduction
Milling/sintering
Conversion
reaction
Mechanical
DRIE-UV lithography
Femtosecond laser
ablation
Ultrathin film annealing
Anodization (alkali)
Electrodeposition
Etching (dry)
Thermal
Macroporous
Mesoporous
Thermal
Etching (wet)
Deposition
Mesoporous
Macroporous
Mesoporous
Early paper on
technique
Uhlir (1956)
Archer (1960)
Theunissen
et al. (1972)
Canham and Groszek
(1992)
Hummel and Chang
(1992)
Noguchi and Suemune
(1993)
Savin et al. (1996)
Chen et al. (1996)
Dimova-Malinovska
et al. (1997)
Ashruff et al. (1999)
Kalkan et al. (2000)
Saadoun et al. (2002)
Kabashin and Meunier
(2002)
Beydaghan et al. (2004)
Year
1956
1960
1972
1992
1992
1993
1996
1996
1997
1999
2000
2002
2002
2004
Nakahata and
Nakajima (2004)
Abdi et al. (2005)
Fukatani et al. (2005)
Voigt et al. (2005)
2005
2005
2005
Mesoporous
Microporous
Mesoporous
Bao et al. (2007)
2007
Zheng et al. (2007)
2007
Macroporous
Jacubowicz
et al. (2007)
Woldering et al. (2008)
Mahmood et al. (2009)
2007
Fang et al. (2010)

Abburi et al. (2010)
Krishnamurthy
et al. (2011)
2004
2008
2009
2010
2010
2011
(continued)
Table 1 (continued)
Fabrication technique
Carbothermal reduction
of silica
Sacrificial template
Sodiothermic reduction
of silica
Magnetron sputtering
Micromachining and
wet etching
Platinum NP-assisted
etching (PaCE)
Ion implantation
Templated silicon
tetrachloride reduction
Rochow reaction-based
etching
Class of
technique
Conversion
reaction
Deposition
Conversion
reaction
Deposition
Etching (wet)
Class of
porosity
Macroporous
Early paper on
technique
Yang et al. (2012)
Year
2012
Mesoporous
Mesoporous
Huang et al. (2013)

Wang et al. (2013)
2013
2013
Mesoporous
Macroporous
Godhino et al. (2013)

Deng et al. (2013)
2013
2013
Etching (wet)
Mesoporous
Li et al. (2013)
2013
Irradiation
Conversion
reaction
Etching (dry)
Macroporous
Mesoporous
Stepanov et al. (2013)

Dai et al. (2014)
2013
2014
Macroporous
Zhang et al. (2014)
2014
etching (2) of electronic-grade crystalline silicon. Depending on wafer resistivity and

anodization conditions, it was subsequently shown that both macropores (see chapter
Macroporous Silicon) and micropores (see chapter Microporous Silicon)
could also be realized via the anodization route. In the 1990s a multitude of different
techniques for creating mesoporous luminescent silicon were identified. All the
etching techniques tend to create open porosity where pores are accessible from
the external surfaces of the structure. Specific techniques to create closed porosity
include melt gasification (Nakahata and Nakajima 2004) and milling/sintering
(Jakubowicz et al. 2007).
The most popular conversion reaction is currently the magnesiothermic reduction
of porous silica, as introduced by Sandhage and co-workers in 2007 (Bao et al. 2007).
This has been utilized with both synthetic silicas and biogenic silicas extracted
from plants (see handbook chapter Porous Silicon Formation by Porous Silica
Reduction). The major challenge in scalability for mesoporous silicon via this route
is control of the strong exothermic nature of the reaction to avoid sintering. Indeed,
carbothermal reduction (Yang et al. 2012) requires much higher temperatures and is
more amenable to macroporous silicon fabrication. Sodiothermic reduction (Wang
et al. 2013) can be carried out at very low temperatures but is probably less scalable
because of the high cost and reactive nature of sodium metal. Similar restrictions are
also applicable to the recent study using NaK alloy (Dai et al. 2014). Aluminothermic
reduction (Zheng et al. 2007) looks much more attractive in this regard since
aluminum is a very inexpensive metal.
Note that there are currently very few techniques to make wholly microporous
silicon (see handbook chapter Microporous Silicon) where the average pore
diameter is under 2 nm. For virtually all top-down techniques, the porous silicon
created is polycrystalline. For some bottom-up techniques such as sputtering/
L. Canham
dealloying (Fukatani et al. 2005), electrodeposition (Krishnamurthy et al. 2011),

or sodiothermic reduction (Wang et al. 2013), it is reported to be amorphous.
Choice of fabrication technique for both mesoporous and macroporous silicon is
very much dictated by application area, which in turn has differing requirements on
porosity levels, pore morphology, skeleton purity, physical form, cost, and volume.
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conference, Hamburg, pp 17791783
Abdi Y, Derakhshandeh J, Hashemi P, Mohajerzadeh S, Karbassian F, Nayeri F, Arzi E, Robertson
MD, Radamson H (2005) Light emitting nano-porous silicon structures fabricated using a
plasma hydrogenation technique. Mater Sci Eng B124125:483487
Archer RJ (1960) Stain films on silicon. J Phys Chem Solids 14:104110
Ashruf CMA, French PJ, Bressers PMMC, Kelly JJ et al (1999) Galvanic porous silicon formation
without external contacts. Sens Actuat A 74:118122
Bao Z, Weatherspoon MR, Shian S, Cai Y, Graham PD, Allan SM, Ahmad G, Dickerson MB,
Church BC, Kang Z, Abernathy HW III, Summers CJ, Liu M, Sandhage KH (2007) Chemical
reduction of three-dimensional silica micro-assemblies into microporous silicon replicas. Nat
Lett 446:172
Beydaghyan G, Kaminska K, Brown T, Robbie K (2004) Enhanced birefringence in vacuum
evaporated silicon thin films. Appl Optics 43(28):53435349
Canham LT, Groszek AJ (1992) Characterization of microporous silicon by flow calorimetry
comparison with a hydrophobic silica molecular sieve. J Appl Phys 72:1558
Chen Q, Zhou G, Zhu J, Fan C, Li X-G, Zhang Y (1996) Ultraviolet light emission from porous
silicon hydrothermally prepared. Phys Lett A 224:133136
Dai F, Zai J, Yi R, Gordin ML, Sohn H, Wang D (2014) Bottom-up synthesis of high surface area
mesoporous crystalline silicon and evaluation of its hydrogen evolution performance. Nat
Commun 5:3605
Deng T, Chen J, Wu CN, Liu ZW (2013) Fabrication of inverted pyramid silicon nanopore arrays
with three step wet etching. ECS J Solid State Sci Technol 2(11):419422
Dimova-Malinovska D, Sendova-Vassileva M, Tzenov N, Kamenova M (1997) Preparation of
thin porous silicon layers by stain etching. Thin Solid Films 297:285290
Fang DZ, Striemer CC, Gaborski TR, McGrath JL, Fauchet PM (2010) Methods for controlling the
pore properties of ultra-thin nanocrystalline silicon membranes. J Phys Cond Mater 22:454134
Fukatani K, Ishida Y, Aiba T, Miyata H, Den T (2005) Characterization of nanoporous Si thin
films obtained by Al-Si phase separation. Appl Phys Lett 87:253112
Godhino V, Caballero-Hernandez J, Jamon D, Rojas TC, Schierholz R, Garcia-Lopez J, Ferrer FJ,
Fernandez A (2013) A new bottom-up methodology to produce silicon layers with a closed
porosity nanostructure and reduced refractive index. Nanotechnology 24:275604
Huang X, Gonzalo-Rodriguez R, Rich R, Gryczynski Z, Coffer JL (2013) Fabrication and size
dependent properties of porous silicon nanotube arrays. Chem Commun 49(51):57605762
Hummel RE, Chang S-S (1992) Novel technique for preparing porous silicon. Appl Phys Lett
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Jakubowicz J, Smardz K, Smardz L (2007) Characterisation of porous silicon prepared by powder
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Kabashin AV, Meunier M (2002) Fabrication of photoluminescent Si-based layers by air optical
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Kalkan AK, Bae S, Li H, Hayes DJ, Fosash SJ (2000) Nanocrystalline Si thin films with arrayed
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Krishnamurthy A, Rasmussen DH, Suni II (2011) Galvanic deposition of nanoporous Si onto 6061
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Li X, Xiao Y, Yan C, Song JW, Talvev V, Schweizer SL, Pielkieska K, Sprafke A, Lee JH,
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Mahmood AS, Sivakumar M, Venkatakrishnan K, Tan B (2009) Enhancement in optical absorption of silicon fibrous nanostructure produced using femtosecond laser ablation. Appl Phys Lett
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Porous Silicon Formation by Anodization

Armando Loni
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Anodization of Silicon Wafers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Anodization Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rinsing and Drying of Porous Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Layer Uniformity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nonaqueous Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrolyte Additives: Surfactants, Oxidizers, and Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Tunable Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process Variability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrode Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Health and Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
12
13
14
15
16
16
17
18
19
19
20
Abstract
The key aspects of porous silicon manufactured by anodization are reviewed, with
the following subjects being addressed: anodization of different wafer types, wafer
cell design, post-anodization handling requirements (rinsing/drying/storage),
parameters affecting layer uniformity, the use of nonaqueous electrolytes and
electrolyte additives (surfactants, oxidizers, and other types), methods for tuning
porosity, process control and natural variability, different electrode materials, and
the requirements for maintaining health and safety.
A. Loni (*)
pSiMedica Ltd, Malvern, Worcestershire, UK
e-mail: aloni@psivida.com
DOI 10.1007/978-3-319-05744-6_2
11
12
A. Loni
Introduction
While the vast majority of published research on porous silicon is based upon
layers produced by bench-top processing of wafer pieces and small-diameter
wafers, this historical work underpins more recent developments in equipment and
processing methodologies for commercial applications, where scaled-up manufacture,
wafer-scale integration, and batch-to-batch reproducibility are key.
Three comprehensive books on porous silicon have been published, wherein
detailed information can be found related to silicon anodization (Canham 1997;
Lehman 2002; Sailor 2012a). The topics covered include dissolution chemistries
and the dependences of porosity, pore morphology, and pore size distribution
on various parameters (e.g., wafer type/doping, electrolyte composition, current
density, time); additionally, different types of electrochemical cells are discussed
(Lehman 2002; Sailor 2012a), as well as some of the more practical aspects related
to anodization (Sailor 2012a; e.g., wafer preparation, equipment and instrumentation, health and safety). The reader is referred to these references for essential
background reading.
Anodization of Silicon Wafers

The porosification of the surface of a silicon wafer is generally referred to as
anodization and occurs when the wafer is anodically biased in a fluoride-based
electrolyte solution. The most commonly used electrolyte component is hydrofluoric
acid (HF), with ammonium fluoride (Kuhl et al. 1998) being less common. The
degree of anodization is defined by the layer formation rate and porosity and, together
with pore morphology, depends on wafer type and resistivity, the applied current
density and time, and the electrolyte composition (HF concentration, with or without
additives). Secondary parameters include electrolyte temperature and pH.
The surface of a silicon wafer, as received from the manufacturer, will always be
covered with a native oxide film. The oxide layer will be removed when the wafer is
immersed in HF, although the cleanliness of the underlying surface can influence
the anodization process and certain applications may therefore require wafer
pre-cleaning prior to anodization (Sailor 2012b).
A heavily doped wafer (p+,++, n+,++) can be readily anodized in a variety of
HF-based electrolytes to form mesoporous silicon. A lightly doped wafer (p, n,
and majority carrier concentration <1018 cm3) generally requires an ohmic contact
to be made on the backside, either by ion implantation or by depositing a thin metal
layer such as Al (for p-type wafers) and AuSb (for n-type wafers); mechanical
abrasion of the backside of the wafer, before metal deposition, can often improve
the ohmic contact.
Lightly doped p-type wafers can be anodized to form either microporous,
mesoporous, or macroporous layers. Lightly doped n-type wafers have the additional
requirement for light assistance, which involves illuminating the back or front side of
13
the wafer to be anodized with high intensity white light (while minimizing radiative
heating of the wafer/electrolyte). The light generates electronhole pairs in the
exposed area, the holes being injected into the silicon valence band, thereby
facilitating the electrochemical dissolution process. With frontside illumination, a
pseudo bilayer structure is formed, comprised of a very thin high porosity microporous
layer at the surface above a much thicker (and lower porosity) macroporous layer, the
relative thicknesses being dependent on the intensity (and wavelength range) of light
and relative absorption coefficient of the wafer. Without illumination, or with backside
illumination, a higher voltage is required and a low porosity macroporous layer results.
Anodization Cells
Anodization can be carried out using very basic equipment, such as an HF-resistant
beaker with a counter electrode and power supply. Small areas can be processed on
part wafers through suitable masking techniques, such that all of the current is
directed across an exposed portion of the silicon work piece. However, in order to
improve layer uniformity and to anodize large area wafers in a reproducible manner,
certain demands and difficulties must be overcome (Carstensen et al. 2005), discussed
below, that generally necessitate a custom fabricated anodization tool.
Many anodization cell designs have been developed and reported in the literature, with some being patented and marketed on a commercial basis. The design of
the anodization tool depends very much on the nature of the application, the type
of layers and process flexibility required, the proposed throughput, and the degree
of automation.
Figure 1 shows a double-cell arrangement used to anodize single wafers up to
150 mm in diameter. Comprised of two cell halves (each with a large area
integrated electrode) clamped together with the wafer mounted between the two,
electrolyte from two (vented) reservoirs supplies each cell half and is pumped
continuously during anodization.
Figure 2 shows a single-cell arrangement used to process up to five 150-mmdiameter wafers simultaneously; the wafers are mounted in subassembly racks
before being loaded into the anodization tank; anodization is carried out with
continuously flowing electrolyte (from a single large reservoir) and the wafers are
transferred to a rinse tank after anodization.
Many applications require the material to be separated from the wafer (e.g., for
conversion to powder). Separation can be achieved in situ (Solanki et al. 2004)
by applying a short high current density pulse at the end of the anodization process,
a process akin to electropolishing; the pulse duration and amplitude are chosen to
facilitate either partial or full detachment in the anodization equipment; once the cell
is drained, the wet layer (sometimes fragmented) remains on the surface of the wafer
through surface tension, with full separation obtained outside of the anodization
equipment via subsequent soaking in alcohol. The remaining substrate wafer can be
reused several times, depending on the detached layer (and wafer) thickness.
14
A. Loni
Fig. 1 Double
electrochemical cell used to
manually process wafers up to
150 mm diameter (pSiMedica
Ltd)
Fig. 2 (a) Multi-wafer anodizer (right, protective cover removed to show ancillaries) and power
supply/control rack (left), (b) wafer racks in etch tank (pSiMedica Ltd)
Rinsing and Drying of Porous Layers

The presence of residual toxic chemical species, such as the electrolyte (HF) itself and
the etch by-products silicon tetrafluoride (SiF4) and hexafluorosilicic acid (H2SiF6),
all water soluble, must be considered after anodization (Koynov et al. 2011) and,
likewise, any residual electrolyte additives. The secondary reaction of H2SiF6
with water in the aqueous environment of the pores may produce metasilicic acid
(H2SiO3) this can polymerize to a less-soluble (poly-silicate) gel (and ultimately a
solid), which may entrap the residual toxic species mentioned above (Koynov
et al. 2011). The complete removal of all toxic species is a prerequisite for most
applications and is particularly important for the biomedical field.
For wafer-based layers, water can be used to rinse the anodized wafer on removal
from the equipment and subsequent wafer spinning will leave the surface in a dry
condition. However, water cannot ingress into the pores due to the hydrophobic nature
15
of the anodized layer, so residual chemical species may remain; alcohol rinsing is
therefore recommended prior to wafer spinning, followed by drying at elevated
temperature (on a hot plate or under vacuum).
For both wafer-based and detached layers, residual toxic species can still reside in
the pores, even after alcohol rinsing, drying, and storage. Rigorous washing, rinsing,
and drying must therefore be employed before use or further processing; this generally utilizes a combination of water and alcohol, with drying carried out under
vacuum at elevated temperature (up to 200 C); the time required is dependent on
the thickness of the layer, pore volume, pore morphology, drying temperature, and
vacuum conditions. Layers of very high porosity (>90 %) would normally exhibit
crazing and pore collapse on air exposure (with loss of pore volume), unless kept
wet before utilizing supercritical drying (Canham et al. 1994a). Chapter Drying
Techniques Applied to Porous Silicon of this handbook focuses on such issues.
In practice, it can be extremely difficult to completely remove residual solution
from within micro-/mesopores due to inherently strong capillary forces hence, the
importance of repeated rinsing and washing, at the very least, to minimize the
concentration of any toxic component.
Layer Uniformity
The physical properties of a porous silicon sample can vary depending on, for
example, the degree of lateral variation in layer thickness and/or porosity, the
interface roughness between porous layers or at the layer/substrate boundary, and
any vertical porosity gradation. As mentioned previously, careful design of the
anodization equipment can minimize most sources of inhomogeneity.
A uniform current presented across the whole area of the exposed wafer surface is
essential, and for this reason, it is best to incorporate a counter electrode of a size (and
shape) that is similar to the wafer. Additionally, electrical contact to the wafer must be
uniform across the whole of the rear surface, especially important for low conductivity
wafers. The use of a large graphite backing/guard plate has been shown to improve
uniformity across the wafer, to some extent (Hossain et al. 2002). If light assistance is
required during anodization, then electrode shadowing must be minimized on the front
face of the wafer (e.g., by using a mesh or spiral arrangement).
Electrical fringe effects can affect the anodization uniformity due to different
relative current densities in comparison with the center of a wafer. If the wafer is
partially immersed in the electrolyte, for example, the meniscus region will form
with a higher current density, as will the thin edge/perimeter of the wafer that is in
contact with the electrolyte; protecting such areas with a suitably defined
electrolyte-resistant mask can improve uniformity. If the wafer is patterned on the
surface, the current density and charge flow differ at the mask edges and undercutting can result (Guendouz et al. 2000).
The existence of chemical concentration gradients and the accumulation of
hydrogen gas bubbles at the surface of the wafer (and also forming within the
porous region itself), as well as the occurrence of a nonuniform temperature
16
A. Loni
distribution caused by heating, are all problematic when anodizing in a static

(non-flowing) electrolyte. While ultrasonic agitation can be used to liberate gas
bubbles during anodization (Takai and Itoh 1986; Liu et al. 2003), a continuous
(laminar) flow of electrolyte is recommended as a simpler means of flushing the
hydrogen away from the wafer surface (eventually to be vented to the outside
ambient), thus improving layer uniformity. A continuous flow also helps to dissipate heat buildup in the electrolyte and can minimize chemical concentration
gradients within the electrolyte and at the pore fronts, both of which will affect
the anodization process and properties of the resulting layers.
For porous silicon multilayer structures (see chapter Porous Silicon
Multilayers and Superlattices of this handbook), improved interface uniformity
has been achieved by incorporating a short period of zero bias between individual
layers, thereby allowing the hydrogen to diffuse from within the pores and the
fluoride to be replenished at the pore tips (Takai and Itoh 1986). The pulsed
etching (Billat et al. 1997) and stop-etching (Hou et al. 1996) techniques are
based on a similar principle, with the latter (Khokhlov 2008) reportedly narrowing
the pore size distribution for layers produced with high current density (although
the role of static chemical leaching during the relatively longer periods under zero
bias was not addressed) and the former finding use in the anodization of pn
junctions patterned on silicon wafers (McGinnis et al. 1999).
Nonaqueous Electrolytes
Aside from the more common aqueous HF-based electrolytes, nonaqueous organic
electrolytes in combination with a suitable fluoride source have been used, primarily for the production of macroporous layers both on silicon wafers (Propst and
Kohl 1994; Rieger and Kohl 1995; Ponomarev and Levy-Clement 1998, 2000;
Flake et al. 1999; Thakur et al. 2012a) and in freestanding form (Thakur
et al. 2012b). Examples include acetonitrile, propylene carbonate, and dimethylformamide, with anhydrous HF (up to 2 M), tetrafluoroborate, and lithium
fluoroborate being used as fluoride sources. The inclusion of a supporting electrolyte, such as tetrabutylammonium perchlorate (up to 0.25 M), has been shown to
offer additional flexibility with regard to the resulting pore morphologies attained
(Ponomarev and Levy-Clement 2000). In contrast to aqueous electrolytes,
nonaqueous electrolytes facilitate silicon dissolution without hydrogen evolution.
Electrolyte Additives: Surfactants, Oxidizers, and Others

The addition of a surfactant (wetting agent) to the electrolyte helps to prevent
evolving hydrogen bubbles from sticking to the porous silicon surface. Alcohol
(e.g., methanol, ethanol) is the most common, with, among others, formic acid
(Baranov et al. 2000), acetic acid (Baranov et al. 2000; Semai et al. 2009), and
sodium laurel sulfate (Ogata et al. 2000); commercially available surfactants such
17
as NCW-1001 (Ogata et al. 2000), Mirasol (Lehman and Foll 1990), Triton X-100
(Chao et al. 2000), and DECON (Kordas et al. 2001) have also been used. While
alcohol-based surfactants are used in substantial quantities (>15 % v/v), the
cationic or anionic surfactants (Chao et al. 2000; Sotgiu et al. 1997) are used in
concentrations as low as 104 M (typically 5 % v/v) and sometimes in combination with alcohol.
An alcohol-based surfactant will instigate chemical leaching of the porous
silicon layer during anodization (discussed below), particularly so with long anodization times and high alcohol content, and this can result in a porosity gradient
within the layer (more porous at the surface). Without surfactant, however, an
anodized layer can be nonuniform in thickness, with substantial interface roughness
at the porous silicon substrate (Halimaoui 1993) or between different layers.
Adding hydrochloric acid to the electrolyte changes the pH and can lead to
favorable changes in the properties of the anodized material such as, for example,
enhanced and stable photoluminescence (Zangooie et al. 1998; Belogorokhov and
Belogorokhova 1999).
Various types of chemical oxidizer have been incorporated into HF-based
electrolytes. CrO3 has been used (Foll et al. 2000; Christophersen et al. 2000;
Ouyang et al. 2005) to produce macroporous silicon, while potassium permanganate (KMnO4) also acts to increase pore size (Ogata et al. 2000; Harraz et al. 2008).
The inclusion of hydrogen peroxide (H2O2) has been shown to produce layers with
monohydride passivation (Yamani et al. 1997), although its role in the formation of
layers with wider pores has been the subject of greater interest (Ogata et al. 2000;
Ge et al. 2010).
Reduced interface roughness, previously observed (Setzu et al. 1998; Servidori
et al. 2000) in samples anodized at low temperature and attributed to an increased
electrolyte viscosity, has been replicated (for some conditions) by adding a small
fraction of glycerol to the electrolyte (Kan et al. 2005). In situ functionalization of
porous silicon during anodization has been achieved by incorporating the
HF-compatible organic molecule 1-heptyne (C7H12) in the electrolyte, in concentrations up to 0.9 M (Mattei and Valentini 2003).
Tunable Porosity
If an alcohol surfactant is incorporated in the electrolyte, then the porosity of a layer
will depend on the dilution used, higher porosities being obtained with higher
alcohol content. As mentioned previously, the in situ chemical leaching of a layer
(with or without electrical bias) in HF-alcohol electrolytes can be used to good
effect to increase porosity (Halimaoui 1994; Herino et al. 1987) and pore size
(Herino et al. 1987; Herino 1997).
Porosity can be more easily tuned through choice of the applied current density
and anodization time (Herino et al. 1987; Herino 1997), and this is the basis of
forming complex multilayer or graded structures. When comparing different
anodization processes, the current densities (assuming the wafer areas are the same)
18
A. Loni
Table 1 Layer parameter dependency on current density and time (detached mesoporous silicon
layers produced with 600 p-type wafers, 0.0050.02 O cm, using 1:1 40 % HF:methanol electrolyte;
porosity determined gravimetrically; surface area and pore volume/diameter determined by
nitrogen gas adsorption authors data)
Current
density
(mA/cm2)
33
99
99
Anodization
time (min)
90
30
60
Porosity (%)
66
78
86
Depth
(m)
161
125
234
Surface
area (m2/g)
296
434
495
Pore
volume
(ml/g)
0.759
1.435
2.267
Average
pore
diameter
(nm)
10
10
18
and anodization times should be chosen such that the overall charge flow is
comparable for each process this facilitates like-for-like comparison of the
resulting properties. If an alcohol surfactant is present, however, it can be difficult
to completely preclude the effects of chemical leaching (Herino et al. 1987), and this
should be considered when making process comparisons.
From Table 1, it can be tentatively surmised that, for a fixed charge flow, the
porosity difference between 33 mA/cm2 (90 min) and 99 mA/cm2 (30 min) is
primarily due to the enhanced electrochemical dissolution of the layer at the higher
current density; when the current density is fixed (99 mA/cm2), the higher porosity
for the 60 min process is primarily due to chemical leaching of the layer. As
expected, the different porosities are accompanied by variations in surface area,
pore volume, and average pore diameter.
Porosity can also be tuned by applying a magnetic field during anodization.
A magnetic field applied perpendicular to the wafer surface, with the electrolyte
temperature maintained at 0 C, can regulate the supply of holes, the resulting
porosity being dependent on the magnetic field strength (Nakagawa et al. 1996).
Process Variability
When comparing individual wafers or layers produced sequentially, or under
different anodization conditions, the condition of the electrolyte must be considered, as this leads to process variation.
The accumulation of silicon in the electrolyte from each dissolution process (e.g., in
the form of H2SiF6), combined with the steady depletion of fluorine, is evinced by a
gradual increase in electrolyte conductivity and pH; this natural evolution of electrolyte composition with continuous use is particularly important for high-throughput
production, where associated variations within a fixed volume of electrolyte include a
gradual reduction in layer thickness and an increase in porosity (reduced yield).
Indeed, very high porosities can be achieved with a well-used electrolyte.
The point that defines the end of the useful life of the electrolyte depends on
the highest porosity or yielded weight of porous silicon that is acceptable for the
intended product or application. In order to maintain the desired blend, the electrolyte
19
can be replenished by auto-dosing (with fresh HF and/or surfactant) on a continual

basis; this requires a feedback control loop whereby some indicator of the condition of
the electrolyte is continuously monitored, e.g., HF concentration (Nehmann
et al. 2012). However, the working volume of the equipment and the need to dispose
of large quantities of waste electrolyte in a safe manner both limit the extent to which
auto-dosing can be used.
When a number of wafers are anodized simultaneously, the amount of electrical
power supplied to the electrolyte is much greater than that required for a single
wafer; this leads to electrolyte heating, which, depending on current density,
anodization time, and wafer batch size, can be significant. The chemical dissolution
process is temperature dependent (Garman et al. 2001; Balagurov et al. 2006),
while the evaporation rate of any volatile surfactant will also increase at elevated
temperature. It has been shown, also, that photoluminescence wavelength and
intensity and layer crystallinity are dependent on the electrolyte temperature used
for anodization (Ono et al. 1993). The control of electrolyte temperature during
anodization is therefore important in many respects. Any heat generated during
anodization will be dissipated to some extent by continuously pumping the electrolyte within the equipment, although the use of a cooling coil (e.g., in the
electrolyte reservoir) or integrated chilling bath can be more effective.
Electrode Materials
Platinum metal is commonly used as an electrode material, due to its relatively high
chemical resistivity. It has been shown (Pourbaiz et al. 1959; Llopis and Sancho 1961;
Kodera et al. 2007), however, that anodically biased platinum slowly corrodes in the
presence of acidic solutions. While the corrosion rate is extremely small, if the same
counter electrode is used continuously, a buildup of platinum (and its oxide) occurs in
the electrolyte; this is deposited within the equipment, as evinced by a dark film lining
the inside of the components; deposition also occurs within the porous silicon layers
(typically <20 ppm). Alternative counter electrode materials include doped silicon,
silicon coated with doped diamond, doped diamond, and vitrified carbon.
Health and Safety

The volume of hydrogen gas generated during anodization can be significant
(Motohashi 2000), especially so when high current density is used and for simultaneous/multiple wafer processing. The anodizing equipment must therefore be
vented or, if sealed, possess a pressure-release valve, to discharge the hydrogen
and avoid pressurization. Inert gas (N2) pumped into the vicinity of the working
volume (e.g., above the electrolyte) can dilute the hydrogen to a level below the
lower explosive limit, before discharging to the extracted ambient.
Care must be taken when using platinum as a counter electrode with H2O2 as
an electrolyte additive; the peroxide decomposes on exposure to the metal
20
A. Loni
(Katsounaros et al. 2012), exothermically, to form water and oxygen; the oxygen
can combine with hydrogen generated from the anodization process to form an
explosive mixture; additionally, the gradual decomposition of the peroxide also serves
to change the electrolyte composition in practice, therefore, the use of this particular
additive must be considered somewhat limited.
The storage conditions of anodized layers must be carefully considered, especially
so for large quantities, as it has been shown that silane gas can be generated and
released as the material reacts with ambient air (Canham et al. 1994b).
Chapter Chemical Reactivity and Surface Chemistry of Porous Silicon of this
handbook provides a comprehensive survey of such reactions.
It is recommended that all appropriate safety precautions be taken when working
with any quantity or concentration of hydrofluoric acid (and ammonium fluoride);
this extends to using HF-resistant equipment and personal protection and handling
of hydrofluoric acid and associated waste products (Sailor 2012c).
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Porous Silicon Formation by Galvanic

Etching
Kurt W. Kolasinski
Contents
Introduction: Classes of Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chemical Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrochemical Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electroless Etching (Stain Etching) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Specific Examples of Galvanic Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
The different classes of electrochemical etching of silicon are briefly compared

and contrasted, and then the literature on galvanic etching is comprehensively
reviewed. Thick uniform mesoporous films with surface areas as high as 910 m2/g
have been achieved with optimized galvanic etching (Fig. 1).
Introduction: Classes of Etching

Chemical Etching
Thermodynamically, Si is less stable with respect to etching in aqueous HF
(H 733 kJ mol1) than is SiO2 (H 394 kJ mol1). Nonetheless,
the etch rate at room temperature of Si is almost 5,000 times slower than that
of SiO2. That the etch rate of Si is so low is the result of the kinetic barrier
caused by hydrogen termination of the Si surface (Kolasinski 2010). This kinetic
K.W. Kolasinski (*)

Department of Chemistry, West Chester University, West Chester, PA, USA
e-mail: kkolasinski@wcupa.edu
DOI 10.1007/978-3-319-05744-6_3
23
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K.W. Kolasinski
Fig. 1 (a) Illustration of

galvanic etching with a
backside Pt layer and
frontside Si3N4 mask to
facilitate patterned porous
silicon formation. (b)
Scanning electron microscope
cross section of porous layer
bordering the Si3N4 mask.
Reprinted with permission
from Becker et al., Nano Lett.
2011, 11 803807. Copyright
2011 American Chemical
Society
valve is of great advantage for controlled restructuring of Si substrates into

porous Si (por-Si) and other etched structures including freestanding beams,
grooves, and sharpened tips. The valve can be opened with either chemical or
electrochemical actuation.
Chemical etching does not involve free charge exchange but only the local
reshuffling of electron density among surface bonds. The hydroxide ion is capable
of chemically attacking H-terminated silicon surfaces. It does so either by
catalyzing hydrolysis of Si or by binding to the surface and then participating
in ligand exchange with fluoride (Kelly and Philipsen 2005). In fluoridecontaining solutions, hydroxide can lead to the formation of ideally terminated
flat surfaces on Si(111) (Chabal et al. 1993) and nearly flat surfaces on Si(100)
(Hines et al. 2012; Clark et al. 2010). In the absence of fluoride, highly
anisotropic, crystallographically defined etching of silicon occurs (Hines 2003;
Dudley and Kolasinski 2008). Another example of purely chemical etching of
Si is that of halogens (Cl2, Br2, and I2) dissolved in HF(aq) (Meltzer and Mandler
1995; Bressers et al. 1996; Kolasinski and Gogola 2012). These reactions are
spontaneous even at room temperature. In all cases, uncontrolled chemical
etching leads to the destruction of both microporous and mesoporous silicon.
25
Electrochemical Etching
Electrochemistry involves the exchange of free charge. Again a kinetic barrier
hinders the formation of the thermodynamically more stable H2SiF6 etch product.
Now the barrier is toward electron exchange rather than attaining the correct
transition state structure to allow for the simultaneous making and breaking of
covalent bonds involved in a chemical reaction. Since (conventionally doped) Si is
a semiconductor, it has a low state density at the Fermi energy and electron transfer
or hole injection must occur via the conduction or valence bands.
Anodic Etching (Anodization)

There are several different methods to activate a system electrochemically (Lehmann
2002). The most common is anodic etching, which is initiated by the removal of
valence electrons from surface bonds of the semiconductor by the application of an
external bias in an electrochemical cell. Essentially, the activation barrier toward
electron transfer is lowered by shifting the electrochemical potential of the electrons
in the Si substrate, which allows the ensuing charge exchange and chemical steps
in the etch mechanism to proceed to their thermodynamically favored state.
This technique is reviewed elsewhere in this handbook (chapter Porous Silicon
Formation by Anodization).
Photoelectrochemical Etching (Photo-Assisted Etching)
Excitation with photons can also create valence band holes, which initiate etching.
This type of photoelectrochemical etching is commonly performed within an
electrochemical cell on n-type Si since photoexcitation is required to make free
carriers available for conduction at low voltages. However, connection to a counter
electrode is not essential for this process to occur and the formation of porous silicon
(por-Si) on freestanding crystals is well documented (Noguchi and Suemune 1993,
1994; Koker and Kolasinski 2000, 2001). This technique is also reviewed elsewhere
in this handbook (chapter Porous Silicon Formation by Photoetching).
Electroless Etching (Stain Etching)

Electroless etching removes valence electrons by the action of a solution phase
oxidizing agent. The oxidant injects holes into the valence band and is reduced in
the process of this open-circuit etching. Spontaneous electroless etching involving a
solution phase oxidant to form por-Si films is commonly called stain etching (Turner
1960; Archer 1960) and is reviewed elsewhere in this handbook (chapter Porous
Silicon Formation by Stain Etching). Because of the favorable thermodynamic
driving force toward more stable products (i.e., because etching is exergonic),
spontaneous electroless etching is in principle possible whenever the acceptor
level in the oxidant resides at an energy at or below the Fermi energy EF of
Si. The Fermi energy depends on the doping density and temperature but is usually
a few tenths of an eV below the conduction band minimum, close to 0 V versus the
26
K.W. Kolasinski
standard hydrogen electrode (SHE). However, because of the low state density
near EF and the necessity to overcome the activation energy for electron transfer,
charge transfer only occurs at an appreciable rate if the oxidant has a sufficiently
positive electrochemical potential (roughly +0.7 V vs SHE) such that its acceptor
level is close to or below the energy of the valence band maximum (Kolasinski 2010;
Kolasinski et al. 2012).
Galvanic Etching
Even when the energetic requirements for electron transfer are satisfied, some
oxidants with sufficiently positive electrochemical potentials, particularly H2O2,
can exhibit poor hole injection kinetics into bare Si. Hole injection can be
efficiently catalyzed by the presence of a metal, which can affect reactivity in
two ways. The first is simply that since it is a metal, it provides state density from EF
all the way down to the valence band maximum. In effect, the metal can shortcircuit the connection between the oxidant and the valence band. Second, the metal
can act electrocatalytically to enhance either electrochemical or chemical steps in
the redox reactions required to achieve etching. Thus, metals such as Au and Pt both
can act as electron/hole conduits, but Pt is particularly effective at electrocatalytically enhancing reactions of H+, H2O, H2O2, and O2.
Kelly and coworkers (Xia et al. 2000; Ashruf et al. 1998, 1999, 2000) recognized
the ability of a metal layer to facilitate charge transfer and etching. They developed
a hybrid approach to electrochemical etching known as galvanic etching. This is a
type of anodic etching at open circuit that results from the exposure of a metal contact
on a silicon surface to an appropriate solution. They demonstrated that it can be
performed in either acidic or alkaline solutions and that it can be used to form porous
layers or for complete etching. Furthermore, the incorporation of etch stop techniques,
e.g., fabricating p/n junctions by doping and/or epilayer growth, allows for the
formation of membranes and freestanding beams (Kelly et al. 2001; Sun et al. 2012).
Complete removal of Si occurs in alkaline solutions since alkaline solutions
attack por-Si and never allow for the formation of porous layers. Complete removal
of Si is also possible in acidic fluoride solutions if the galvanic reaction is run in the
electropolishing regime. Electropolishing occurs for high concentrations of H2O2 or
O2 and comparatively low HF concentrations. The Pt-to-Si surface area ratio also
affects electropolishing as the higher the ratio, the greater the generated current and
the more likely that electropolishing will occur.
Porous layer formation is possible in acidic fluoride solutions. This occurs when
the oxidant concentration is low and the HF concentration is comparatively high.
A surfactant such as ethanol or Triton X-100 can be added to enhance the layer
homogeneity as the surfactant aids in the release of H2 bubbles from the pore walls.
Galvanic Versus Metal-Assisted Etching
The term galvanic etching is associated with the open-circuit etching process engendered by the catalytic effect of metal layers. It is important to keep in mind that as
opposed to stain etching, in which the oxidant injects holes directly into Si, in galvanic
etching the oxidizing agent is reduced at the metal and the semiconductor is etched
27
remotely from the initial site of hole injection. The charge transfer processes are local
and occur at the solution/metal and metal/silicon interfaces. Shortly after the initial
reports of Kelly and coworkers, Bohn and coworkers recognized that if a metal
nanoparticle was used as an electrocatalyst, either pores or nanowires could be etched
(Chattopadhyay et al. 2002; Harada et al. 2001; Li and Bohn 2000). This type of
etching called metal-assisted etching and reviewed elsewhere in this volume
(chapter Porous Silicon Formation by Metal Nanoparticle-Assisted Etching)
relies on the same electrochemistry as galvanic etching but its exploitation of the
localized nature of charge injection and ensuing chemistry leads to a much richer
range of structural products.
Specific Examples of Galvanic Etching

As mentioned above, Kelly and coworkers (Xia et al. 2000; Ashruf et al. 1998, 1999,
2000) were the first to introduce galvanic etching. They incorporated standard
microfabrication techniques such as chemical vapor deposition and lithographic
patterning of photoresists to create device structures. They connected an inert metal
electrode (Au or Pt) to a Si sample by metal deposition over a Cr wetting layer.
Reduction of oxygen, H2O2 (for acidic solutions), OCl (in alkaline solutions), H+,
and H2O at the inert electrode resulted in the etching of Si at the silicon/electrolyte
interface. A 1 % H2O2 in 1 % HF was used in conjunction with a Pt/Cr electrode to
fabricate freestanding beams. Fe(CN)63 and MnO4 also supported galvanic cell
formation but led to passivation layers even at low concentrations. Solutions must be
sparged with Ar or N2 if the effects of dissolved O2 are to be avoided. With n-type Si
in acidic fluoride solutions, illumination was required. They demonstrated that
galvanic etching could be used to form microporous layers in aerated 40 % HF
with a Pt/Cr electrode on p-type Si. Macroporous layers were formed on backside
illuminated n-type Si with a Pt/Cr electrode held in a 5 % HF, 0.1 M H2O2 solution.
Macropore formation requires lithographic placement of inverted pyramidal
macropore nucleation sites.
A galvanic cell was formed with both n- and p-type Si in alkaline solutions in the
dark. A solution of 25 % tetramethylammonium hydroxide (TMAH) at 80 C was
used by Kelly and coworkers for galvanic cell formation with a Au/Cr electrode.
Etching in aerated 2.0 M KOH(aq) at 70 C led to surfaces that exhibited pyramidal
protrusions. When a Pt or Au electrode was used to form a galvanic cell during
etching, the formation of such large pyramids was suppressed.
Splinter et al. (2001a, b) also investigated galvanic etching with an HF/H2O2/
ethanol electrolyte. Similarly they found that thick (10 m) uniform films could be
fabricated. They also confirmed that the porous structure of these films was
comparable to pores generated by anodization.
From the above consideration, we see that almost any metal on silicon (particularly for noble and coinage metals) will lead to reaction of the Si substrate
whenever the system is exposed to an aqueous solution and the Si is not covered
by a passivating insulating (e.g., oxide, photoresist, or nitride) layer. This can lead
28
K.W. Kolasinski
to either intentional or unintentional changes in the structural and mechanical

properties of the system. It is especially important for Si films used in microelectromechanical systems (MEMS), for which nanometer-scale layers have a profound
impact upon their fracture and fatigue resistance. MEMS are typically fabricated
from structural elements made of Si and electrical interconnects made of a metal
such as Au. SiO2 is used as a sacrificial layer and the device is released from the
substrate by etching in HF. Therefore, postprocessing steps in MEMS fabrication
routinely lead to the exposure of metal/Si interfaces to HF.
Pierron et al. (2005) found that oxide layers up to ~80 nm thick could form at
room temperature during manufacturing due to a galvanic effect between highly
doped n-type Si and Au. Electron microscopy confirmed that the layers were porous
and composed of SiO2 covering Si cores. Concentrated HF solutions are usually
associated with oxide dissolution. However, the measured current density-voltage
behavior of the galvanic couple in their device corresponded to the transition region
in which por-Si formation was accompanied by oxide growth. They suggested that
the formation of a galvanic cell could account for unexplained findings from other
groups (Muhlstein et al. 2002; Chasiotis and Knauss 2003) and that controlling
these effects should enhance the performance of MEMS.
Polycrystalline Si (poly-Si) is also of interest in micromachining applications.
Galvanic etching in HF(aq) is just as applicable to this material as it is for singlecrystal substrates. Heuer and coworkers (Huh et al. 2006; Kahn et al. 2005) confirmed
that immersion in HF(aq) caused rougher and weaker poly-Si films in the presence of
Au or Pd metallization and led to relatively thick oxide layers. Porous Si formation
first developed along the poly-Si grain boundaries and then progressed into the grain
interiors. Oxide formation was attributed to oxidation during rinsing and air exposure,
which again led to a SiO2/Si composite as well as a gradient in composition from a
high fraction of SiO2 near the surface to pure Si deeper into the poly-Si. Galvanic
etching is minimized by reducing the number of holes by either (i) introducing n-type
dopants in the poly-Si or (ii) performing the HF immersion in the absence
of illumination. On p-type substrates, an external negative potential during HF
immersion could be used to decrease the rate of corrosion.
Liu et al. (2012) reported that photoresist effectively covered and insulated noble
metal deposited onto a poly-Si layer. Poly-Si was well protected for >80 min in
concentrated HF solutions by a 3-m-thick AZ 6130 photoresist film.
The morphological, electrical, and mechanical effects of etched poly-Si structures
have been extensively investigated by Stoldt and coworkers (Miller et al. 2005, 2007,
2008; Becker et al. 2010a, b, 2011). Micromachined p-type polysilicon in contact
with a Au layer demonstrated heterogeneous cracking or porosity across the poly-Si
surface as a result of etching. This resulted in greatly increased electrical resistance
and decreased the characteristic frequency of mechanical resonators.
Because the mechanical properties of MEMS depend strongly on their structure,
changes that occur during postprocessing must be taken into account. Miller
et al. (2007) measured the decrease in the frequency of mechanical resonance that
occurred as a function of immersion time in HF for microcantilevers as well as
comb drives in contact with Au. Time-dependent variation was also observed in
29
the modulus and hardness measured during indentation testing. They observed that
grain delineation accompanied the formation of a nanoscale porous layer in the near
surface region of the poly-Si. The por-Si layer exhibited decreased stiffness, which
changed the effective thickness of the beams. Galvanic etching can greatly influence the material properties, design, performance, lifetime, tribology, manufacture,
and required operating environment of microscale and nanoscale devices.
Morphology, resistive probe, surface wetting, and electrochemical characterization of single-crystalline and polycrystalline Si subjected to galvanic corrosion
in concentrated 48 wt% HF, 23 wt% HF diluted with water, and a 20:1 solution
of 23 wt% HF with Triton X-100 were performed by Miller et al. (2008).
The measured current density of micromachined Si was compared with (100)
wafers using polarization characterization, identifying the por-Si formation regime.
Porosity ranged from 20 % to 47 % but in some cases was as high as 70 %.
The porosity generally increased as the surface area ratio of Au to Si increased.
Chronopotentiometry, resistive probe, and microtensile characterizations were used
to identify regimes of rapid initiation, subsequent steady-state corrosion, and the
final catastrophic failure of the microtensile specimens. Corrosion current depended
exponentially on the amount of metal present. This implied that the corrosion rate was
limited by the surface area of the metal cathode. Addition of surfactant led to higher
current densities and more uniform layers.
Subsequently, this group (Becker et al. 2010b) used focused ion beam (FIB)
milling of microscale silicon-on-insulator (SOI) devices to determine the depth
uniformity of the galvanically formed por-Si as a function of the geometry of the
device. They developed a finite-element-method simulation to model the galvanic
corrosion process. The model reproduced the current-limited condition resulting
from the finite surface area of metal relative to Si and predicted the uniform etch
rate across the device for surfactant-enhanced HF solutions as observed after FIB
milling.
Becker et al. (2010a) have optimized the process to produce thick, high-surfacearea por-Si films for applications as an explosive material (see chapter entitled
Energetics with Porous Silicon). Films up to ~150 m thick with specific
surface area ~700 m2 g1 and pore diameters ~3 nm were fabricated.
Subsequently, this group optimized their galvanic process for even greater
specific area (Becker et al. 2011). A 170-nm-thick Pt layer was sputtered on the
back of the Si to form the cathode and an H2O2/HF/ethanol solution acted as the
etchant. The H2O2 concentration was 2.4 vol% of 30 % H2O2 in water. The HF to
ethanol ratio was either 20:1 or 3:1. The surface area ratio of Pt to Si was ~5. In the
20:1 solution, films with specific surface areas of ~840 m2 g1 and porosities of
6567 % were obtained. Somewhat higher specific areas (890910 m2 g1) and
porosities (7983 %) were observed for the 3:1 solution.
Galvanic cells can be formed on Si powders just as they can for c-Si and poly-Si.
Nielsen et al. (2007) used galvanic displacement to deposit Pt on Si powder grains,
which were dispersed in an aqueous mixture of HF and H2PtCl6 for 15 min. The
grains were then removed and dispersed in a 1:3:2 mixture of HF/H2O2/methanol
to affect galvanic etching. They used this procedure to produce dispersions of
30
K.W. Kolasinski
photoluminescent Si nanoparticles in the size range of 36 nm by subsequent

sonication of the grains in isopropanol. Only a thin porous layer was produced
and the core of the originally 80-m-diameter particles remained unaffected.
Nanoparticles could be generated in a similar fashion by substituting a Si wafer
for the Si powder.
Nakamura et al. investigated both Ag/por-Si (2010) and Pt/por-Si (2011) composite powders. Metallurgical grade Si powder was added to the 18 % HF, and then
AgNO3 was added to the mixture held at 30 C. Nanometer-sized Ag particles
deposited singly or as aggregates on the Si powder surface. Higher concentrations
of AgNO3 resulted in decreased Si volume and increased Ag layer thickness. The
powders were photoluminescent. The PL intensity was weaker but more stable than
that of conventionally stain-etched por-Si powders. Pt layers were deposited on a Si
surface together with the formation of a porous structure. It was found that the
oxidation state of Pt layers strongly depended on the conditions for the preparation
of Pt/PSi composite powders.
Galvanic cell formation and Si etching are also strongly linked to metal deposition
on Si surfaces (Ogata and Kobayashi 2006; Allongue and Maroun 2006; Gorostiza
et al. 2000, 2003; daRosa et al. 2008). Applications to micro- and nanoscale devices in
fields ranging from electronic devices to chemical sensors, including schemes developed for the metallization and nanopatterning of semiconductor substrates with high
selectivity and with optimal interfacial properties, have been discussed by Carraro
et al. (2007). To understand the rate as well as pH and concentration dependence of
deposition, it is essential to apply mixed-potential theory (Gorostiza et al. 2000, 2003;
daRosa et al. 2008). The morphology of the deposit is of great interest in metalassisted etching (Peng et al. 2003; Huang et al. 2011). Large-area nanostructured
noble-metal films of Ag, Pt, and Au can be deposited (Song et al. 2005) with various
morphologies on Si. The morphology of Ag films, which is different from that of Pt
and Au, depends sensitively on the deposition conditions. The roughness of Cu films
was found to decrease with increasing HF to CuSO4 concentration ratio. Concurrently, the Si surface became less oxidized and lateral connectivity between Cu nuclei
increased (daRosa et al. 2008). Au nanostructures, clusters, or dendrites with leaflike
or branch-like structure can be prepared by adjusting the temperature and the concentration of HAuCl4, ultrasonic agitation, and addition of ethanol (Wang et al. 2006).
Conclusion
Galvanic and metal-assisted etching follow the same electrochemistry. The differences
between them are related to the initial structure of the metal electrocatalyst that is
responsible for making the electrochemical etching spontaneous. While studies of
galvanic etching are dwarfed by the number devoted to metal-assisted etching, it will
continue to be an essential process to understand for any application that involves the
formation of a metal/silicon interface that is subsequently exposed to HF, such as in the
fabrication of MEMS devices. Thick uniform films with surface areas as high as
910 m2 g1 have been achieved with optimized galvanic etching (Becker et al. 2011).
31
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Sun NN, Chen JM, Jiang C, Zhang YJ, Shi F (2012) Enhanced wet-chemical etching to prepare
patterned silicon mask with controlled depths by combining photolithography with galvanic
reaction. Ind Eng Chem Res 51:793799
Turner DR (1960) On the mechanism of chemically etching germanium and silicon. J Electrochem
Soc 107:810816
Wang CH, Sun DC, Xia XH (2006) One-step formation of nanostructured gold layers via a
galvanic exchange reaction for surface enhancement Raman scattering. Nanotechnology
17:651657
Xia XH, Ashruf CMA, French PJ, Kelly JJ (2000) Galvanic cell formation in silicon/metal
contacts: the effect on silicon surface morphology. Chem Mater 12:16711678
Porous Silicon Formation by Stain Etching

Kurt W. Kolasinski
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Etchant Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rational Formulation of Stain Etchants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Practical Advice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35
37
42
42
43
Abstract
Spontaneous electroless etching of silicon surfaces with hydrofluoric acid and

chemical oxidant-based solutions is often referred to as stain etching due to the
color change it imparts. The field is comprehensively reviewed with regard to
the etching mechanisms and the range of chemical oxidants explored to date.
Introduction
The topic of this review is the etching of silicon by a fluoride solution in which
etching is initiated by hole injection from a sufficiently strong oxidant. This
spontaneous electroless etching process is commonly called stain etching when it
leads to the formation of a porous silicon film (por-Si). Fuller and Ditzenberger
(1957), Turner (1960), and Archer (1960) were unaware of the porous nature of the
films they formed but named the process after the colored stains (Fig. 1) that
appeared on their substrates. Because some of the most effective oxidants contain
a metal ion, it has sometimes also been denoted metal-assisted etching. This term is,
however, ambiguous and easily confused with a related catalytic etching process in
K.W. Kolasinski (*)
Department of Chemistry, West Chester University, West Chester, PA, USA
e-mail: kkolasinski@wcupa.edu
DOI 10.1007/978-3-319-05744-6_4
35
36
K.W. Kolasinski
Fig. 1 Four Si(100)

substrates stain etched for
different times to produce
homogeneous smooth films of
different depths, hence
different colors caused by thin
film interference in the porous
silicon layers
which a metal nanoparticle acts to catalyze hole injection from an oxidant. I will
call this catalytic etching process metal-assisted etching. It is possible to use
oxidants that are capable of stain etching (spontaneous electroless etching) in
conjunction with metal catalyst particles. Interestingly, as reviewed elsewhere in
this volume (see chapter Porous Silicon Formation by Metal NanoparticleAssisted Etching), the most frequently used oxidant for metal-assisted etching
(HOOH) has such poor hole injection kinetics (Kooij et al. 1998) that it does not
lead to significant por-Si formation in the absence of the metal catalyst.
Stain etching is spontaneous, but what differentiates it from chemical etching is
that free charge transfer is involved in stain etching. Hydroxide exhibits both
chemical and electrochemical etching pathways (Allongue et al. 1993a, b). Etching
in acidic fluoride is exclusively electrochemical (Kolasinski 2008), with an
extremely low etch rate in the absence of a bias, light or dissolved oxygen
(Kolasinski 2003). Chemical etching can be used to produce nearly perfectly flat
and hydrogen-terminated Si surface (Burrows et al. 1988; Chabal et al. 1993; Hines
et al. 2012). Chemical etching is initiated by the action of OH.
It took over 30 years from the first reports of stain etching until the realization that
it can produce photoluminescent por-Si films (Sarathy et al. 1992; Fathauer
et al. 1992). A sketchy report of electroluminescence in a stain layer was attributed
by Gee (1960) to amorphous Si. However, the film was likely a por-Si layer created
by a 0.1 % HNO3 + 49 % HF solution. It is in some respects unfortunate that Turner
discovered stain etching by using HNO3 as the oxidant. The HNO3 + HF system has
the advantage that the solution composition can be varied to cover both an
electropolishing regime, in which very high etch rates are observed accompanied
by the formation of flat surfaces, as well as a por-Si formation regime. Unfortunately,
the reduction of NO3 and the myriad other nitrogen-containing species that are
37
formed as by-products are extremely complex. Only recently have Acker and
co-workers been able to establish the role of these various species in the
electropolishing regime (Acker et al. 2012; Hoffmann et al. 2011; Steinert
et al. 2007, 2008; Henssge and Acker 2007; Acker and Henssge 2007; Steinert
et al. 2005, 2006). This complexity (i.e., high sensitivity to composition, temperature,
extent of reaction, various dissolved gases, etc.) also leads to irreproducibility
in the ability of HNO3 + HF solutions to form photoluminescent por-Si films.
The formation of thick films is rather difficult with this system.
One application of stain etching in HF + HNO3 solutions has been in the
production of black silicon, that is, broadband antireflection coatings, which are
particularly useful in solar cell applications (Menna et al. 1995). This application is
reviewed elsewhere in this handbook (chapter Porous Silicon and Solar Cells).
Control of the porosity profile, and therefore refractive index profile, can be
particularly useful for tuning the reflectivity of the por-Si film (Schirone
et al. 1997, 2000; Striemer and Fauchet 2002). Stain etchants can be used not
only on crystalline Si but also multicrystalline Si solar cells to reduce reflectivity
(Gonzalez-Diaz et al. 2009; Bilyalov et al. 2003). Porous Si layers have long been
used in micromachining (Steiner and Lang 1995), and etching of Si in HF + HNO3
or NaNO2 solutions has also found uses in these applications (Melnikov et al. 2008;
Yamamura and Mitani 2008). Stain-etched layers have been doped with Er3+ and
Yb3+ to produce layers that may help to extend and enhance the wavelength
response of Si solar cells (Diaz-Herrera et al. 2009, 2011). They can also be
transformed into superhydrophobic surfaces (Liu et al. 2009). This property is
reviewed elsewhere in the handbook (chapter Tunable Properties of Porous
Silicon).
Much of the focus of this review will concentrate on HF + oxidants-other-thanNO3 solutions. One prime motivation for this is that some of these solutions
produce por-Si in a much more reliable, reproducible, and controllable manner.
In particular, Loni et al. (2011) have demonstrated that Fe3+ can be used to create
high-surface area por-Si from low-cost metallurgical grade Si. Similarly, Sato and
co-workers have used HNO3 + acetic acid + HF solutions (with added methanol
and ultrasonic agitation) to produce Si nanocrystals with variable visible
photoluminescence (Sato et al. 2009a, b). This property is reviewed elsewhere in
this handbook (chapter Photoluminescence of Porous Silicon).
Etchant Composition
The fluoride in a stain etchant is usually supplied by HF, although solutions with
strong fluorine-containing acids such as HBF4 and HSbF6 have also been reported
nal et al. 2001). NH4HF2 can be used to replace HF as long
(Parbukov et al. 2001; U
as the solution is acidified (Mills and Kolasinski 2004; Nahidi and Kolasinski
2006). An unusual example is that of CeF4 dissolved in concentrated H2SO4
(Kolasinski et al. 2012; Dudley and Kolasinski 2009a). In this case, the oxidant
and fluoride are supplied by the same species. This stain etchant leads to extremely
38
K.W. Kolasinski
uniform and highly luminescent por-Si layers but is limited to very slow etch rates
because of the low solubility of CeF4.
By far the most commonly used oxidant is HNO3, either to etch Si uniformly
(Yamamura and Mitani 2008; Robbins and Schwartz 1959, 1960, 1961; Schwartz
and Robbins 1976; Jenkins 1977; Kooij et al. 1999; Kulkarni and Erk 2000;
Svetovoy et al. 2006) or to form por-Si (Turner 1960; Archer 1960; Beckmann
1965; Beale et al. 1986; Shih et al. 1992, 1993; McCord et al. 1992;
Kidder et al. 1992; Dubbelday et al. 1993; Steckl et al. 1994; Chandler-Henderson
et al. 1994; Liu et al. 1994, 2007; Kalem and Rosenbauer 1995; Anaple et al. 1995;
Amato 1995; Schoisswohl et al. 1995; Jones et al. 1995; Di Francia et al. 1995;
Di Francia and Citarella 1995; Winton et al. 1996, 1997; Velasco 2003; GuerreroLemus et al. 2003; Gonzlez-Daz et al. 2006; Zeng et al. 2005; Melnichenko
et al. 2005; Luchenko et al. 2007; Balaguer and Matveeva 2010; Mogoda
et al. 2011; Lippold et al. 2011, 2012; Terheiden et al. 2011). Other sources of
nitrogen oxo ions such as NaNO2 (Archer 1960; Melnikov et al. 2008; Kelly
et al. 1994; Campbell et al. 1995; Vzsonyi et al. 2001; Abramof et al. 2006,
2007), NO2 (Archer 1960; Yoshioka 1969), NOBF4 (Kelly et al. 1994;
Safi et al. 2002), or NOHSO4 (Patzig et al. 2007) have been used, but these are
essentially running off of the same chemistry. A variation on standard HNO3-based
stain etching was demonstrated by Chen et al. (1996, 2001; Li et al. 1999).
They applied a hydrothermal treatment to produce por-Si. In the first report, they
dissolved 0.3 mol L1 LiF in 10.0 mol L1 HNO3 then heated this solution with the
Si substrate to 140 C inside of a stainless steel vessel for 2 h. The resulting ~ 70 %
porous material was heavily oxidized, photoluminescent, and ~10 m thick.
Subsequently they switched to 0.3 mol L1 Fe(NO3)3 in 40 wt% HF heated
to 142 C for 45 min. This treatment leads to the incorporation of iron into the
por-Si. Anisotropic etching has been reported in solutions composed of
H2SiF6(aq) + HNO3(aq) (Famini et al. 2006).
Acker and co-workers (Acker et al. 2012; Hoffmann et al. 2011; Steinert
et al. 2005, 2006, 2007, 2008; Henssge and Acker 2007; Acker and Henssge 2007;
Weinreich et al. 2007; Jadzinsky et al. 2007) have significantly advanced our
understanding of silicon etching in HF + (nitrate, etc.) solutions. The temperature
and composition of the solutions are critical. A number of different N-containing
species form in solution. The concentrations of these as well as the interactions of etch
products with etching are found to be temperature dependent. Both N(III) species and
dissolved gases play roles in the mechanism. Denoting (3NO+ NO3) as [N4O62+],
they found a linear relationship between etch rate and [N4O62+] concentration and
concluded that NO+ is a reactive species in the rate-limiting step. High concentrations
of this intermediate led to uniform etching (electropolishing).
The rate of stain etching is enhanced by the presence of defects. This characteristic
has been used to create a hybrid amorphous porous/defect-followed mesoporous
structure (Woo et al. 2012a, b).
Gerischer and Lubke (1988) found that oxidants with an electrochemical potential
more positive than the potential that corresponds to the Si valence band maximum
can inject holes into the valence band. These included MnO4, Br2, IrCl62, and I2.
39
However, since these experiments were carried out in 1 M NH4F solutions, no

por-Si was formed. Corrosion was noted for all these oxidants but, curiously, not for
Fe3+. As detailed in the Table 1, a number of other oxidants have been tried or may
still be capable of producing stain etchants.
Of the alternatives listed in Table 1, by far the most interesting for producing
photoluminescent, nanocrystalline thick films are Fe3+, supplied by FeCl3 6H2O,
and VO2+, supplied by V2O5. The former is used at a concentration of roughly 1 M,
the latter closer to 0.1 M (Kolasinski et al. 2010, 2012; Dudley and Kolasinski 2009a).
Reproducible por-Si formation is possible with both oxidants when concentrated HF
(aq) (49 wt% 29 mol L1 in HF) is used as the acidic fluoride source. Lowering
the concentration of fluoride lowers the etch rate. The etch rate is also directly
proportional to the concentration of either Fe3+ or VO2+; however, unlike HNO3,
there is no threshold concentration below which stain etching does not occur.
The formation of por-Si films in Fe3+ + HF solutions under illumination with a Xe
lamp has also been studied (Xu and Adachi 2007). Kolasinski and Barclay (2013a)
have demonstrated that the stoichiometry of stain etching is distinct from that of
anodic por-Si formation. This occurs because the injection of a conduction band
electron in the current doubling step is used to reduce H+ to H2 in anodic etching,
whereas this electron is consumed by the oxidant in stain etching. Therefore, two
moles of oxidant are required to etch one mole of Si (twice as much as expected), but
much less H2 is formed (with concomitant reduced bubble formation and improved
film homogeneity).
Several candidates for por-Si formation lead to poor results, such as HCrO4,
MnO4, and S2O82. The cation that accompanies these oxidants (usually Na+, K+,
or NH4+) can precipitate in the form of a hexafluorosilicate and interfere with film
formation (Koker et al. 2002). For example, Hoshino and Adachi produced
photoluminescent films with 57 wt% K2Cr2O7 in 50 % HF solution; however,
they also observed the deposition of K2SiF6 as did Mogoda et al. (2011). Usually,
HF + CrO3 solutions lead to uniform etching or only roughening of the Si surface
(Nahidi and Kolasinski 2006; Kooij et al. 1999; Kelly et al. 1994; van den
Meerakker and van Vegchel 1989a, b; Nahm et al. 1997; Gabouze et al. 2003).
There are several reports of the appearance of thin (Fathauer et al. 1992; Beale
et al. 1986) or patchy porous layers (Kelly et al. 1994) as well.
Just as for H2O2, the kinetics of hole injection from ClO4 are so slow as to
preclude significant etching (Dudley and Kolasinski 2009a, b). This suggests that the
presence of a metal catalyst might lead to enhanced etching for ClO4 just as it does
for H2O2. Potential oxidants that have yet to be attempted include Co3+, Ru(CN)63,
and UO2+. Co3+ complexes are explosive (Smirnov et al. 2004). In comparison, the
expense of Ru(CN)63 and the potential radioactivity of UO2+ seem appealing. Metals
such as Cu, Ag, Au, Rh, Pd, Pt, Hg, and Tl that will plate out onto Si (Ogata and
Kobayashi 2006; Allongue and Maroun 2006) have not been included in Table 1.
The halogens and halogenates are extremely reactive with Si when mixed
with HF solutions (Kolasinski and Gogola 2012). In particular, the iodate ion
IO3 produces extremely high etch rates when ethanol is added to the etchant to
avoid the precipitation of I2. However, the halogens are able to react thermally with
Yes
Yes
Yes
Yes
Hydrothermal etching
Rapid, uniform, thick layers, visible PL
0.957
0.991
NO3
VO2+
Yes
Yes
Slow etch rate, no visible PL

Irreproducible, visible PL
Yes
Yes
0.8665
0.957
Yes
Yes
Comments
Destroys por-Si
Not yet attempted
Uniform, thick, visible PL
Not yet attempted
porSi
No
Etch
Yes
0.86
E /V
0.5355
0.612
0.771
Ru
(CN)63
IrCl62
NO3
Oxidant
I2
UO2+
Fe3+
Kolasinski et al. (2012)

Turner (1960), Archer (1960), Beckmann (1965), Beale
et al. (1986), Shih et al. (1992, 1993), McCord et al. (1992),
Kidder et al. (1992), Dubbelday et al. (1993), Steckl
et al. (1994), Chandler-Henderson et al. (1994), Liu
et al. (1994, 2007), Kalem and Rosenbauer (1995), Anaple
et al. (1995), Amato (1995), Schoisswohl et al. (1995), Jones
et al. (1995), Di Francia et al. (1995), Di Francia and Citarella
(1995), Winton et al. (1996, 1997), Velasco (2003), GuerreroLemus et al. (2003), Gonzlez-Daz et al. (2006), Zeng
et al. (2005), Melnichenko et al. (2005), Luchenko
et al. (2007), Balaguer and Matveeva (2010); Mogoda
et al. (2011), Lippold et al. (2011, 2012), Terheiden
et al. (2011)
Chen et al. (1996, 2001), Li et al. (1999)
Kolasinski et al. (2010, 2012), Dudley and Kolasinski (2009a),
Kolasinski and Barclay (2013a, b), Kolasinski (2010),
Kolasinski and Yadlovskiy (2011), Kolasinski and
Gogola 2011)
Loni et al. (2011), Nahidi and Kolasinski (2006), Kolasinski

et al. (2010, 2012), Dudley and Kolasinski (2009a), Kolasinski
(2010)
Reference
Gerischer and L
ubke (1988), Kolasinski and Gogola (2012)
Table 1 Oxidants that may be or have been proven to be capable of initiating etching by hole injection into silicon (E values taken from Haynes 2010)
40
K.W. Kolasinski
Yes
Yes
Yes
1.3583
1.47
1.482
1.507
1.72
1.776
1.92
2.01
Cl2
ClO3
BrO3
MnO4
Ce4+
H2O2
Co3+
S2O82
Yes
Yes
Yes
Yes
No
Yes
Yes
1.189
1.195
1.350
ClO4
IO3
HCrO4
Yes
1.0873
Br2
No
No
Yes
Yes
No
No
No
No
Yes
Yes
No
Not yet attempted
Dissolved in conc H2SO4, visible PL only after a

few days, uniform, slow
Significant etching only with metal catalyst
Patchy and irreproducible
Destroys por-Si
Destroys por-Si
Destroys por-Si
Minimal etching maybe

By-products destroy por-Si
Patchy, irreproducible
Destroys por-Si
Kolasinski and Gogola (2012)
Kolasinski and Gogola (2012), Meltzer and Mandler (1995),

Bressers et al. (1996), Zhang et al. (2006)
Dudley and Kolasinski (2009b)
Fathauer et al. (1992), Nahidi and Kolasinski (2006), Jenkins
(1977), Beale et al. (1986), Kelly et al. (1994), Safi
et al. (2002), van den Meerakker and van Vegchel (1989a, b),
Gabouze et al. (2003), Sirtl and Adler (1961), Secco
dAragona (1972), Hoshino and Adachi (2007)
Nahm et al. (1997), Kolasinski and Gogola (2012), Seo
et al. (1993)
Nahidi and Kolasinski (2006), Mogoda et al. (2011), Kelly
et al. (1994), Nahm et al. (1997)
Kolasinski et al. (2012), Dudley and Kolasinski (2009a),
Kolasinski (2010)
Ashruf et al. (1999), Li and Bohn (2000), Rao et al. (2007),
Nielsen et al. (2007), Huang et al. (2011), Li (2012)

41
42
K.W. Kolasinski
Si and do so in a manner that destroys por-Si films. On the other hand, Xu and
Adachi (Xu and Adachi 2006) investigated etching in KIO3 + HF solutions. While
they observed no por-Si formation in the dark, with illumination at 600 nm from a
Xe lamp, they reported the formation of a photoluminescent film.
The addition of surfactants to stain etchants has occasionally been attempted.
Sometimes this resulted in rather thin films (Vzsonyi et al. 2001). Acetic acid
(Robbins and Schwartz 1960; Jenkins 1977) or ethanol can be used in this respect.
Caution: Ethanol reacts with the oxidant, particularly HNO3. Such solutions should
never be placed in a closed container. Whereas ethanol addition is commonly used
during anodic formation of por-Si to reduce the deleterious effects of bubbles, its
use in stain etching is rather limited. The apparent reduction of bubble formation
and sticking to the substrate is more closely related to a strong reduction in the etch
rate, rather than a superlative surfactant action (Kolasinski et al. 2010).
Rational Formulation of Stain Etchants

Through experiments on a broad range of oxidants and a better understanding of the
fundamentals of the charge transfer process, Kolasinski developed a set of guidelines for the formulation of effective stain etchants (Nahidi and Kolasinski 2006;
Kolasinski et al. 2010, 2012; Dudley and Kolasinski 2009a; Kolasinski and Gogola
2012; Kolasinski 2005, 2010, 2014).
The oxidant must be able to inject holes into the Si valence band at an appreciable rate; thus, its electrochemical potential should be more positive than
approximately +0.7 V.
The fluoride solution must be acidic to avoid OH catalyzed etching.
Oxide formation needs to be slow or nonexistent.
Sufficiently high fluoride concentration compared to the oxidant concentration
avoids electropolishing caused by the buildup of oxide.
The oxidant and all products must be soluble. Not only must the oxidant be
soluble so as to collide with the surface and inject holes, but also metals or other
products should not plate out on the surface.
Film homogeneity is enhanced if the oxidants half-reaction does not evolve gas.
The net etching reaction from hole injection to Si atom removal (including the
reactions of any by-products) has to be sufficiently anisotropic (attacking all
kinds of sites but only at the bottom of the pore) to support pore nucleation and
propagation.
Practical Advice
Cleanliness, especially regarding removal of organic hydrophobic contaminants,
is essential. Teflon beakers and crystals have to be degreased before etching.
Ultrasonication in acetone then ethanol then water is usually sufficient.
43
Keep cleaned crystals in distilled water and avoid Langmuir-Blodgett film deposition.
Do not ruin a perfectly good clean crystal by pulling it through the surface film that
naturally forms on water exposed to the atmosphere. Before removing a crystal from
water, always break the surface layer by agitating the top of the water with forceps.
The semiconductor industry does this routinely by using overflowing baths.
Get a tank of argon and use it liberally. Samples should be dried in streaming
Ar. Argon is heavier than air and, therefore, preferable to N2 because it forms a
buffer layer above solutions that helps avoid Langmuir film formation. Bubbling
Ar through etchants not only sparges them of dissolved O2 and CO2 but also stirs
the etchant and helps remove H2 when large-scale etching is performed. Filling
the headspace in HF bottles and distilled water containers with Ar helps to
reduce dissolved O2. Covering etchants, particularly Fe3+-based etchants, with
a buffer layer of Ar helps to avoid precipitation for long etch times.
For uniform thick films, slow etching using VO2+ or Fe3+ with low H2 production
is preferred. Critical point drying is a must (see chapter Drying Techniques
Applied to Porous Silicon).
V2O5 dissolves in concentrated HF(aq) but not water. To make diluted solutions,
always dissolve first in concentrated HF then add water.
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Porous Silicon Formation by Metal

Nanoparticle-Assisted Etching
Claude Levy-Clement
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1-Step Metal-Assisted Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2-Step Metal-Assisted Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reviews . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49
50
50
58
59
59
Abstract
Essential aspects in the fabrication of porous silicon and nanostructures by

metal-assisted particle etching are presented. Basic processes using 1-step or
2-step method are described as well as mechanism of metal-assisted chemical
etching. Influence of various parameters such as nature of metal, temperature,
etching solution composition, intrinsic properties of silicon substrate on the
morphology of porous silicon, or nanostructures is discussed. Applications of
silicon nanostructures obtained by metal-assisted etching are briefly introduced,
showing the promising potential of this etching method whose main properties
are simplicity, low cost, easy process control, reproducibility, and reliability for
fabrication of silicon nanostructures including silicon nanowires.
Introduction
Metal-assisted chemical etching (MAE or MACE) is based on a localized
oxidation and dissolution of silicon in HF in the presence of an oxidizing agent,
whereas the metal (generally noble metal) catalytically enhances the etching process
C. Levy-Clement (*)
Institut de Chimie et des Materiaux Paris-Est, CNRS, Thiais, France
e-mail: levy-clement@glvt-cnrs.fr
DOI 10.1007/978-3-319-05744-6_5
49
C. Levy-Clement
50
(Dimova-Malinovska et al. 1997; Li and Bohn 2000; Xia et al. 2000; Harada
et al. 2001; Chattopadhyay et al. 2002; Peng et al. 2002; Hadjersi et al. 2004; Qiu
et al. 2005; Tsujino and Matsumura 2005a, b; Yae et al. 2003). The Si underneath the
metal is etched much faster than that without metal coverage. As a result the metal
sinks into the Si substrate generating pores into Si substrate or Si nanowires (SiNWs)
corresponding to the un-etched Si between pores (Chapter MACE Silicon
Nanostructures on SiNWs). The metal, especially noble metals, may be dissolved
in HF (1-step MAE method) or deposited on silicon, as nanoparticles or thin films,
before the etching process in HF solution containing an oxidizing agent (2-step MAE
method).
1-Step Metal-Assisted Etching

The metal deposition and etching are carried out in the same chemical solution
(Fig. 1). A typical solution is 0.02 M AgNO3 + 4.6 M HF. This method leads to the
formation of porous Si (Qiu et al. 2005; Peng et al. 2003; Peng and Zhu 2004) or
pillar-like or craterlike microstructures (Peng et al. 2003) or arrays of silicon
nanowires (SiNWs) standing vertically on the Si substrate (Peng et al. 2002, 2003,
2004, 2005a, 2006a; Peng and Zhu 2003, 2004; Cheng et al. 2008; Benoit et al. 2008).
Metal ions are dissolved in HF. When the redox potential of the ions is more
positive than the valence band of Si, a galvanic reaction occurs in which the ions are
reduced to metal as particles, dendrites, and film, while the Si is oxidized and
dissolved in HF (case of noble metals) following the reaction:
4 M aq Si0 s 6F ! 4 Ms SiF6 2 aq
(1)
The formation of dendrites in the case of Ag and Au is at the origin of the

formation of SiNWs. AgNO3 (Peng et al. 2002, 2003, 2004, 2006a; Peng and Zhu
2004; Cheng et al. 2008; Benoit et al. 2008; Smith et al. 2013), KAuCl4 or HAuCl4
(Peng et al. 2002; Qiu et al. 2005; Peng and Zhu 2003, 2004), and K2PtCl6 or
H2PtCl6 (Peng et al. 2003) have been used, as well as other nitrate metal salts (Cu,
Ni, Mn, Fe, Co, Cr, Mg) (Peng et al. 2002, 2003; Table 1). It is a very easy method
to produce Si nanostructures especially nanowires, but there is little possibility to
control their dimension and homogeneity as well for the Si microstructures.
2-Step Metal-Assisted Etching

The metal particles are deposited on the Si surface generally by electroless
metal deposition (EMD) or chemical vapor deposition or sputtering, prior to
the etching in the HF solution in the presence of an oxidizing agent. During the
etching, dissolution of Si underneath the metal particles is strongly enhanced, and
pores are formed while the particles sink into the Si pores (Li and Bohn 2000;
Harada et al. 2001; Chattopadhyay et al. 2002; Tsujino and Matsumura 2005a, b;
Porous Silicon Formation by Metal Nanoparticle-Assisted Etching
51
In situ metal particle

deposition
Si Substrate
+ Si localized
dissolution
Si nanopores or nanowires
+ Metal nanoparticles
Fig. 1 Schematic of 1-step metal-assisted etching
Yae et al. 2003; Fig. 2). The etching can be done in various HF solutions containing
an oxidizing agent, typically H2O2 (Li and Bohn 2000; Tsujino and Matsumura
2005a, b, 2006a, 2007; Peng et al. 2008; Huang et al. 2007; Chartier et al. 2008;
Lee et al. 2008; Megouda et al. 2009a). Other oxidizing agents such as Fe(NO3)3
(Peng et al. 2005b, 2006b), Mg(NO3)2 (Peng et al. 2006b), Na2S2O8 (Hadjersi
et al. 2004, 2005a; Douani et al. 2008; Hadjersi 2007), KMnO4 (Hadjersi et al.
2004, 2005a; Douani et al. 2008), K2Cr2O7 (Douani et al. 2008; Hadjersi
et al. 2005b; Waheed et al. 2010), KBrO3 or KIO3 (Waheed et al. 2010), Co(NO3)2
(Megouda et al. 2009b), molecular O2 dissolved in H2O (Yae et al. 2003, 2005, 2006,
2008a, b, 2010a, 2012; Masayuki et al. 2011), and electrical holes, h+ by anodization
(Zhao et al. 2007; Chouroua et al. 2010; Huang et al. 2010a), are also used. The
deposited metals under the form of nanoparticles or colloidal particles or patterned
thin film are most generally noble metals such as Ag (Hadjersi et al. 2004, 2005b;
Tsujino and Matsumura 2005a, 2006a, 2007; Peng et al. 2005b, 2006b, 2008; Huang
et al. 2007; Chartier et al. 2008; Lee et al. 2008; Douani et al. 2008; Hadjersi 2007;
Waheed et al. 2010; Yae et al. 2005; Yang et al. 2008; Asoh et al. 2007a), Au (Li and
Bohn 2000; Qiu et al. 2005; Peng et al. 2008; Lee et al. 2008; Megouda et al. 2009a;
Yae et al. 2005; Zhao et al. 2007; Bauer et al. 2010), Pt (Li and Bohn 2000; Xia
et al. 2000; Chattopadhyay et al. 2002; Tsujino and Matsumura 2005a, b; 2006a; Lee
et al. 2008; Yae et al. 2005, 2006, 2012), Pd (Hadjersi et al. 2004; Tsujino and
Matsumura 2005a; Waheed et al. 2010; Yae et al. 2005, 2008a, b; 2010a, 2012;
Masayuki et al. 2011), Pd-Pt (Li and Bohn 2000; Asoh et al. 2008, 2009), or Rh (Yae
et al. 2012), but other metals such as Al (Dimova-Malinovska et al. 1997), Bi
(Megouda et al. 2009b), Cu (Tsujino and Matsumura 2005a; Peng et al. 2008; Mitsugi
and Nagai 2004), Ni (Zhao et al. 2007), and Fe can also be used.
The chemical or electrochemical reactions occur preferentially near the noble
metal. By analogy to electrochemical formation of porous Si, the role of the cathode
is attributed to the metal and that of the anode to the silicon underneath the metal
particle. The oxidant is reduced at the metal particle with production of electrical
holes (Li and Bohn 2000; Peng et al. 2008; Tsujino and Matsumura 2007; Chartier
et al. 2008). As an example when the oxidizing agent is H2O2, the reaction at the
cathode is the following:
H2 O2 2H ! 2H2 O 2h
(2)
At the interface between Si and the metal particle, the holes, h+, are injected into
the valence band of Si, which is dissolved as SiF62. Depending on H2O2 concentration, the localized Si dissolution occurs as either a two-hole or four-hole process
5M
0.01
0.2 M
0.2 M
0.080.15
M
K2PtCl6
CuNO3
NiNO3
MnNO3
FeNO3
CoNO3
CrNO3
Mg
(NO3)2
12 M
12 M
5M
0.02
KAuCl4
HF M
4.55
5M
5M
5M
NH4F
5M
5M
Metal ion
M
0.02 M
0.015 M
0.02 M
Idem
Idem
Catalyst
AgNO3
140
60 min
50
50
1030 min
50
50
50
120
15
Temp C/
etching time
50
2060 min
Au dendrites
Continuous Pt
grain films
Continuous Cu
grain films
No metal
deposition
Ag dendrites
Idem
Idem
Continuous Ag
grain film
Au
nanowhiskers
Metal deposit
Ag dendrites
Porous Si consisting of m pillars, cones,

craters pits nanostructures
Disordered shallow pits
SiNWs
Si morphology
SiNWs
1030 m long
30300 nm wide
Regular porous
Disordered porous
m stalagmites
Uniformly etched
Table 1 Various morphologies produced on single crystal Si by the 1-step metal-assisted etching method
Peng et al. (2002, 2003)
Peng et al. (2003)
Peng et al. (2003)
Peng and Zhu (2003, 2004)

Peng et al. (2003)
Qiu et al. (2005)
Peng et al. (2003)

Peng and Zhu (2004)
Peng et al. (2003)
Peng et al. (2003)
References
Peng et al. (2002, 2003, 2006a),
Cheng et al. (2008)
52
C. Levy-Clement

Selective
Dissolution of
silicon
Metal
deposition
Si Substrate
53
Metal
Nanoparticles
Pore formation
Fig. 2 Schematic of 2-step metal-assisted etching
with direct dissolution of Si in a divalent or tetravalent state, respectively.

H2 evolution occurs during metal-assisted etching and has been first attributed
to H+ proton reduction (Li and Bohn 2000), but then latter it has been attributed
to an anode reaction due to the strong similitude between stain etching in HF/HNO3
and metal-assisted etching (Chartier et al. 2008). A mixed reaction composed of
divalent and tetravalent dissolution for the dissolution of Si in MAE, which takes
also into account the H2 evolution, is proposed for the anodic reaction:
Si 6HF nh ! H2 SiF6 nH

4 n =2 H2 "
(3)
The overall reaction being

Si 6HF n=2H2 O2 ! H2 SiF6 nH2 O

4 n =2 H2 "
(4)
The morphology of the Si nanostructures depends on various etching conditions

such as the metal used (chemical nature and initial morphology), etching solution
composition, etching time, temperature, and Si properties (crystallography, orientation
doping density, conductivity type) (Table 2). The main results using metal-assisted
etching are summarized:
The Si dissolution rate increases from Ag, Au, Pt, Pd, to Rh in the presence of
HF/H2O2 or HF/O2 (Yae et al. 2012; Asoh et al. 2009).
The morphology of metal-assisted etched structures is defined by the shape of
the metal catalyst. Well-separated metal particles usually result in well-defined
pores (Tsujino and Matsumura 2005a, b; Chartier et al. 2008; Bauer et al. 2010).
In the case of etching solutions also used in stain etching, it is possible that
porous Si forms in the regions without noble metal.
When the metal particles (20200 nm) are randomly distributed on Si, a disordered
network of pores is formed into Si surface in the case of Ag, Au, and Pt, after
etching in HF/H2O2 (Tsujino and Matsumura 2005a), HF/O2 (Yae et al. 2005) and
HF/Fe(NO)3 (Peng et al. 2006b). Metal particles are observed at the bottom of the
pores. Various porous Si structures are found depending on the nature of the metal
and etching conditions (Fig. 3). The pore diameter is the same as that of Ag or Au
particles, whereas for Pt the pores are cone shaped of micrometer size and lined
with mesoporous Si (Tsujino and Matsumura 2005a, b). For Pd a polishing occurs
when the etching is done in 7.3 M HF/molecular O2 (Yae et al. 2005, 2010a).
When the distances between noble metals in the case of Ag and Au are small, the
H2O2
0.9 M
0.6 %
H2O2
Idem
Idem
H2O2 3.3
M
Idem
H2O2 5 M
Pt
Ag EMD
Ag collodal
particles
Pt EMD
Au 3 nm,
6 mm pitch,
Au/Pd (320 nm)

Pt
Au
Particle
Ag EMD 30100
nm
Oxidizing
agent
H2O2 2.72
M
7.9 M
61
%
Idem
10.8 M
77
%
HF M
28.9 M
91
%
28.9 M
97
%
10 %
5 min
30 s
30 s
50
30 min
30 min
Temp C/
etching time
25
30 min
n+Si, p-Si
p+-Si
p-Si
p-Si, 714
p+-Si (100)
p-Si, (100)
(113), (110)
714 cm
(100)
(100)
(111)
Si type
resistivity
cm
p-Si (100)
Idem, etching depth 10 nm

Columnar structures, 1 m deep
Macropores 100 nm
Similar to Ref. (Li and Bohn 2000), but bigger
structures
Narrow straight cylindrical nanoholes 35 m

long
Tortuous channels
Nanopores 30 nm, Si surface,
interconnected, etching depth 350 nm
SiNWs vertical
SiNWs slanted to Si surface
m spherical cavities + 3 m thick porous Si

Cylindrical holes inclined to Si surface
Nanostructure
Pores 540 m long, covered with microporous
Si
Table 2 Examples of various Si morphologies obtained by 2-step metal-assisted etching, the symbol f is used for diameter
Chattopadhyay
et al. (2002)
Li and Bohn (2000)
Peng et al. (2008)
References
Tsujino and
Matsumura
(2005a)
54
C. Levy-Clement
Fe(NO)3
0.2 M
K2Cr2O7,
0.05 M
KMnO4
0.05 M
Na2S2O8
0.05 M
Co(NO3)2
0.03 M
Ag EMD
Pt EMD
Ag (20 nm)
Vacuum
evaporation
Bi (20 nm)
Vacuum
evaporation
O2
(5 ppm)
Pt electrodeposited
0.050.2 m
22.5 M
22.5 M
5M
7.3 M
50
15 min
60 min
10 min
30 min
30 min
25
24 H
50
50 min
p-Si (100)
100 cm
n- and p-Si
1 cm
p-Si (111)
p-(100)
36 cm
n-Si (100)
1.6 cm
Etch pits 9 m contain pillars and porous Si
Etch pits 100 nm deep
Winding macropores 0.36 m, covered

with microporous Si
Megouda
et al. (2009b)
Douani
et al. (2008)
Cylindrical macropores 0.4 and 2 m

covered with microporous Si
Etch pits 0.15 m
Peng et al. (2006b)
Yae et al. (2005)
SiNWs array
Separated deep pores
Macropores 1 m covered with

microporous Si

55
C. Levy-Clement
Fig. 3 (continued)
56
57
structures evolve from pores into wall-like or wirelike structures vertically standing with diameter between 100 and 200 nm and several microns long (Peng
et al. 2005b, 2006b, 2008).
The etching solution composition has a strong influence on the metal-assisted
etched Si morphology. In the case of the HF/H2O2 solution, a unified notation
with [HF]/([HF] + [H2O2]) allows to compare the conditions and
resulting morphology published in the literature (Chartier et al. 2008).
Different regimes of Si dissolution are distinguished leading to the formation
of cylindrical pores for low oxidizing agent concentration ( > 70 %), to
cone-shaped pores with walls lined with porous Si for medium oxidizing
agent concentration (20 % < < 70 %), and to craters ( < 20 %) and
polishing for high H2O2 concentration ( < 7 %) (Chartier et al. 2008). For
20 % < < 100 % a duplex structure is formed at the surface of the Si wafer.
The top layer is micro-mesoporous, and once dissolved in NaOH, a
macrotexturized surface (from pores to craters) is observed. At 80 % the
maximum etching rate is reached and n equals 3 in the overall reaction
4 meaning that the etching process occurs as a mixed 2 and 4 electrons.
Switching from cylindrical pores to helical is accomplished by changing the
solution concentration. The generation of helical holes is attributed to the
microscopically difference in etching rate of silicon on a Pt particle (Tsujino
and Matsumura 2005b).
When Ag, Au, and Pd/Pt metal particles are deposited in ordered arrays through
a mask as a patterned thin film (~2040 nm thick), quasi-ordered silicon micro-/
nanostructures (pores) are formed in silicon, whatever is the kind of deposited
noble metal (Huang et al. 2007; Yae et al. 2010a; Asoh et al. 2007a, b, c, 2008,
2009; Bauer et al. 2010; Peng et al. 2007; Ono et al. 2007, 2009; Levy-Clement
Fig. 3 SEM images (plan view and cross section). (a) Ag particles deposited by EMD in
5 104 M AgNO3 + 0.14 M HF during 5 min (Chartier et al. 2008); (b) porous Si, Ag deposited
on (Li et al. 2012) p-type Si etched in HF/H2O2 ( 80 %) for 30 s (Chartier et al. 2008); (c)
straight and curved cylindrical pores with Ag particles at their bottom, same as (b) at higher
magnification; (d) cone-shaped macropores lined with microporous Si, Ag deposited on p-Si
etched in HF/H2O2 ( 20 %) for 20 s (Chartier et al. 2008); (e) array of SiNWs, Ag deposited
on Si etched in HF/H2O2 ( 70 %) for 5 min (Levy-Clement and Chartier 2013); (f) typical
helical pore, Au deposited on Si etched in HF/H2O2 ( 97 %) for 5 min (from Tsujino and
Matsumura 2005b, with permission); (g) cone-shaped pore with Au aggregates at the bottom, Au
EMD deposited on Si etched in HF/H2O2 ( 97 %) for 1 h (from Lee et al. 2008, with
permission); (h) macroporous Si, Ag deposited on Si etched in HF/H2O2 ( 70 %) for
15 min, after dissolution of microporous Si in diluted KOH. Si etched thickness is 8 m (LevyClement and Chartier 2013); (i) cone-shaped pores with a Pt particle at the bottom, Pt deposited on
Si etched in HF/H2O2 ( 70 %) for 15 min (Levy-Clement and Chartier 2013); (j) ordered array
of macropores with uniform diameter, Pt-Pd-coated Si etched in HF/H2O2 for 1 min; polystyrene
sphere honeycomb mask periodicity is 3 m (from Asoh et al. 2009, with permission); (k) array of
SiNWs (60 nm and 4.5 m long), 40 nm Ag film deposited with polystyrene sphere mask
( 100 nm) on Si etched in HF/H2O2 ( 91 %) for 10 min (Levy-Clement and Chartier 2013);
(l) porous Si, Ag deposited on Si etched in HF/Na2S2O8 (22.5 M/0.15 M) for 10 min (from
Hadjersi 2007, with permission)
58
C. Levy-Clement
et al. 2011; Boarino et al. 2011; Pacholski 2011; Geng et al. 2011; Hildreth
et al. 2009, 2013; Rykaczewski et al. 2011; Scheeler et al. 2012; Geyer
et al. 2012, 2013; Guder et al. 2013; Wang et al. 2013a). This observation is
the basis of the fabrication of a rich variety of ordered Si structures with different
length scales, as topographic lines, concentric rings, square arrays, etc., can be
created at a micro- and nanoscale after etching the silicon and subsequent
removal of the mask. This method is widely used to form regular arrays of
macropores and SiNWs with controllable diameter, length, and density (Huang
et al. 2007; Peng et al. 2007).
In situ formation of Au or Ag nanoparticles occurs by adding an Au colloidal
solution (Branz et al. 2009; Li et al. 2012) or AgNO3 (Lu and Barron 2013) in the
HF/H2O2/H2O solution allowing to transform the 2-step method directly in a
1-step metal-assisted etching. The H2O2 plays a dual role in reducing the Au3+
and Ag+ ions into nanoparticles onto Si wafer and facilitating the Si etching.
Mesopores of 20100 nm diameter and 500 nm long are obtained when adding a
sonication process (Lu and Barron 2013). A high concentration of H2O2 in
the solution leads to electropolishing and the formation of ultrathin Si wafer
(Bai et al. 2013).
The advantages of using metal-assisted etching are numerous. The method is
easy to handle and is suitable for batch fabrication of porous Si devices. Porous Si
layers can be formed on highly resistive Si. Compared to stain-etched layers, those
obtained by metal-assisted etching have better uniformity and much higher thickness. MAE can be used to make high surface-to-volume ratio structures, especially
when associated with a lithography method to deposit patterned metal catalyst.
Control of the orientation of Si nanostructures (e.g., pores, nanowires) relative to
the substrate is achieved. There is no obvious limitation on the size of features
fabricated by MAE, and fabrication of straight and well-defined pores or wires with
diameters as small as 5 nm or as large as 1 m can be obtained.
Applications
Metal-assisted etching is frequently used to prepare photoluminescent porous Si
(Dimova-Malinovska et al. 1997; Li and Bohn 2000; Harada et al. 2001;
Chattopadhyay et al. 2002; Hadjersi et al. 2004, Hadjersi et al. 2005b, c; Hadjersi
2007; Megouda et al. 2009b; Zhao et al. 2007; Gorostiza et al. 1999; Chattopadhyay
and Bohn 2006; Hadjersi and Gabouze 2007; Lipinski et al. 2009). MAE displays
little crystallographic dependence and can be performed on crystalline or
multicrystalline Si substrates, and the various Si morphologies and nanomicrostructures obtained are promising for photovoltaic applications in several
areas: antireflective coating (Yae et al. 2003, 2005, 2006; Peng et al. 2005a, b;
Benoit et al. 2008; Lu and Barron 2013; Tsujino and Matsumura 2006b; Chaoui
et al. 2008; Nishioka et al. 2008, 2009; Srivastava et al. 2010; Cao et al. 2011; Kim
et al. 2011, 2012; Geng et al. 2012; Wang et al. 2013b; Li et al. 2013a), texturization
59
for multicrystalline wafers (Tsujino and Matsumura 2006a; Waheed et al. 2010;
Branz et al. 2009; Li et al. 2012; Wan et al. 2008; Koynov et al. 2006, 2007;
Lipinski 2008; Bastide et al. 2009; Yuan et al. 2009; Lin et al. 2010;
Toor et al. 2011; Oh et al. 2012; Srivastava et al. 2012; Tang et al. 2013;
Shi et al. 2013a, b; Hsu et al. 2012), porous emitter (Hadjersi and Gabouze 2008;
Li et al. 2013b), advanced solar cells based on cylindrical macropores (Peng
et al. 2010) or Si nanorods or nanowires (Garnett and Yang 2008), and layer
detachment technique to prepare solar cells based on low-quality substrates or on
ultrathin Si layers (Shiu et al. 2011; Lin et al. 2012). Silicon nanostructures
obtained by MAE has been successfully used in lithium rechargeable batteries
(Ripenbein et al. 2010; McSweeney et al. 2011; Liu et al. 2011), nanocapacitors
(Chang et al. 2010), diffusion membrane applications (Cruz et al. 2005;
Chen et al. 2011), formation of nanostructured adhesive metal film on porous Si
surface (Yae et al. 2010b, 2011a, b), production of Si powders (Loni et al. 2011),
porous Si nanowires with photocatalytic properties (Qu et al. 2009, 2010), and
biosensing chips (Xiao et al. 2013). The catalytic properties of Pt have been used to
develop a slicing method showing the possibility to produce Si wafers from an ingot
(Salem et al. 2010) or to form through a hole in Si (Sugita et al. 2011). MAE
combined with patterning of metal catalyst thin film deposition is widely used to
form regularly organized nanostructures on Si (Yae et al. 2010a; Asoh et al. 2007a,
b, c, 2008, 2009; Bauer et al. 2010; Peng et al. 2007; Ono et al. 2007, 2009;
Pacholski 2011; Scheeler et al. 2012; Chattopadhyay and Bohn 2004; Hung
et al. 2010; Lee et al. 2011) or arrays of vertically standing Si nanowires with
controlled diameter and controlled distances between them (Huang et al. 2007,
2010b; Peng et al. 2007; Levy-Clement et al. 2011; McSweeney et al. 2011;
Qu et al. 2009, 2010; Zhang et al. 2008; Chang et al. 2009; de Boor et al. 2010).
Reviews
Huang et al. recently did a comprehensive and systematic review of metal-assisted
chemical etching mechanism and process parameters (Huang et al. 2011). The
review by Ono is focused on combination of patterning methods of metal deposition
and metal-assisted etching (Ono and Asoh 2012), whereas the review by Li is
related to high aspect ratio structures with an emphasis on photovoltaic applications
(Li 2012). Other papers contain a mini-review on metal-assisted etching
(Kolasinski 2005; Qiu and Chu 2008; Korotcenkov and Cho 2010).
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Porous Silicon Formation by Photoetching

Sadao Adachi
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photoetching Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
n-Si/Electrolyte Interface and Photoetching Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
PS Layers Formed by Photoetching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
67
68
68
70
73
73
Abstract
The literature on the photoetching technique of preparing photoluminescent

mesoporous silicon films using both hydrofluoric acid-based and alkali electrolytes
is reviewed. The benefits of using an incoherent light source and specific oxidizing
agents are highlighted. The technique is particularly useful for creating thin porous
regions in n-type Si wafers, SOI wafers, micromachined wafers, or those that
contain electronic circuitry.
Introduction
Visible photoluminescence (PL) from porous silicon (PS) observed at room
temperature has inspired sustained research into its potential application in Si-based
optoelectronic devices and its theoretical basis (Canham 1990). This property is
reviewed in the handbook chapter Photoluminescence of Porous Silicon. Most
PS layers are prepared by anodic etching on p-type Si substrates, a technique in which
S. Adachi (*)
Division of Electronics and Informatics, Faculty of Science and Technology, Gunma University,
Gunma, Kiryu-shi, Japan
e-mail: adachi@el.gunma-u.ac.jp
DOI 10.1007/978-3-319-05744-6_6
67
68
S. Adachi
metal is often deposited on the rear surface of the Si substrate in order for it to be used
as an ohmic back contact (see handbook chapter Porous Silicon Formation by
Anodization). However, the requirement for a back contact electrode is a limitation
of this method; for example, it is difficult to form a PS layer on a silicon-on-insulator
(SOI) structure or on Si integrated circuits. A photoetching method, on the other hand,
requires no electrodes and allows the formation of a visible luminescence layer on not
only single-crystalline Si substrates but also SOI structures.
Photoetching Setup
An experimental setup used for the formation of PS by photoetching is shown in
Fig. 1 (Xu and Adachi 2006). The sample surface is illuminated by a Xe lamp
through an optical filter that blocks wavelengths shorter than 600 nm. The use of an
optical filter is to block the heat rays from the Xe lamp. A laser, a W lamp, or
another light source may be used instead of a Xe lamp. The use of an incoherent
light source such as a Xe or W lamp enables the formation of a large and
homogeneous PS layer. Typically, an n-type Si wafer is immersed in an etchant
solution of HF. The addition of an oxidant (e.g., H2O2 or I2) to the HF solution
results in the stable formation of PS layers in a short time period.
n-Si/Electrolyte Interface and Photoetching Reaction

Figure 2 shows the energy band diagrams for n-Si electrodes in pure HF (pH 2.3)
and HF/oxidant solutions without and with light illumination (Xu and Adachi
2006). The electron affinity (s) of Si is 4.05 eV. At zero pH, the redox coupling
is defined as the normal hydrogen electrode with a potential of 4.5 eV with respect
to vacuum. This potential shifts towards more positive values with the increase in
pH (+0.059 eV/pH). Thus, the electron energy of the pure HF solution with respect
to vacuum is 4.36 eV (l). The Fermi levels (EF and EF,redox) on both sides of the
n-Si/electrolyte interface are brought to the same energy level by a transfer of
electrons from the Si substrate to the electrolyte (Fig. 2a).
The half-reaction for the oxidizing agent KIO3 is

3 6 6e I 3H2 O
E 1:085 eV
where e represents the electron and Eo is the standard reduction potential

with respect to the standard hydrogen electrode. The redox potential (Eabs) with
respect to vacuum for the HF/KIO3 redox system is then given by
Eabs 4.5 Eo 5.6 eV (Fig. 2c). It is to be noted that the larger the Eo
value is in the positive (negative) scale, the stronger is the oxidation (reduction)
agent (Adachi and Kubota 2007; Xu and Adachi 2007; Tomioka et al. 2007).
69
Fig. 1 Experimental setup

used for porous silicon
formation by photoetching in
an HF/oxidant solution
Fig. 2 Energy band diagram for n-Si immersed in pure HF solution (a, b) and those in HF/KIO3
solution (c, d). In (b), porous silicon (PS) is formed stably on the back side in opposition to the
illuminated surface. In (d), PS is formed only on the illuminated surface
70
S. Adachi
The absorption of photons results in the generation of electronhole pairs.

The holes at the n-Si/electrolyte interface can participate in PS formation.
In the case of the pure HF solution (Fig. 2b), the photoexcited holes are hard
to drift towards the surface by the very small downward band bending, or possibly
by the almost-flat band. Thus, efficient PS formation cannot be expected in pure
HF solution. When the Si wafer is dipped in the HF/oxidant solution (Fig. 2d),
on the other hand, many photoexcited holes move towards the n-Si/electrolyte
interface at the front surface, resulting in the formation of PS with good
reproducibility (Xu and Adachi 2006, 2007; Adachi and Kubota 2007; Tomioka
et al. 2007).
Reproducibility has been observed to be problematic in the formation of PS by
photoetching. In an extreme case, no PS layer was formed on the front surface,
although surprisingly PS was formed on the surface of the sample that was not
exposed to illumination (i.e., on the back surface) (Andersen et al. 1995). The
effectiveness of surface cleaning by sulfuric peroxide mixture (SPM) treatment or
by KOH etching before PS formation has been reported in Tomioka et al. (2007)
and Andersen et al. (1995).
PS Layers Formed by Photoetching

A summary of PS formation by photoetching is presented in Tables 1 and 2
(Xu and Adachi 2006, 2007; Adachi and Kubota 2007; Tomioka et al. 2007;
Andersen et al. 1995; Noguchi and Suemune 1993; Zhang et al. 1993; Cheah
and Choy 1994; Jones et al. 1996; Kolasinski et al. 2000; Yamamoto and Takai
2000, 2001; Mavi et al. 2001, 2006; Marotti et al. 2003; Cho et al. 2006; Xu
and Adachi 2008; Matsui and Adachi 2012; Zheng et al. 2005; Adachi and
Tomioka 2005).
To the best of our knowledge, there has not been reported any good plan-view
high-resolution scanning electron microscopy images of the photosynthesized
PS layers showing the morphology of their typical structures. In (Xu and
Adachi 2007), the atomic force microscopy images were reported to show
many irregularly shaped hillocks and voids distributed randomly over the
entire PS surface. The observed root-mean-squares roughnesses were a few
nanometers.
Lateral patterning of PS layers has been performed using photoassisted electrochemical etching rather than pure photoetching (Baranauskas et al. 1995; Diesinger
et al. 2003). Lateral modification of the porosity has also been obtained by photochemical dissolution of the anodic PS layers under illumination with a beam made
of interference fringes (Ferrand and Romestain 2001).
A metal-insulator-semiconductor-type electroluminescent (EL) device has been
fabricated from PS layers synthesized by photoetching in an HF/I2 solution (Adachi
and Kubota 2008). An insulating layer was formed on the PS layer by chemical
oxidation in an acidic solution. Spectral output of the EL device was in the
red-yellow region peaking at 2 eV.
Anhydrous and
hydrous HF
32 % HF
40 % HF
2HF:1HNO3:4H2O
48 % HF
6HF:1H2O2
100HF: (17250)
H2O2
40 % HF
n (0.4 0.7)
n (2), p (2)
n (4.5 6.4)
n (35 45)
n (0.22 0.38,
35 45)
n (10)
n (5 8)
Solution
50 % HF
Type ( cm)
n (0.01 15)
1.9 2.0
1.9 2.0
Nd:YAG laser (1,064

nm), Ar laser (514 nm)
1.8 1.95
1.8 2.3
1.9 2.2
1.7 1.9
1.7 1.9
2.0
PL peak
energy (eV)
1.8
HeNe laser
Gas and solid-state

lasers
HeNe laser
Gas, dye, and solid-state

lasers
Ar laser, Xe lamp
(465780 nm)
HeNe laser
W lamp (undispersed)
Light source
HeNe laser, Xe lamp
Table 1 Photoetching for porous silicon formation in acidic solutions

Comments
No PS formation when excited at
300400 nm. No PS formation on p-Si
PS is formed only on the metal-backed Si
substrates. PS layer thickness: 300 500 nm
PL peak energy depends on photoetching
wavelength
PS is easily formed on the back surface of the
sample
PS is formed on both n-Si and p-Si. PL peak
energy depends on excitation
(PL) wavelength
The shorter the photoetching wavelength, the
higher the PL peak energy. The higher the
photoetching laser power, the higher the PL
peak energy
The shorter the photoetching wavelength, the
higher the PL peak energy
Blue luminescence (420 nm) after dipping in
1C2H5OH:1H2O for 148 h
PL intensity is shown to strongly depend on
etching solution composition and time
A two-peak (1.91 and 2.02 eV) structure in
the PL spectrum (Ar laser). A single PL peak
at 2.0 eV (Nd:YAG laser)
(continued)
Kolasinski
et al. (2000)
Yamamoto and
Takai (2000)
Yamamoto and
Takai (2001)
Mavi et al. (2001)
Jones et al. (1996)
Cheah and Choy

(1994)
Andersen
et al. (1995)
References
Noguchi and
Suemune (1993)
Zhang et al. (1993)

71
Solution
1HF:1H2O2
49 % HF
40 % HF
HF:KIO3:H2O
HF:I2:H2O
HF:FeCl3:H2O
HF:H2O2:H2O
HF:KIO3:H2O
8HF:1H2O2
Type ( cm)
n (1 5)
n (4 6)
n (3 5)
n (1 3)
n (1 3)
n (1 3)
n (1 3)
n (1 3)
n (10 20)
Table 1 (continued)
Xe lamp (<600 nm)
Laser diode (532 nm)
Xe lamp (<600 nm)
Xe lamp (<600 nm)
Xe lamp (<600 nm)
Xe lamp (<600 nm)
Ar laser
Synchrotron X-ray
beam
Light source
HeNe laser
2.1
1.9 2.0
1.8 2.0
1.8 2.0
1.0 2.0
1.9 2.0
1.91, 2.05
1.94
PL peak
energy (eV)
1.7 1.9
Demonstrates the effectiveness of SPM

clearing for stable PS formation
A strong light-emitting PS layer can be
formed in the limited KIO3 concentration
A new approach to forming PS layer using a
closed-circuit anodic system under light
illumination without an external voltage
PL intensity is about 380 times stronger than

that synthesized in pure HF solution
PS layer thickness: 650 nm
Comments
PL peak energy is dependent on excitation
light wavelength
Strong white X-ray beam illumination
electropolishes, while a weak
monochromatic X-ray beam makes the Si
surface porous
Nanoparticle size is dependent on laser
power density and irradiation time
PS layer thickness: 75 nm
Xu and Adachi
(2006)
Adachi and
Kubota (2007)
Xu and Adachi
(2007)
Tomioka
et al. (2007)
Xu and Adachi
(2008)
Matsui and Adachi
(2012)
Mavi et al. (2006)
References
Marotti
et al. (2003)
Cho et al. (2006)
72
S. Adachi
73
Table 2 Photoetching for porous silicon formation in alkaline solutions. TMAH Tetramethyl
ammonium hydroxide
Type ( cm)
Solution
25 % TMAH
n (13 20)
Spa water
(pH ~ 10.5)
Light source
Nd:YAG
laser (1,064 nm)
HeNe laser
PL peak
energy
(eV)
No PL
study
~2.0
Comments
Macroporous
structure
An HF-free
technique
References
Zheng
et al. (2005)
Adachi and
Tomioka
(2005)
Conclusion
Photoetching enables the formation of a visible light-emitting PS layer on n-type
Si wafers. The use of an incoherent light source and the addition of an oxidizing
agent in the HF solution also facilitate the formation of a thicker homogeneous
PS layer with good reproducibility. The thickness of the porous layer is still
usually less than 1 m. The PL and EL peak energies were observed to be in the
range 1.72.3 eV.
References
Adachi S, Kubota T (2007) Light-emitting porous silicon synthesized by photoetching in aqueous
HF/I2 solution. Electrochem Solid-State Lett 10:H39H42
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Porous Silicon Formation by HNO3/HF

Vapor Etching
Brahim Bessas
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Equipment and Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Film Morphologies and Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diverse Uses of Vapor Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
77
78
80
82
Abstract
The formation of porous silicon (PS) via a HNO3/HF vapor-etching (VE)-based

technique is described. VE of silicon was found to lead to the growth of PS layers
(PSLs) and/or a thick white layer identified as the (NH4)2SiF6 compound. Which
phase dominates depends on the HNO3/HF volume ratio. High-resolution SEM
observations show that p- and p+-type PSLs are composed of dot-like crystalline
Si particles embedded in an amorphous phase, having sizes not exceeding 5 nm.
Almost pure (NH4)2SiF6 may be obtained in a wide range of thicknesses for a
HNO3/HF volume ratio exceeding 1/4. The (NH4)2SiF6 is highly soluble in
water, enabling fabrication of grooves in Si wafers. Control over the growth of
the (NH4)2SiF6 is demonstrated to realize groove patterns, which could be used
in a variety of applications.
Introduction
Low-temperature HF-based vapor etching was used for the first time in 1983 by
Heimann et al. (1984), by exposing Si wafers to vapors issued from NO2HFH2O
gas mixtures; they discovered the formation of films essentially composed of
B. Bessas (*)
Research and Technology Centre of Energy, Borj-Cedria Technoprak, Hammam-Lif, Tunisia
e-mail: brahim.bessais@crten.rnrt.tn
DOI 10.1007/978-3-319-05744-6_7
75
76
B. Bessas
crystalline ammonium silicofluoride ((NH4)2SiF6) and SiOx. At the end of the

1990s, one of the major technological issues is how to use a sacrificial layer via
wet micromachining and microstructuring while reducing and overcoming the
detrimental effects of the drying and handling steps. The main problems of wet
etching are to eliminate the capillary, van der Waals, and electrostatic forces
formed during the drying step, which may damage the microstructures (Alley
et al. 1992; Legtenberg et al. 1993; Mastrangelo and Hsu 1993). This topic is
reviewed elsewhere in the handbook (see chapter Drying Techniques Applied to
Porous Silicon). The vapor-phase etching (VPE) constitutes an interesting solution
to remove the sacrificial layer (Mulhern et al. 1993) and to replace the whole
sequence of wet etching, rinsing steps, and elaboration of drying procedures.
Similarly, removal of sacrificial oxide with hydrofluoric acid (HF) vapor has been
tested by researchers for years to release polysilicon structures. However, in reality,
the process is not so dry; indeed, liquid condensation occurs at the etched surface,
leading to not so satisfactory results. To avoid liquid condensation, one efficient
way consists of heating the wafer during vapor HF etching (Lee et al. 1997).
HF vapor etching was also used to enlarge the porosity of porous silicon layers
by attacking SiO2 just after an oxidation step; no drying is needed and therefore
no cracking or other damages can occur (Feyh et al. 2005). HF vapor etching was
also used to etch SiO2 and to make freestanding silicon microstructures of SOI
wafers (Fukuta et al. 2003). In silicon solar cell processing, it is well known that a
brief HF etching improves the carrier lifetime and hence ameliorates the current
density of silicon solar cells (Yablonovitch et al. 1986). The HF etching is often
applied after sintering the metallic contacts, just before encapsulation of the cells, to
avoid possible metallic contact degradation. However, in all cases the HF etching
time cannot exceed 10 s then preventing destructing the front contacts, particularly.
In 1999 and for the first time, Saadoun et al. exposed the emitter of Si solar cells to
HF vapors supplied by a spray etching apparatus executing an XY scanning
(Saadoun et al. 1999). Unexpectedly, Saadoun et al. discovered that when no
XY scanning is executed, a porous silicon film (PS) forms around the sprayed
area, due to the high velocity of the HF droplets striking the substrate. Thereby,
Saadoun et al. exposed directly the Si substrate to low-velocity fine droplets issued
from HNO3/HF vapors (Saadoun et al. 2002). This simple and low-cost method,
labeled vapor etching (VE), led to the formation of highly luminescent PS layers,
whatever the doping type may be (Saadoun et al. 2002). Independently, Kalem
and Yavuzcetin (2000) obtained light-emitting PS from the exposure of Si surface
to gaseous etchants prepared from (HF:HNO3:H2O, 2:1:5) mixtures. Later, it was
found that HNO3/HF vapor etching of Si can lead to the formation of PS,
(NH4)2SiF6, and Si/SiOx nanoparticles, depending essentially on the HNO3/HF
volume ratio, the etching time, and the temperature of the HNO3/HF mixture
(Ben Jaballah et al. 2004; Saadoun et al. 2003). In this chapter, we will give an
overview on HNO3/HF vapor etching and focus on the physical and technological
interests of this fabrication method.
Porous Silicon Formation by HNO3/HF Vapor Etching
77
Equipment and Processing

The VE method consists of exposing Si substrates, having various crystallographic
orientations and doping types, to acid vapors derived from a mixture of HNO3
(65 %) and HF (40 %). The VE etching process is achieved in a specific polypropylene container resistant to HF and HNO3 (Fig. 1).
The detailed experimental conditions of VE have been studied by Saadoun
et al. (Yablonovitch et al. 1986) and Ben Jaballah et al. (2004); this technique
enables generating PS and/or a luminescent white powder (WP) corresponding to
the (NH4)2SiF6 compound; later this surprising luminescence was attributed to
embedded SiOx/Si nanoparticles (Saadoun et al. 2003). One of these two phases
can be dominant depending on the HNO3/HF volume ratio. Figure 2 shows the
thickness of dissolved silicon as a function of HNO3/HF volume ratio after 60 min
of etching. One may point out that the dissolved mass of silicon depends on the
HNO3/HF volume ratio; one may distinguish three etching regimes. In the first
regime, the dissolution rate strongly increases with increasing HF content. After a
certain etching time, a compact and unknown film having very low dissolution rate
in diluted HF solutions (Ben Jaballah et al. 2004) appears. For HNO3-rich solutions
and for a volume ratio 2/3, these films behave as protective layers against etching.
This hypothesis was confirmed by measuring the dissolved silicon mass versus
etching time in the first regime (Ben Jaballah et al. 2004). When the HNO3/HF
volume ratio exceeds 1/4, a phase transition from luminescent PS to luminescent
(NH4)2SiF6 occurs (Aouida et al. 2006). Yet this phase transition is not well
understood, although some attempts tried explaining the formation mechanism of
(NH4)2SiF6 (Kalem 2004; Aouida et al. 2005; Kabacelik and Ulug 2008).
5
6
1 - Container
2 - Thermostatic bath
3 - Regulator
4 - Heating Resistance
5 - Thermometric probe
6 - HNO3/HF Solution
7 - Si Substrate
Fig. 1 Setup scheme of the HNO3/HF vapor-etching technique (Saadoun et al. 2002)
B. Bessas
78
35
80
70
60
50
3 (%)
40
30
regime (I)
20
regime (II)
10
regime (III)
Thickness (m)
30
25
20
15
10
20
30
40
50
60
HF (%)
70
80
90
100
Fig. 2 Thickness of dissolved silicon versus HNO3(65 %)/HF(40 %) volume ratio for an etching
time of 60 min. The temperature of the acid mixture and Si substrate is 40 C (Ben Jaballah
et al. 2004)
In fact, HNO3/HF vapor etching is similar to HNO3/HF wet chemical etching

(see handbook chapter Porous Silicon Formation by Stain Etching); in that
case detailed kinetic studies were performed to elucidate the complex etching
mechanism of silicon in a HF-rich HF/HNO3 mixture (Steinert et al. 2006).
One may guess that the complex role of the intermediate reactive species
(Steinert et al. 2005) generated during wet chemical etching of silicon in a
HF-rich HNO3/HF plays a significant role regarding the preponderance of PS or
(NH4)2SiF6. Therefore, for HNO3/HF volume ratio 80 %, Si etching favors the
formation of PS (region 3 in Fig. 2), while for volume ratios between 2/3 and 1/4,
a luminescent (NH4)2SiF6 prevails (region 2 in Fig. 2). The morphological
features of PS and (NH4)2SiF6 depend on the Si doping type, the temperature
of the acid mixture, the temperature of the Si substrate, and on-time exposure to
the HNO3/HF vapors (Saadoun et al. 2002; Ben Jaballah et al. 2004; Saadoun
et al. 2003).
Film Morphologies and Structures

Figure 3 illustrates SEM front views of HNO3/HF vapor-etched Si substrates, which
in turn show the electrochemical heterogeneity of vapor etching.
Obviously the diverse PS morphologies essentially depend on the doping type
(Fig. 3). Earliest morphological studies (Steinert et al. 2005; Berbezier and
Halimaoui 1993) on PS prepared from the conventional electrochemical etching
(EE) technique show that p- and p +-type PS present some structural differences.
79
Fig. 3 SEM views of HNO3/HF (volume ratio 1/4) vapor-etched Si at different scales and for
various doping types: (a) p type, (b) n type (c) p type (Saadoun et al. 1999), (d) p + type, (e) n type,
and (f) n + type
In contrast, no significant differences (Fig. 3) were noticed between VE-based

p- and p +-type PS (Saadoun et al. 1999); both p- and p +-type PS were found to
be mesoporous and formed with interconnected cluster-like structures with sizes
roughly ranging from 20 to 50 nm. The p +-type PS presents a more disordered
morphology (Fig. 3d) than p-type PS (Fig. 3c), indicating that etching of p +-type
is more aggressive, due to the fact that it has a larger density of impurity.
Despite these small differences, the overall morphologies of p- and p +-type PS
appear to be similar. Figure 4 shows a cross-sectional TEM micrograph of
VE-based p +-type PS. From TEM and HRTEM (Fig. 4a, b), one may notice
that the clusters forming PS consist of small Si particles, having size dimensions
less than 5 nm and having different crystallographic orientations and embedded
in an amorphous phase (Saadoun et al. 1999).
80
B. Bessas
Fig. 4 (a) TEM cross-sectional view of VE-based p + -type PS and (b) HRTEM view of the fine
Si particles shown in (a) (Saadoun et al. 2002)
The interconnections of the Si nanoparticles seem to be scarce, and there

is no evidence of the Si skeleton conventionally seen in EE- or SE-based PS.
Therefore, one can also expect that the luminescence properties related to the
Si quasi-isolated nanoparticles are different (Saadoun et al. 2002; Cullis
et al. 1997) from what has been reported in PS prepared from the EE and SE
methods (Canham et al. 1991).
Diverse Uses of Vapor Etching

Figure 5 shows SEM view of (NH4)2SiF6 prepared at different HNO3/HF
vapor-etching conditions. As has been previously said, the HNO3/HF volume ratio
(Fig. 2) could be adjusted to favor either the formation of PS or a (NH4)2SiF6 (WP).
In order to obtain the WP as a majority part, p-type silicon wafers were vapor-etched
at a HNO3/HF volume ratio > 1/4.
One may notice (Fig. 5) a very thin layer at the interface between the WP
and the Si substrate, which corresponds to a SiOx suboxide. The thickness of
this layer mainly depends on the HNO3/HF volume ratio and the etching time.
The (NH4)2SiF6 (WP) was found to be highly soluble in water, enabling to
achieve different groove patterns on the Si wafers (Fig. 6a, b) using specific
HNO3/HF inalterable masks (Ben Jaballah et al. 2005). Figure 6c shows a
SEM view of a vapor-etched NaOH-textured monocrystalline (100)-oriented
Si wafer, wherein finer textures composed of rough porous islands were
generated on the <111> facets and within inter-pyramidal regions (Saadoun
et al. 2011).
81
Fig. 5 SEM images of the (NH4)2SiF6 WP observed at two HNO3/HF/volume ratios and different
substrate temperature: (a) 1/2, ambient temperature, and (b) 1/8, 40 C. Both HNO3/HF exposures
were performed for long periods. Figure (c) shows a top view of the WP shown in Fig. 3a (Ben
Jaballah et al. 2004)
In the following, we give some applications of the HNO3/HF vapor etching:

Fabrication of composite porous siliconcrystalline silicon cantilevers
(Stolyarova et al. 2008).
Achievement of grooves and holes with a resolution as low as 1 mm (Ben
Jaballah et al. 2005).
Realization of buried metallic contacts in multicrystalline Si solar cells (Ben
Rabha and Bessas 2010).
Efficient reduction of surface reflectivity and improvement of the minority
carrier diffusion length in Si solar cells (Ben Rabha et al. 2012).
The use of HNO3/HF vapor etching as an intermediate step to control the
thinning and the surface smoothening of silicon nanopillars (Kalem et al. 2009).
HNO3/HF vapor etching can be advantageous for biosensor fabrication due to
reduction in cost and easy scalability (large-area PS layers can be easily fabricated) (Maia et al. 2007).
82
B. Bessas
Fig. 6 SEM cross-sectional views of two grooved structures: (a) hemispherical grooves made
from monocrystalline silicon, (b) flow channels produced from poly- and monocrystalline silicon
(Ben Jaballah et al. 2005), and (c) HNO3/HF vapor-etched NaOH-textured c-Si wafer (Saadoun
et al. 2011)
References
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surface microstructure stiction. In: Proceedings of the technical digest IEEE solid-state sensor
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Aouida S, Saadoun M, Saad KB, Bessas B (2005) Structural and luminescence properties of
vapour-etched porous silicon and related compounds. Phys Stat Sol (c) 2(3409)
Aouida S, Saadoun M, Ben Saad K, Bessais B (2006) Phase transition and luminescence properties
from vapor etched silicon. Thin Solid Films 495:357
Ben Jaballah A, Saadoun M, Hajji M, Ezzaouia H, Bessais B (2004) Silicon dissolution regimes from
chemical vapor etching: from porous structures to silicon grooving. Appl Surf Sci 238:199
Ben Jaballah A, Hassen M, Hajji M, Saadoun M, Bessais B, Ezzaouia H (2005) Chemical vapour
etching of silicon and porous silicon: Silicon solar cells and micromachining applications. Phys
Stat Sol (a) 202(8):1606
Ben Rabha M, Bessas B (2010) Enhancement of photovoltaic properties of multicrystalline
silicon solar cells by combination of buried metallic contacts and thin porous silicon. Sol
Energy 84(3):486
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performance via chemical vapor etching method-based porous silicon nanostructures. Sol
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Berbezier I, Halimaoui A (1993) A microstructural study of porous silicon. J Appl Phys 74:5421
Canham LT, Cox TI, Leong WY (1991) UK Patent 91,081,760, 17 Apr 1991
Cullis AG, Canham LT, Calcott PDJ (1997) The structural and luminescence properties of porous
silicon. J Appl Phys 82(3):909
Feyh A, Laermer F, Kronm
uller S, Mokwa W (2005) A novel process for the preparation of thick
porous silicon layers with very high porosity. Phys Stat Sol (a) 202(1597)
Fukuta Y, Fujita H, Toshiyoshi H (2003) Vapor hydrofluoric acid sacrificial release technique for
micro electro mechanical systems using labware. Jpn J Appl Phys Part 1 42:3690
Heimann RB, Ives MB, McIntyre NS (1984) The effect of deposition mechanism on the composition of surface films on silicon. Thin Solid Films 112:329
Kabacelik I, Ulug B (2008) Further investigation on the formation mechanisms of (NH4)2SiF6
synthesized by dry etching technique. Appl Surf Sci 254:1870
Kalem S (2004) Possible low-k solution and other potential applications. Eur Semicond 26:31
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Kalem S, Werner P, Nilsson B, Talalaev VG, Hagberg M, Arthursson O
Controlled thinning and surface smoothening of silicon nanopillars. Nanotechnology
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Lee Y-I, Park K-H, Lee J, Lee C-S, Yoo HJ, Kim C-J, Yoon Y-S (1997) Dry release for surface
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Legtenberg R, Elders J, Elwenspoek M (1993) Stiction of surface micromachined structures after
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Porous Silicon Formation by Porous Silica

Reduction
Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Si Nanostructures via Magnesiothermic Reduction of Silica: A Survey . . . . . . . . . . . . . . . . . . . . . . .
Merits of Magnesiothermic Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Challenges of Magnesiothermic Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alternative Reducing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
85
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Abstract
The direct creation of highly porous silicon by chemical conversion of highly porous
silica is receiving increasing attention for application areas that require relatively
inexpensive material. Silica can be reduced to silicon at moderate temperatures with
magnesium vapor which is the most popular route. The range of different silica
feedstocks utilized to date is surveyed, as is the morphology of the porous silicon
structures achieved. Key technical challenges are then highlighted and alternative
reduction chemistries mentioned.
Introduction
Magnesiothermic reduction of silica to silicon was first introduced in the 1980s by
researchers in India (Banerjee et al. 1982; Bose et al. 1982). They were targeting the
realization of solar-grade solid silicon from rice husks a significant volume
agricultural waste product in their country. The purity achieved was insufficient
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_8
85
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L. Canham
Fig. 1 Magnesiothermic
fabrication of porous silicon
Solid or porous
Synthetic or biogenic
SILICA
Magnesium
Heat
Silicon/Magnesium Oxide NANOCOMPOSITE
Acid extraction
POROUS SILICON
(Hunt et al. 1984; Iram and Akhter 1988) and the process lays dormant for almost
two decades. It was not until 2007 that Sandhage and co-workers demonstrated that
silicon nanostructures could be realized from a porous silica structure (Bao et al.
2007) and this discovery coincided with a period of renewed interest in achieving
alternative routes to the established carbothermic blast furnace route for solar-grade
silicon.
The chemical reaction and process are shown schematically in Eq. 1 and Fig. 1,
respectively.
SiO2 s 2 Mgg ! Sis 2 MgOs
(1)
At an initiation temperature in the range (400600 C), within an inert atmosphere or

vacuum, gaseous magnesium at relative molar concentrations close to those shown in
Eq. 1 creates primarily silicon and magnesium oxide, rather than magnesium silicide.
The morphology of the silica feedstock, the thermal budget, and the MgO by-product
size distribution in the nanocomposite are all influential in determining the pore
morphology and pore size distribution of the silicon product. At small batch size, the
reaction can be utilized in evacuated ampoules or standard furnaces with inert gas flow.
Over the last 5 years, there have been an increasing number of studies on
converting both synthetic and biogenic silica to silicon using magnesium vapor.
Studies motivated by solar-grade silicon supply are focussed on primarily achieving
very high purity and crystalline quality in nonporous silicon, those on silicon
nanostructures by the dimensionality and key properties required for the specific
application areas. In this review, we survey the latter recent studies (Bao et al. 2007;
Richman et al. 2008; Hai et al. 2009; Ibisate et al. 2009; Won et al. 2009, 2011; Yu
et al. 2010; Zhu et al. 2010, 2011; Yermekova et al. 2010; Chen et al. 2011a, b,
2012a, b, 2013a, b; Gallego-Gomez et al. 2011; Gao et al. 2011; Guo et al. 2011; Jia
et al. 2011; Lu et al. 2011; Pallavidino et al. 2011; Zhang and Huang 2011; Zhu and
Meng 2011; Batchelor et al. 2012; Fang et al. 2012; Shen et al. 2012, 2013;
Tao et al. 2012a, b; Wang et al. 2012; Yoo et al. 2012; Huachao et al. 2013;
Jung et al. 2013; Du et al. 2013; Hong et al. 2013; Jiang et al. 2013; Lee
et al. 2013; Liu et al. 2013; Luo et al. 2013; Ma et al. 2013; Meekins et al. 2013;
Porous Silicon Formation by Porous Silica Reduction
87
Wen et al. 2013; Xing et al. 2013a, b; Yoo et al. 2013; Yu et al. 2013; Yue
et al. 2013; Xia et al. 2014), highlighting the silica feedstocks used, the scale of
porosity/surface area achieved, and the targeted application where stated. The
merits and two major challenges with the technique are then commented upon.
Finally, we mention alternative reduction chemistries that might be utilized but
have received virtually no attention.
Si Nanostructures via Magnesiothermic Reduction of Silica: A

Survey
Table 1 below lists selected recent studies in chronological order, showing the types
of silica feedstock used, typical surface areas of the silicon product, class of
porosity, and the different application drivers where stated.
Merits of Magnesiothermic Reduction

Examination of the literature (Bao et al. 2007; Richman et al. 2008; Hai et al.
2009; Ibisate et al. 2009; Won et al. 2009, 2011; Yu et al. 2010; Zhu
et al. 2010, 2011; Yermekova et al. 2010; Chen et al. 2011a, b, 2012a, b, 2013a, b;
Table 1 Silicon porosification via magnesiothermic reduction for different applications
Reference
(author, year)
Bao et al. 2007
Hai et al. 2009
Ibisate et al. 2009
Zhu et al. 2010
Chen 2011b
Guo et al. 2011
Batchelor
et al. 2012
Chen 2012
Fang et al. 2012
Shen et al. 2012
Jiang et al. 2013
Liu et al. 2013
Ma et al. 2013
Xing 2013a
Feedstock
Diatoms
Sand
Stober silica
Opal
Zeolite
Aerogel
SBA-15
Bamboo
extract
Aerogel
Templated
silica
Diatoms
Aerogel
Rice husk
ash
Serpentine
Silicon
monoxide
Product surface area

(m2/g)
>500
86
200
Class of
porosity
Meso-/
microMeso-
Luminescence
615
MesoMeso-
Photonics
Luminescence
Lithium battery
Drug delivery
Cosmetics and
food
Luminescence
Thermoelectrics
96
861, 656
54
245
143
218
5
MacroMesoMacroMesoMesoMesoMacro-
Lithium battery
Biomedical
Lithium battery
Lithium battery
Luminescence
Lithium battery
Lithium battery
308
602
606
356
MacroMesoMesoMesoMeso-
Primary
application area
Sensing
88
L. Canham
Gallego-Gomez et al. 2011; Gao et al. 2011; Guo et al. 2011; Jia et al. 2011;
Lu et al. 2011; Pallavidino et al. 2011; Zhang and Huang 2011; Zhu and
Meng 2011; Batchelor et al. 2012; Fang et al. 2012; Shen et al. 2012, 2013;
Tao et al. 2012a, b; Wang et al. 2012; Yoo et al. 2012; Huachao et al. 2013; Jung
et al. 2013; Du et al. 2013; Hong et al. 2013; Jiang et al. 2013; Lee et al. 2013; Liu
et al. 2013; Luo et al. 2013; Ma et al. 2013; Meekins et al. 2013; Wen et al. 2013;
Xing et al. 2013a, b; Yoo et al. 2013; Yu et al. 2013; Yue et al. 2013; Xia et al. 2014)
reveals that all three classes of porosity (see handbook chapters on Macroporous
Silicon, Mesoporous Silicon, and Microporous Silicon) are achievable with
magnesiothermic reduction, as are extremely high surface area structures. Although
both solid and porous silica feedstocks can be processed, higher throughput and
degrees of nanostructuring seem achievable when magnesium can react with silica
surfaces via vapor transport through the pores of feedstock particles. The process can
be based on intimate mixing of reactant powders and does not need large quantities of
hydrofluoric acid nor organic solvents.
Challenges of Magnesiothermic Reduction

One significant challenge of utilizing this process to fabricate large quantities of
high surface area silicon is the avoidance of sintering. The magnesiothermic
reaction (Eq. 1) is highly exothermic with a Gibbs free energy change of 3,340
kJ/mole of silica converted to silicon. Despite the inexpensive feedstocks used
(silica and magnesium), the batch sizes reported in the vast majority of studies
(Bao et al. 2007; Richman et al. 2008; Hai et al. 2009; Ibisate et al. 2009;
Won et al. 2009; Yu et al. 2010; Zhu et al. 2010, 2011; Chen et al. 2011a, b,
2012a, b, 2013a, b; Gallego-Gomez et al. 2011; Gao et al. 2011; Guo et al. 2011;
Jia et al. 2011; Lu et al. 2011; Pallavidino et al. 2011; Won et al. 2011; Zhang and
Huang 2011; Zhu and Meng 2011; Fang et al. 2012; Shen et al. 2012, 2013;
Tao et al. 2012a, b; Wang et al. 2012; Yoo et al. 2012; Huachao et al. 2013; Jung
et al. 2013; Du et al. 2013; Hong et al. 2013; Jiang et al. 2013; Lee et al. 2013; Liu
et al. 2013; Luo et al. 2013; Ma et al. 2013; Meekins et al. 2013; Wen et al. 2013;
Xing et al. 2013a, b) are in the mg to gram range. Two exceptions are from the
studies of Batchelor et al. (2012) where salt was used as a thermal moderator to
keep reactant powder temperature as low as possible and, at the other extreme,
Yermekova et al. (2010) where thermal runaway was exploited for combustion
synthesis. The former study had a continuous flow of 30 g tray batches with high
salt content in a belt furnace setup. The latter study used compacted feedstock
cylinders of dimensions 14 cm diameter and 2.55 cm length in a combustion
furnace. Calculations suggest the batch sizes in the Yermekova et al. (2010) study
were thus as high as 85 g. Combustion synthesis could be an attractive process for
macroporous silicon with surface areas of 5100 m2/g but is unlikely to have
sufficient thermal control to achieve tunable mesoporous nanostructures.
A second challenge regards applications where porous silicon is required
with minimum oxide content. The aqueous HCl at elevated temperatures used
89
to remove the MgO by-product has often reintroduced significant amounts

of silica in highly porous silicon. The use of aqueous HF as a final processing
step to remove such a phase detracts from the otherwise environmentally
friendly nature of the process, especially when biogenic silicas are utilized
(Batchelor et al. 2012).
Alternative Reducing Agents

In 2003, Nohira et al. (2003) demonstrated the electrochemical reduction of silica
by calcium in a molten salt bath at 850 C. This process could generate porous
silicon deposits. Lithium is another potential reductant, as shown by Yasuda
et al. (2005) in 2005. They were able to use a molten salt temperature of
only 500 C and the silicon product had a spongy morphology with a particle
size below 50 nm.
Wang et al. (2013) have also very recently suggested the use of sodium to
thermally reduce silica according to
SiO2 s 4Na g ! Si s 2 Na2 O s
(2)
This approach looks attractive to realize amorphous porous silicon since the
reaction can progress at very low temperatures, but the high cost and reactivity of
elemental sodium suggests there could be issues with scalability.
Another alternative reducing agent that deserves much more attention is aluminum. Liquid aluminum has long been known to react rapidly with silica (Standage
et al. 1967) according to
3 SiO2 s 4 Al l ! 3Si s 2 Al2 O3 s
(3)
A comparison of Eqs. 1 and 3 highlights a potential economic advantage of

aluminothermic reduction. Note how the aluminothermic silicon yield requires
more of the inexpensive silica feedstock, but less of the more expensive reducing
agent (Mg versus Al). A second attribute is the avoidance of minor silicide
by-products (magnesium can form a silicide with silicon, but aluminum does not).
Conclusions
The reduction of porous silica with magnesium vapor is a highly exothermic
reaction. The process with thermal moderators is an attractive route to generating
highly mesoporous silicon (surface areas >500 m2/g). Without thermal moderators,
large batches of macroporous silicon can be generated by combustion synthesis.
Electrochemical reduction with molten calcium or lithium salts rather than thermal
reduction with magnesium is also under evaluation. The use of liquid aluminum to
reduce mesoporous silica deserves much further study.
90
L. Canham
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Porous Silicon Formation by Mechanical

Means
Jaroslaw Jakubowicz
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Mechanical Synthesis of Porous Silicon Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Compacting and Consolidation of the Silicon Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Abstract
In this chapter a mechanical method of porous silicon formation is described.

By applying high-energy ball milling to polycrystalline silicon powder or single
crystalline silicon wafers, highly dispersed and nanocrystalline silicon powders are
produced. Pressing and sintering then lead to a porous matrix. The macroporous
structures made in this way can then be permeated by meso- and micropores.
The sinters have isotropic character of the pore distribution and morphology; this
method is not limited by the wafer dimensions, and it is possible to make largescale porous bodies, which is an advantage in comparison to lithographic methods.
Introduction
In the past half century, there has been a great effort to develop porous silicon
structures for a wide range of applications such as electronic and optoelectronic
devices. It is commonly accepted that the main method of porous silicon formation
is based on electrochemical etching in HF-containing electrolytes (Parkhutik 1999;
Jakubowicz et al. 2003). Typical thicknesses of surface porous layers are up to tens
J. Jakubowicz (*)
Poznan University of Technology, Institute of Materials Science and Engineering, Poznan, Poland
e-mail: jaroslaw.jakubowicz@put.poznan.pl
DOI 10.1007/978-3-319-05744-6_9
93
94
J. Jakubowicz
of micrometers, whereas typical porosities are in the range of 2080 % (Lang

et al. 1995). Higher porosities of 8595 % lead to silicon scaffold cracking and
collapse due to high surface tension forces during drying.
Electrochemical etching is well known, giving random or oriented pores (Sailor
2011; Christophersen et al. 2001). The devices lithographically made of porous
silicon with different orientation, morphology, and size, such as photonic crystals,
luminescent elements, and gas sensors, are typically obtained.
In recent years, new techniques of porous silicon formation have appeared, for
example, those based on mechanical synthesis (Yadav et al. 2012; De Castro
and Mitchell 2002; Jakubowicz et al. 2007; Saffie et al. 2005; Russo et al. 2011;
Diaz-Guerra et al. 2002; Svrcek et al. 2005; Odo et al. 2012; Unifantowicz et al. 2008;
Gaffet and Harmelin 1990; Shen et al. 1995; Stevulova et al. 1997; Huang et al. 1999).
The synthesis of nanomaterials using mechanical milling, like high-energy ball
milling (HEBM) or mechanical alloying (MA), was first reported in 1970 (Benjamin
1970). Ball milling of powders leads to ball-powder-ball-powder-wall collisions
(powder and balls inside the milling hardened reactor) resulting in high
plastic deformations, cold welding, strengthening, and finally particle fracturing and
cracking. After the process highly dispersed powders are produced (Yadav 2012).
The process can be applied for particle size reduction (HEBM) as well as for
compound preparation (MA) with grain size below 100 nm, often between 1 and
10 nm (Yadav et al. 2012; De Castro and Mitchell 2002).
The new approach for porous silicon formation is the nonequilibrium process
ball milling, resulting in highly dispersed nanostructure particles. Combination of
the ball milling with pressing and sintering of the nanocrystalline silicon particles
leads to sinters (Coblenz 1990; Moller and Welsch 1985; Santanav and Jones 1996)
with pores inside, i.e., porous matrices (Fig. 1). This method is not limited by the
wafer dimensions, and it is possible to make very large porous structures, which is
an advantage in comparison to lithography. The flow diagram (Fig. 1) shows that
combination of top-down process (milling) with bottom-up process (pressing)
leads to porous matrices with extraordinary dimensions, strongly fixed in the
sintering process.
The mechanical treatment for grain size reduction can be applied to both Si
single crystalline wafer and Si polycrystalline particles. The obtained final powders
depend on the consolidation processes and subsequent chemical or electrochemical
treatment (Table 1): morphology, phase, and chemical composition are tunable for
different applications.
The main disadvantages of the mechanical processes in some applications could
be the isotropic character of the pore distribution and morphology, nonuniform
grain size, and the impossibility to achieve regular columnar pores, perpendicular to
the surface, as in the case of electrochemically etched wafers (see handbook chapter
Porous Silicon Formation by Anodization).
In the so-called top-down methods, based on mechanical milling, the brittle
silicon wafer or particles absorb high energy of impacts with balls, leading to crack
formation and fast reduction of grain size.
95
Fig. 1 Flow diagram showing steps of mechanical way of porous silicon formation
Table 1 Possible combinations of mechanical and chemical treatment of Si particles and wafers
Processes
Feedstock
material
Si wafer
Si particles
Porous Si
compacts
Porous Si
sinter
Milling
HEBM
Pressing
Isostatic
Sintering
Classic
HF etching
Stain
Mixing
Reactive
milling
Uniaxial
HIP
SPS
Electrochemical
+
+
+
+
Space
holder
+
+
Surface composition
modification
Electrochemical
deposition
Ion implantation
Heat-chemical
treatment
CVD, PVD
+
+
+
+
+
+
The initial single crystalline silicon wafer under milling transforms into
polycrystalline particles. The sintering of Si powders leads to the porous sinter
with typical porosity of about 1030 %. Varying the compaction pressure and
sintering temperature, a broad range of densities can be achieved in porous
Si sinters. Although milling and pressing stages generate highly defective silicon,
containing dislocations, twins, stacking faults, points defects, and grain boundaries
(Odo et al. 2012; Unifantowicz et al. 2008; Shen et al. 1995; Huang et al. 1999), the
subsequent treatment at elevated temperature (e.g., sintering) releases strain
and defects and, in the case of amorphous particles, leads to a transition from
amorphous to crystalline structures (Gaffet and Harmelin 1990; Shen et al. 1995).
The porosity of the mechanically made matrices can be enhanced by applying the
electrochemical etching in HF-containing electrolytes (Saffie et al. 2005), so that
even gradients in porosity could be obtained.
Another possible way to achieve high porosity and graded porous silicon
structures of large size could be sintering of silicon particles with different size
space holder particles, such as in the case of metal foam preparation. During
sintering at elevated temperature, the evaporation of the spacing particles leads to
formation of open spaces giving a very high porosity. To the authors knowledge,
this method has not yet been used for the preparation of porous Si.
96
J. Jakubowicz
Mechanical Synthesis of Porous Silicon Powders

Highly dispersed silicon particles can be prepared by high-energy ball milling, where
the large particles (e.g., coarsely crushed Si wafers) are trapped between hardened
balls and walls of the milling reactor. The pressure imposed on the Si particles was
estimated at 26 GPa (Unifantowicz et al. 2008; Huang et al. 1999). Ball to powder
ratios are typically in the range from 2:1 to 20:1, providing different milling energies
and resulting in differentiation of the Si grains deformation, strain refinement, or
amorphization (Jakubowicz et al. 2007; Russo et al. 2011; Diaz-Guerra et al. 2002).
Additionally, lattice cell changes during milling from cubic to tetragonal were
observed using Raman spectroscopy (Unifantowicz et al. 2008). The lattice strain in
HEBM of silicon can lead to changes in Si-Si bond length. The deformation of the
crystal lattice by high compressive stress during ball-powder-ball collisions results in
an increased density of lattice defects (Unifantowicz et al. 2008). A milling time from
minutes up to a few days are typically used. The milling reactor and balls can be made
from hardened steel or ceramic material. Mills with different milling mechanisms and
energies can be applied (e.g., vibrating, planetary, or attritor mills), resulting in
different particle size reduction, ratio of amorphization, agglomeration, or stress
(Yadav et al. 2012; De Castro and Mitchell 2002; Stevulova et al. 1997).
Bulk silicon is a very brittle material and thus grinding is very effective for
structure refinement (Figs. 2 and 3). In the process the increasing milling time
results in structure refining, leading to nanocrystalline grain formation. The fastest
reduction of grain size is observed in the first hour (Jakubowicz et al. 2007). The
milling process, although highly energetic and very effective, does not lead to
amorphization after short milling time (few hours) (Odo et al. 2012), but after a
longer time (over a dozen hours) the amorphous phase appears (Unifantowicz
et al. 2008; Gaffet and Harmelin 1990). The nanoparticles formed in HEBM process
generally are not separated but rather sticks together and forms larger agglomerates
with a size up to 0.5 m. The undesired powder agglomeration can be prevented by
milling with a surface active agent, like stearic acid, introduced during the milling
into the milling reactor. Unfortunately its contamination may be presented in the Si
nanocrystals after the process (Svrcek et al. 2005) affecting consolidation and
properties of the final product. Liquid surface active agents and the so-called wet
milling could also prevent agglomeration. Any liquid agent will affect the grinding
kinetics (Stevulova et al. 1997). Another way for achieving the separated and
well-sized defined particles is ultrasonic post ball milling treatment with lengthy
particle sedimentation techniques applied after milling (Pawlak et al. 2001).
As was reported by Russo et al. (Russo et al. 2011), the ball milling can be
improved by applying in the first stage the electrochemical etching of the single
crystalline wafer and then its milling. Due to the very brittle porous silicon layer
and small thickness of the scaffold walls, the etched porous wafer is milled in
shorter time giving porous silicon particles. In the milled porous silicon, significant
SiO2 was observed, in contrast to milling of unetched Si wafer, which can be
unfavorable in subsequent particle consolidation. The longer milling of the porous
etched wafer (e.g., >4 h) results in destruction of the porous skeleton, giving a
97
Fig. 2 Grain size reduction

of the Si particles during
HEBM (Jakubowicz
et al. 2007)
Fig. 3 Silicon wafer: coarsely crushed in agate mortar (a) and after 48 h HEBM (b) (Jakubowicz
et al. 2007)
moderate specific surface area of 28.7 m2/g. In comparison, after a short 6 min
milling, the BET analysis showed 105.2 m2/g (Russo et al. 2011). The additional
milling of the electrochemically etched silicon wafer results in formation of new
dangling bonds as well as other defects on the surface and in the bulk (due to
mechanical stress) (Bychto et al. 2008). These defects are very important, taking
into account electronic applications, for example.
The oxidation of as-milled Si particles at higher temperature (e.g., 1,273 K for
5 min2 h in air) leads to reduction of Si crystals size (crystal core) and SiO2 shell
formation, surrounding the Si core (Pawlak et al. 2001). So, the treatment is useful
in reducing the concentration of unsaturated bonds. But for compacting process and
strength of the compacts, much more useful is H-termination than oxidation (see
next section).
98
J. Jakubowicz
For improving the grinding process, the hydrogen milling atmosphere (reactive
milling) can be useful (Bollero et al. 2000) leading to diffusion of hydrogen,
H-induced cracking, and faster size reduction of the particles. Additionally in the
case of silicon, the H-termination is possible and expected, too. As an alternative,
grinding and handling of the Si powders in vacuum or organic liquids (like
benzene) also protect the surface against oxidation (Stevulova et al. 1997).
Compacting and Consolidation of the Silicon Powders

The porous silicon bulk matrix (unitary body) is formed using powders (e.g.,
made in HEBM process) compacted at a high pressure. For example, pressures
of 501,000 MPa are used and uniaxial or isostatic pressing can be applied.
The low and moderate pressures result in moderate porosity (Fig. 4a). For proper
densification and enough particles bonding, green densities above 42 % of
the theoretical value and temperature above 1,373 K are required (Moller and
Welsch 1985). An imperfect and nonsymmetrical shape of the Si powder
particles is advisable for good compacting and strength of the green compact
(mechanically bonded silicon particles by applying a high pressure). The wide
range size of pressed particles is more effective in void filling between particles
(Barraclough et al. 2007), but not necessarily useful if the highly porous matrix
is required.
After the next stage of sintering, the porosity can retain a significant value
(Fig. 4b), but mechanical strength and integrity of the sinter (compacts thermally
treated for the formation of necks between Si particles) is sufficient for practical
applications. Higher density and strength of the sinters can be obtained by applying
hot isostatic pressing (HIP) process, which is typically a faster process, requiring
lower pressures and temperatures. The sintering of solid nanoparticles has to some
extent synergies with that of mesoporous and macroporous silicon (see handbook
chapter Sintering of Porous Silicon) wherein closed internal voids can be
created.
The XPS measurements indicate that the valence band spectra of the bulk
mechanically formed porous silicon matrix (Jakubowicz et al. 2007) are in very
good agreement with those reported for electrochemically prepared porous Si
wafers (van Buuren et al. 1994). The shape of the valence bands of mechanically
made porous Si is broader in comparison to those for the Si single crystalline wafer
or polycrystalline 20 nm Si thin film. This is probably observed due to a strong
deformation of the grains in the mechanically made porous silicon.
In the Si compacting process made at room temperature, oxygen removal plays
an important role in binding of the Si particles. Both doping (such as boron)
and oxygen are surface active and as shown by Coblenz (Coblenz 1990)
effective in inhibiting surface transport. For that reason, commonly known and
used for Si wafers, H-termination can be applied for the Si powder, too
99
Fig. 4 Silicon green compact (a), after sintering (b) (Jakubowicz et al. 2007) and after stain
etching in HF solution
(Barraclough et al. 2007). In this process the surface native oxides are removed,
giving the surface particles resistance to short-time oxidation. The reducing
sintering atmosphere consisting of, for example, 2 % hydrogen improves the
sintering process, through increasing rate of reduction of the native oxide and
increasing surface transport (Santanav and Jones 1996). As was shown by
Barraclough et al. (Barraclough et al. 2007), the compacts made from
H-terminated powders show longer time of disintegration (up to 5 min), whereas
the compacts made from untreated powders disintegrated after shorter time (30 s1
min), due to a dissolution of the main bonding agent native SiO2.
100
J. Jakubowicz
To avoid cracks in the Si compacts, the die lubricant and hot isostatic pressing or
spark plasma sintering (SPS), both at very low pressure of 50100 MPa, look
attractive. The sinter porosity can be controlled by sintering temperature, resulting
in significant decrease in porosity with rising temperature (Chakravarty et al. 2011).
The strength of the sintered porous silicon increases with sintering temperature. So,
sintering temperature increase results in higher density and strength but unfortunately
lower porosity. The plasma formed during the SPS process results in sample cleaning
and removing of oxides, giving a stronger bonding between particles (Chakravarty
et al. 2011). When using a hot pressing, a densification rate is greater than pressureless sintering (Santanav and Jones 1996), which is unfortunately a disadvantage for
obtaining a highly porous silicon matrix.
Another route to obtain compacts of porous silicon is a combination of powder
metallurgy with subsequent electrochemical or stain etching of previously made
compacts in HF acid solutions with addition of surfactant (Saffie et al. 2005).
For effective anodization, the green compacts or sinters must have the necessary
electrical conductivity and structural stability in the etching electrolyte, and
then a large number of strong covalent bonds between silicon particles are
required (Saffie et al. 2005). So, the Si-H bonds allow the formation of more
Si-Si bonds. The macroporous structures made in this way are permeated by
meso- and micropores (Saffie et al. 2005). Figure 4c shows porous Si sinter
after additional 30 min stain etching in a 20 % aqueous HF solution. Etching
of the porous-sintered matrix proceeds through pores and grain boundaries
enlarging pores and porosity, mainly on the surface, giving a gradient porosity
in the matrix.
Conclusions
The positive aspects of the mechanically made porous silicon can be related to both
technology and applications.
Technology the major advantages of the process are potentially large quantities
of macroporous or complex macro-mesoporous 3D compacts and powders in
forms that are difficult to achieve by electrochemical etching. The mechanical/
thermal route uses processing techniques well developed and understood by the
ceramic industry. Porous silicon elements with several centimeter dimensions
are possible from inexpensive powder feedstocks.
Applications especially promising are large-shaped structures for biomedical
applications, like tissue engineering, if mesoporous enough to be medically biodegradable (see handbook chapter Porous Silicon and Tissue Engineering
Scaffolds). The 3D macroporosity is key for cell and tissue ingrowth, for example. Such porous compacts or particles/beads can also be loaded with chemical
compounds/biomolecules/drugs/nutrients for active delivery or biosensing (see
handbook chapters Drug Delivery with Porous Silicon, Porous Silicon
and Functional Foods, and Porous Silicon Optical Biosensors).
101
References
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1:29432951
Bollero A, Gutfleisch O, Kubis M, M
uller K-H, Schultz L (2000) Hydrogen disproportionation
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48:49294934
Bychto L, Balaguer M, Pastor E, Chirvony V, Matveeva E (2008) Influence of preparation and
storage conditions on photoluminescence of porous silicon powder with embedded Si
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Chakravarty D, Sarada BV, Chandrasekhar SB, Saravanan K, Rao TN (2011) A novel method of
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Macroporous Silicon
Noureddine Gabouze and Francois Ozanam
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Current-Line- and Crystallography-Driven Macropores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Macropore Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Macropore Formation Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Principal Application of Macropores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Design of Regular Macropore Arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
104
104
104
104
106
108
109
110
Abstract
The electrochemical formation of macropores in porous silicon is briefly

reviewed. Various morphologies are obtained as a function of the substrate
type and etching conditions. On n-Si, macropores are generally growing along
preferential crystallographic directions. On p-Si, in aqueous conditions far from
electropolishing, the growth direction is rather determined by the current lines
in the space-charge region. A summary of macropore characteristics is given as
a function of the preparation conditions. Various models have been developed
in order to account for the morphologies and characteristic sizes. These joint
experimental and theoretical works have provided a good understanding of
macropore growth, opening the way to many applications, and the most significant
N. Gabouze (*)
Centre de Recherche sur la Technologie des Semi-conducteurs et lEnergie (CRTSE),
Algiers, Algeria
e-mail: gabouzenoureddine@crtse.dz
F. Ozanam
Physique de la Matie`re Condensee, CNRS-Ecole polytechnique, Palaiseau, France
e-mail: francois.ozanam@polytechnique.edu
DOI 10.1007/978-3-319-05744-6_10
103
104
N. Gabouze and F. Ozanam
ones are mentioned. An impressive level of control has eventually been achieved
for the fabrication of regular macropore arrays of high aspect ratio, including the
incorporation of intentional defects or pore-wall shaping.
Introduction
According to the IUPAC standard, macropores correspond to pores exhibiting
characteristic sizes (pore diameter and average distance between pores) larger
than 50 nm. The term macropore is usually associated with smooth cylindrical
pores with characteristic sizes on the order of 1 m.
This kind of pore can be obtained under a variety of conditions and with
differing morphologies (see chapter Routes of Formation for Porous Silicon).
In this review, we focus on electrochemically etched macropores. The key parameters are the electrolyte type (aqueous (aqu), organic (org), oxidant (ox)) the HF
concentration, the surfactant, the Si doping type and level (n, n+, p, p+), and in some
cases the illumination (backside illumination (bsi) or frontside illumination (fsi)).
Detailed reviews regarding their formation are available (Foll et al. 2002; Lehmann
2005; Chazalviel and Ozanam 2005; Lehmann 2002; and handbook chapter
Porous Silicon Formation by Anodization).
Current-Line- and Crystallography-Driven Macropores

Two distinct classes of macropores are observed, as summarized in Table 1.
Macropores obtained from n-Si always exhibit a strong growth dependence on
crystallographic orientation. On p-Si, this dependency is lower (Lehmann and
Ronnebeck 1999), and in aqueous conditions at low enough current density
and/or high enough HF concentration, the growth turned to be determined by the
direction of the current lines in the space-charge region Media et al. 2011.
Macropore Formation
Table 2 summarizes the main characteristics of the electrochemically grown
macropores on Si, as a function of the formation conditions.
Figure 1 illustrates the variety of pores obtained for p-Si under different conditions.
Macropore Formation Models

Porous silicon formation models have been reviewed (Smith and Collins 1992;
Allongue 1997; Zhang 2001). A conceptual analysis has been attempted (Zhang
2004). Major theoretical contributions applying to macropore formation are listed
in Table 3.
Macroporous Silicon
105
Table 1 Macropores classes and their main characteristics

Class of
macropores
Current-linedriven pores
Macropore
morphology
Rounded
bottoms
Macropore
orientation
Normal to
the surface
Crystallographydriven pores
(111) Facets at
their bottoms
and (110)
oriented walls
(100)
Preferred
growth
direction
Remarks
Filled with
microporous
silicon
Empty
Reference
p-Si, aqu (Wehrspohn
et al. 1998)
n-Si, aqu, bsi: (Lehmann
and Foll 1990)
n-Si, aqu, fsi: (LevyClement et al. 1994)
p-Si, org: (Propst and
Kohl 1994; Ponomarev
and Levy-Clement 1998;
Christophersen
et al. 2000a)
p-Si, aqu: (Lehmann and
Ronnebeck 1999)
Table 2 General conditions for macropore formation. Passivation power denotes the degree to
which a given electrolyte can remove interface states in the bandgap of Si by covering a freshly
etched surface with hydrogen
Formation
conditions
n-Si (aqu)/
bsi
n-Si (aqu)/fsi
n-Si (org)/bsi
p-Si (aqu)
p-Si (org)
n+-Si (aqu +
oxidant)
Specificity of obtained macropores

Grow exclusively in <100>
direction, dependence of the pore
morphology on the sample orientation
SCR limits distances; max. depth >
600 m achieved obtained for J <
JPSL; arrays with pore diameters
100 m250 nm can be obtained
Well-developed macropores oriented
<100>
Not much investigated
Prone to pore branching and strange
morphologies, but regular
macropores arrays can be obtained
Not much investigated
Obtained at current densities <JPSL
and for low-to-medium HF
concentration. Easy to make; arrays
of high aspect ratio can be obtained
Large macropore observed; decisive
parameters are electrolyte resistivity,
oxidizing power, and passivation
power
Small diameter (60100 nm), highaspect-ratio macropores
Reference
(Lehmann 1993, 1995; Ronnebeck
et al. 1999; Kleimann et al. 2000;
Laffite et al. 2011)
(Levy-Clement et al. 1994;

Outemzabet et al. 2005)
(Christophersen et al. 2000a, 2000b,
2001; Izuo et al. 2002)
(Lehmann and Ronnebeck 1999;

Chao et al. 2000; Chazalviel
et al. 2002; Urata et al. 2012)
(Ponomarev and Levy-Clement 2000;
Christophersen et al. 2001; Lust and
Levy-Clement 2002)
(Christophersen et al. 2000c;
Ge et al. 2010)
106
Fig. 1 Morphologies for (100) p-Si in 0.05 M HF, 0.05 M NH4F, and 0.9 M NH4Cl, pH 3, V 0.15
V for 48 h: (a) Plan view and (b) cross section (After Slimani et al. 2009). (c) Macropores on p-Si (aqu),
view after cleavage, for samples prepared from p-Si (400 cm, (100)-oriented), 100 mA/cm2, 6 min,
15 % ethanolic HF (After Chazalviel et al. 2002). Macropores on (100) n-Si etched in ethanolic
hydrofluoric solution with frontside illumination and with an anodization current J 20 mA/cm2 for
t 45 min. (d) Cross-section and (e) plan view (After Outemzabet et al. 2005). (f) Macropore on p-Si
(org) prepared from p-Si (100 cm, 20 mA/cm2, 40 min, HF/ethylene glycol 50/50 by vol)
Principal Application of Macropores

Macropore arrays found applications in various fields, some of which are listed in
Table 4.
Macroporous Silicon
107
Table 3 Major theoretical contributions to macropore formation analysis

Pore
formation
models
Hole
focusing at
pore tips
Surface
chemical
reactions
Linear
stability
analysis
The Current
Burst Model
(CBM)
Basis of model
Hole transport across space charge
General review
(Lehmann and Foll 1990; Lehmann
1993; Lehmann and Ronnebeck 1999)
Pore initiation through limited

diffusion of reaction intermediates
(Kooij and Vanmaekelbergh 1997 ;

Vyatkin et al. 2002)
Quantitative assessment of the effect

of transport across space charge and
reaction kinetics on interface stability
Spatial and temporal inhomogeneity
of current, hydrogen surface
passivation
(Kang and Jorne 1993, 1997; Valance

1997; Wehrspohn et al. 1999;
Chazalviel et al. 2000, 2002)
(Carstensen et al. 2000;
Foll et al. 2002)
Table 4 Main application domains of macropore arrays

Specific design
Densely spaced regular
macropore arrays
Macropores with a sawtoothlike cross section
Macropores filled with lead,
scintillating guide
Macropores coated with
(immobilized) biomolecules
Macropores coated with a
catalyst
Macropores coated with
high-quality dielectrics
Macropores on
multicrystalline Si
Macropores filled with a
succession of different
metals
Optimized macropore
lattices
Matrix-embedded Si
nanowires or particles made
from macroporous Si
Sacrificial or template
macroporous Si layer
Applications area
Brownian motor or
pumps
Membrane (pump of
particles)
X-ray imaging
Reference
(Schilling et al. 2000a)
Detection of specific
biomolecules, DNA, etc.
Chemical reactor
(Kettner et al. 2000; Schilling

et al. 2000b)
(Lehmann and Ronnebeck 2001;
Kleimann et al. 2000)
(Bengtsson et al. 2000;
Yoo et al. 2013)
(Lehmann et al. 1999)
Capacitors
(Lehmann et al. 1996)
Solar cell antireflection

layer
Metallic barcodes
(Foll et al. 1983; Lipinski

et al. 2003; Ao et al. 2012)
(Nicewarner-Pena et al. 2001)
Photonic bandgap (PBG)

materials for optics and
sensing
Lithium-ion batteries
(Gr
uning et al. 1996; Birner
et al. 2000; M
uller et al. 2000;
Wehrspohn et al. 2013)
(Foll 2010; Thakur et al. 2012)
Micromachining or
microelectronics
(Steiner and Lang 1995; Defforge

et al. 2013)
108
Design of Regular Macropore Arrays

The fabrication of regular macropore arrays requires prestructuring of the Si
substrate using lithography and alkaline etching (Chao et al. 2000; van den
Meerakker et al. 2000; Starkov 2003). The pitch of the prestructured hole array
has to match the average spacing of random macropore arrays grown on the same
substrate under similar electrochemical conditions. The width of the walls of the
porous structure (which depends on the pitch structure and the pore lateral size) is
mostly determined by the width of the space-charge layer (i.e., mostly dependent on
substrate doping level) and the pore diameter by the etching conditions. Figures 2
and 3 give some design rules in the case of p-Si. In the case of n-Si, the pore
diameter is mostly determined by the current density, i.e., the illumination level,
according to Lehmanns model (Lehmann 1993). However, diffusion effects in the
liquid phase, as theoretically modeled (Barillaro and Pieri 2005), must be taken into
account in order to keep the fluoride concentration stationary at the pore tips.
Figure 4 gives the typical pore-density range accessible on n-Si under usual
backside illumination conditions or p-Si in the dark.
Fig. 2 Comparison of
characteristic macropore sizes
on p-Si in the current-linedriven regime, when
changing current density for a
substrate resistivity of 100
cm (a) and silicon doping for
an applied current density of
10 mA/cm2 (b) (After
Chazalviel et al. 2002).
Triangles refer to the wall
width and diamonds to the
pore diameter; the closed
(open) symbols refer to the
data obtained in 35 % (25 %)
ethanolic HF. The solid lines
refer to the theoretical
prediction (Chazalviel
et al. 2002) for the pore
diameter, and the dotted line
is two times the space-charge
width
1000
10
100
1
10
ELECTROLYTE
RESISTIVITY ( cm)
Fig. 3 Effect of changing

electrolyte resistivity on
average macropore diameter
on p-Si 1,500 cm, for J0
10 mA/cm2 in an electrolyte
made of 50 % aqueous HF
mixed with ethylene glycol in
variable proportions (After
Chazalviel et al. 2002)
109
CHANNEL DIAMETER (m)
Macroporous Silicon
100
HF % (WITH ETHYLENE GLYCOL)
Fig. 4 Pore density versus silicon electrode doping density for porous silicon layers of different
geometries. Notice that macropores are essentially obtained on low to moderately doped substrates. The dashed line shows the pore density of a triangular pore pattern with a pore pitch equal
to two times the SCR width for a 3 V applied bias. Note that only macropores on n-type substrates
may show a pore spacing significantly exceeding this limit. The regime of stable macropore array
formation on n-Si is indicated by a dot pattern. Doping type and etching current density
(in mA/cm2) are indicated in the legend (After Lehmann 1993)
Conclusions
Since the first report of Theunissen (Theunissen 1972) and the pioneering work of
Lehmann in the 1990s, many efforts have been devoted to macropore fabrication
by electrochemical etching. Impressive macropore arrays have been achieved, with
high aspect ratios and smooth or patterned vertical walls. Examples are shown
110
Fig. 5 Examples of regular and ordered macropore arrays. (a) Two-dimensional macropore array
with an intentional line defect (From Gr
uning et al. 1996); (b) array of pores grown on n-Si (1015
cm3); the pore initiation pattern shown in the inset has been produced by photolithography and
alkaline etching (From Lehmann et al. 2000)
in Fig. 5. Alternative techniques have been proposed such as galvanic etching

(Xia et al. 2000), stain etching (Mills et al. 2005), and metal-assisted (electro)
chemical etching (Li et al. 2013). These techniques are separately reviewed in
this handbook (see Chapters Porous Silicon Formation by Galvanic Etching,
Porous Silicon Formation by Stain Etching, and Porous Silicon Formation by
Metal Nanoparticle-Assisted Etching).
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Mesoporous Silicon
Alexey Khokhlov and Rustem Valiullin
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mesopore Characterization and Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mesoporous Silicon Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pore Size Distribution and Mesopore Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Structure Improvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microstructured Mesoporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
115
116
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127
Abstract
Many physical properties of mesoporous silicon are intimately related to details

of the structural organization of its silicon skeleton. This information can hardly
be accessed directly but can be deduced by studying the complementary pore
space surrounding this skeleton. By profiting from the potentials of nuclear
magnetic resonance cryoporometry to probe fine details of the pore structure
in mesoporous silicon, the results of systematic studies of the correlations
between the fabrication conditions by electrochemical etching and the resulting
mesostructure are presented. A deeper insight into advanced fabrication methods
aimed at structure improvement and microstructure design is provided.
Introduction
Reduced dimensionality of nanocrystalline Si results in its peculiar properties with
a wealth of potential applications, especially in photonics (Cullis et al. 1997;
Kovalev et al. 1999; Bisi et al. 2000). Electrochemical etching of bulk Si provides
A. Khokhlov R. Valiullin (*)
Faculty of Physics and Earth Sciences, University of Leipzig, Leipzig, Germany
e-mail: valiullin@uni-leipzig.de
DOI 10.1007/978-3-319-05744-6_11
115
116
A. Khokhlov and R. Valiullin
an extremely simple approach to form mesoporous silicon (PSi), a material composed of a nanocrystalline skeleton enclosing a network of mesopores with pore
sizes from 2 to 50 nm according to the IUPAC classification (Sing et al. 1985).
Because the dimensions of the pores lie in the same range as those of the skeleton
walls, the pore network thus formed and its properties may be exploited for various
applications including separation of bulky molecules or their use as a template for
forming hybrid structures. Among the various features, brought about by the
electrochemical procedure of PSi nanostructuring, it is in particular the intrinsic
mesoscale disorder which may be of crucial influence for the material properties,
determining, e.g., peculiarities of recombination dynamics of charge carriers
(Roman and Pavesi 1996). Having better control over this disorder may greatly
improve and broaden the technological applications of PSi.
A fundamental understanding of the physicochemical principles of the process
of electrochemical etching of silicon, as a prerequisite for an improvement of the
fabrication technology improvement, is far from being trivial. As a first step, a
better understanding of the effects of the different physical quantities, such as the
current density or the electrolyte composition, on properties of the resulting PSi is
needed. This understanding has to be based on the application of advanced characterization techniques with the option to reveal fine details of the PSi
mesostucture. In this contribution, we present the results of a systematic study of
the correlations between the conditions of electrochemical fabrication of PSi and
the resulting structure using NMR cryoporometry technique. In addition, diffusion
studies using the pulsed field gradient technique of NMR will be used to probe the
structural anisotropy of mesoporous silicon.
Mesopore Characterization and Use

Most important properties of PSi include geometry of the mesopore network and
surface chemistry. There are two most commonly used approaches for structural
characterization of mesoporous solids, including PSi. In the first one, such as gas
adsorption and thermoporometry, the pore size-dependent shifts of phase transitions
are exploited. In this way, the pore size distributions and some details of the pore
space organization can be obtained. An alternative method is direct visualization by
means of electron microscopy techniques (see Fig. 1). Mesopore diameters created by
electrochemical etches are typically found in the range 320 nm, but higher diameters
up to 50 nm can be achieved (Granitzer and Rumpf 2010). Morphology of the pore
network can be tuned from highly anisotropic (tubular) to isotropic one (Lehmann
et al. 2000). The pore size distribution is found to be broad and has been discussed by
some authors in terms of fractal-like pore space organization (Tondare et al. 2008;
Moretti et al. 2007; Wesolowski 2002). The inner surface is relatively rough (Kumar
et al. 2008; Naumov et al. 2008). Surface chemistry of the mesopore walls can
be assessed using optical techniques, such as FTIR (Jarvis et al. 2012). PSi is
finding applications for biofiltration, drug delivery, optics, chromatography, catalysis,
sensing, and lightweight mechanical components (see, e.g., handbook chapters
Mesoporous Silicon
117
Fig. 1 Electron microscopy

image of a mesoporous
silicon membrane surface
(top view)
Porous Silicon in Immunoisolation and Bio-filtration, Porous Silicon Pho

tonic Crystals, Porous Silicon Diffraction Gratings, Porous Silicon Optical
Biosensors).
Mesoporous Silicon Samples

For tracing the relationship between the fabrication parameters and the pore
structure, we will focus on (but not exclusively refer to) one family of PSi, obtained
using highly doped p-type silicon wafers with (100) crystallographic orientation
and with a resistivity of 25 mcm. The PSi samples were fabricated using
a limited range for variation of the etching parameters, notably the anodization
current and the electrolyte composition. Anodization was performed using a
homebuilt wet-etching cell with horizontal orientation of the silicon wafers.
The lower electrical contact to the wafers was provided via a well-polished
copper base. On the top of the silicon wafer, a cylindrical cell with the electrolyte
was placed. The diameter of the porous silicon layer formed on the wafer
surface was controlled using an O-ring with an inner diameter of 15 mm. As an
electrode, a platinum wire with a diameter of 1 mm immersed in the electrolyte
was used. The wire had a circular shape with a diameter of 31 mm and was
fixed parallel to the silicon wafer surface at a distance of 18 mm. Etching was
performed at dark conditions and at room temperatures. Notions and some
relevant fabrication parameters for PSi samples quoted in the text are given in
Table 1. Characterization will exclusively be based on NMR cryoporometry (see
chapter NMR Cryoporometry and Estimation of Pore Sizes in Mesoporous
Silicon). It is worth noting that, for pore sizes below 20 nm, this method is mostly
controlled by smallest pores and, therefore, underestimates the pore size distribution (Khokhlov et al. 2008).
118
Table 1 Properties of mesoporous silicon samples used for the case study
Sample
PS100, PS60,
PS20
Substrate
resistivity, cm
(25) 103
Electrolyte composition
HF:C2H5OH
1:1
Etching current density,

mA/cm2
100, 60, 20
Pore Size Distribution and Mesopore Structure

It is well known that with increasing anodization current and all other conditions
kept constant, typically porous films with higher porosities and larger pore sizes are
formed (see handbook chapter Porous Silicon Formation by Anodization).
It has long been recognized that also the resulting pore size distributions (PSD)
may be altered by the current strength: PSDs typically broaden with increasing
porosity (Herino et al. 1987). By showing an increase of both the average pore size
and the distribution width with increasing anodization current density, the data of
Fig. 2 nicely confirm this scenario.
It is worth noting that all samples used to obtain the results of Fig. 2 were
fabricated using identical etching times of 40 min. Due to the differences in the
speeds of the porous film formation for different anodization currents, also the
thicknesses of the resulting PSi films are different. Indeed, Fig. 3 demonstrates that
the speeds of the porous film formation almost linearly increase with increasing j.
Thus, the samples PS20, PS60, and PS100, compared in Fig. 2, have thicknesses of
50, 105, and 146 m. Therefore, it may be conjectured that, with increasing film
thickness, there might be a progressive change in the etching conditions, resulting
in porosity gradients and PSD broadening (Thonissen et al. 1997).
In order to study the influence of the etching depth on the characteristics of the
porous film in more detail, the PSDs of identically fabricated PSi films, but with
different thicknesses, have been compared. Figure 4 shows such PSDs for two PS100
materials etched over 40 and 20 min. These two films were found to have thicknesses
of 145 and 90 m, respectively. The experimental data reveal that, although the
maxima of the two PSDs coincide, the distribution in the thicker sample is significantly broader. A change of the electrolyte concentration in the zone of the chemical
reaction at the pore bottom may be anticipated as a possible reason for the broadening
(Billat et al. 1997). Indeed, when pores become longer, it takes a longer time to
refresh the electrolyte in the pores. Thus, the electrochemical reaction may occur
under conditions of continuously changing electrolyte composition.
The consequences of the electrolyte degradation can be modeled by comparing
the mesostructure for PSi samples obtained with different HF concentrations.
Figure 5 shows the relevant PSDs, indicating that, with decreasing HF concentration, the average pore size increases and the PSD becomes slightly broader.
Decrease of the HF concentration to values less than 35 % does not, however,
lead to a further increase of the average pore size. Rather, at low HF concentrations,
the etch rate slows notably down and one observes an increase in porosity.
Mesoporous Silicon
Fig. 2 Pore size distribution
in samples PS20, PS60, and
PS100 obtained using an
etching time of 40 min
Fig. 3 Speed of the porous

film formation as a function
of anodization current density
j. The line shows the function
s 0.3 + 0.045j (The data
shown in the figure are
deduced from the porous
silicon films obtained with
thicknesses up to 50 m. It
was noted that, with
increasing film thickness, the
formation speed decreases
(Khokhlov 2009))
Fig. 4 Pore size distributions

for PS100 samples prepared
with etching times of 20 min
(circles) and 40 min
(squares). All other etching
parameters are kept identical
119
120
Fig. 5 Pore size distributions for samples obtained using etching current densities of 20 mA/cm2
applied for 40 min. As an electrolyte, 35 % (open circles), 40 % (rectangles), 45 % (diamonds),
50 % ( filled circles), and 60 % (triangles) aqueous hydrofluoric acid solutions were used
Structure Improvement
It has been shown in the preceding section that changes of the electrolyte composition in the reaction zone may alter the resulting pore structure. For promoting
electrolyte refreshment, stirring of the electrolyte in the cell above silicon wafers is
often used. This, however, may turn out to be not effective enough due to the small
pore sizes prohibiting a convection-assisted mixing of the electrolyte in the pores.
It has, therefore, been suggested to use the stop-etch method, in which the naturally
occurring diffusion is exploited for electrolyte renewal (Thonissen et al. 1997).
As a main feature of this method, anodization is carried out by a sequence of current
pulses, rather than by a continuous current. The time intervals between the current
pulses enable electrolyte refreshment in the pores by diffusion. Such a procedure
allows the fabrication of PSi with narrower PSD, as demonstrated by the results of
Fig. 6 showing two PSDs as obtained using the normal and the stop-etch
procedures.
An important advantage of the stop-etch method is the possibility to fabricate
thick porous films with uniform structural properties. Thus, Fig. 7 shows PSDs for
two PS100 samples prepared using the stop-etch method. To obtain the thicker
porous film, we have etched the substrate for 16.5 h, which resulted in the formation
of a 390 m thick porous film. For comparison, also shown is the PSD of a sample
Mesoporous Silicon
121
Fig. 6 Pore size distributions in PS100 samples obtained by applying a constant current density
(open circles, porous film thickness 70 m) and using the stop-etch procedure ( filled circles,
porous film thickness 90 m) with the same current density pulses applied for 1 s intermittent with
10 s refreshment periods
Fig. 7 Pore size distributions in PS100 samples obtained using the stop-etch procedure with 5 s
etching pulses intermittent with 10 s refreshment periods applied for 2 h ( filled circles, porous film
thickness 54 m) and for 16.5 h (open circles, porous film thickness 390 m)
122
prepared in just 2 h (54 m thick). The comparison reveals that, upon increasing
etching time, both an increase of the average pore size and a broadening of the PSD
are observed. These changes are, however, much less significant than those
obtained by applying the traditional etching procedure.
The main drawback of the stop-etch method are the notably longer times
required for the fabrication. The traditional stop-etch method can, however,
be optimized by replacing the constant time periods required for electrolyte
refreshment by depth-dependent times for the refreshment period. Indeed,
diffusion theory says that the time required to replace the electrolyte in a
one-end open channel may be estimated as L2/6D, where L is the channel
length and D is the diffusivity of HF in the electrolyte confined to the channels.
With D 5 1010 m2/s, measured by PFG NMR, and with the data of Fig. 3,
the times required at different fabrication stages can readily be estimated.
A nice feature of this approach, owing to its dependence on the channel length,
the refreshment period may be very short at the beginning. To exemplify, total
etching time for a PSi film with a thickness of 200 m produced with identical
refreshment intervals of 13.3 s and anodization periods of 5 s will amount to
15 h. While using the stop-etch method with varying stop intervals, this time is
reduced to only 6 h.
Knowledge of the depth-dependent values of offers another advantage for the
fabrication of thick porous films. If in the traditional stop-etch scheme the refreshment times are set too short, unwanted structure gradients may result. With the
advanced scheme, these effects are automatically excluded due to the matched
values of . This is further proved by the data of Fig. 8 showing two PSDs for two
PS60 samples obtained using the advanced stop-etch method for 2 and 6 h,
corresponding to porous film thicknesses of 54 and 200 m, respectively. In
contrast to the data of Fig. 7, the thus obtained PSDs and the average pore sizes
are seen to be almost identical.
It is interesting to note that PSD broadening due to the electrolyte deterioration
can be reduced not only by improving the electrolyte quality but also by
compensating the degradation effects by other means, e.g., by varying the
anodization current during fabrication. The principal possibility of such structural
manipulation is demonstrated in Fig. 9. For these experiments, two PSi samples
have been obtained by varying the electrical current density continuously from
20 to 60 mA/cm2 and from 60 to 20 mA/cm2 as shown in Fig. 9a1. As a result,
although being etched using the same currents, the PSD in the latter case
(see Fig. 9b) is found to be notably narrower than in the former one. Clearly,
in these two cases the effects of the variation in electrolyte composition and
current density are either additive (Fig. 9b, open symbols) or subtractive (Fig. 9b,
filled symbols).
These particular functional forms were used to maintain frustum-like morphologies of the
resulting channels in the porous films.
Mesoporous Silicon
123
Fig. 8 Pore size distributions for PS60 samples prepared by the stop-etch procedure with
equal refreshment time intervals between etching steps for 2 h ( filed circles, porous film
thickness 54 m) and by the optimized stop-etch procedure for 6 h (open circles, porous
film thickness 200 m)
Microstructured Mesoporous Silicon

One of the technologically important properties of PSi is the possibility
to modulate the porosity and the pore size during fabrication of the samples.
Due to, e.g., correlations existing between the porosity and optical properties
of PSi, the thus obtained materials, sometimes referred to as optical superlattices
(Frohnhoff and Berger 1994), find diverse applications in optics (Canham
et al. 1996; Barthelemy et al. 2007) (see Chapter Porous Silicon Multilayers
and Superlattices). An important question, in this respect, is whether the
structural properties of the composite pore systems may be deduced from those
of the individual blocks composing the systems. On considering mesoporous
silicon with pore sizes below 50 nm, the lack of appropriate experimental
techniques and a poor understanding of phase transitions in disordered
mesopore systems precluding, in particular an in-depth analysis by conventional
structure analysis (gas sorption, thermoporometry), do not allow a definitive
answer. Thus, in the NMR cryoporometry method exploited in this work, a
nontrivial coupling between solid and liquid transitions in adjacent pore sections
with different pore dimensions cannot be accounted for in model assumptions.
Nevertheless, approximate analysis is still possible as it will be discussed in
this section.
124
Fig. 9 Current density profiles (a) used to obtain porous silicon films and the resulting pore size
distributions (b). The solid and dashed lines correspond to filled and open symbols in (b), respectively
In Fig. 10, two PSDs for PSi materials with intentionally microstructured pores
are shown. The first sample was obtained by first forming a layer of PS20 for
20 min, corresponding to a layer thickness of 25 m, immediately followed by the
formation of a PS100 layer for further 20 min (with a layer thickness of about
75 m). The PSD obtained using NMR cryoporometry (Fig. 10a) shows a bi-modal
distribution with two peaks, which are found to be in a reasonable agreement with
Mesoporous Silicon
125
Fig. 10 Pore size distributions obtained for two- (a, PS20 and PS100) and multilayer (b, PS20
and PS80) porous silicon formed by alternating anodization current. The lines show the peak
position of the PSD for PS20, PS80, and PS100
those measured for isolated PS20 and PS100 materials. Moreover, the ratio of the
areas under the two peaks is in agreement with the ratio of the pore volumes in the
two layers expected from the fabrication conditions.
The second sample was prepared in a way similar to the first one, but instead of
two, 20 such alternating layers were formed using etching conditions corresponding
to the fabrication of PS20 and PS60 films. Notably, the number of such modulations
126
Fig. 11 Pore size distributions for samples PS20 (open rectangles) and PS60 (open triangles) and
for a sample obtained by using a sawtooth variation of the etching current density
up to a thousand was reported in the literature (Svyakhovskiy et al. 2012). The

thicknesses of these layers were 3.25 and 1.75 m, respectively, which were chosen
to provide equal pore volumes in the two different layers. The data of Fig. 10b, once
again, reveal a reasonable agreement with the expected structure. The PSD
corresponding to the pore sections with larger pores is found, however, to be shifted
to lower values as compared to single-standing PS60 films. Whether this reflects
real changes in the pore structure due to the current alternations or is an artifact of
NMR cryoporometry2 cannot be definitely answered.
Finally, it is worth mentioning that the modulation of the fabrication parameters can be used for the fabrication of PSi materials with desired pore size
distributions. Thus, Fig. 11 shows PSD for a PSi sample obtained using a
sawtooth variation of the etching current density between the two extreme values
of 20 and 60 mA/cm2. The current profile was chosen to provide a periodicity
of 1 m in the pore sizes. The thus formed porous film consisted of 50 such
sections. For comparison, PSDs corresponding to PS20 and PS60 materials
are also shown. The PSD for the PSi with modulated pore structure is found to
represent a sum of the two individual materials PS20 and PS60, providing
evidence for the thus established option of designing PSDs by a purposeful
variation of the etching conditions.
See Chapter NMR Cryoporometry and Estimation of Pore Sizes in Mesoporous Silicon for the
discussion on NMR cryoporometry characterization.
Mesoporous Silicon
127
References
Barthelemy P, Ghulinyan M, Gaburro Z, Toninelli C, Pavesi L, Wiersma DS (2007) Optical
switching by capillary condensation. Nat Photonics 1(3):172175
Billat S, Thonissen M, ArensFischer R, Berger MG, Kruger M, Luth H (1997) Influence of etch
stops on the microstructure of porous silicon layers. Thin Solid Films 297(12):2225
Bisi O, Ossicini S, Pavesi L (2000) Porous silicon: a quantum sponge structure for silicon based
optoelectronics. Surf Sci Rep 38(13):1126
Canham LT, Cox TI, Loni A, Simons AJ (1996) Progress towards silicon optoelectronics using
porous silicon technology. Appl Surf Sci 102:436441
Frohnhoff S, Berger MG (1994) Porous silicon superlattices. Adv Mater 6(12):963965
Granitzer P, Rumpf K (2010) Porous silicon: a versatile host material. Materials 3(2):943998
Herino R, Bomchil G, Barla K, Bertrand C, Ginoux JL (1987) Porosity and pore-size distributions
of porous silicon layers. J Electrochem Soc 134(8A):19942000
Jarvis KL, Barnes TJ, Prestidge CA (2012) Surface chemistry of porous silicon and implications
for drug encapsulation and delivery applications. Adv Colloid Interf Sci 175:2538
University of Leipzig, Leipzig
Khokhlov AG, Valiullin RR, Stepovich MA, Karger J (2008) Characterization of pore size
distribution in porous silicon by NMR cryoporosimetry and adsorption methods. Colloid J
70(4):507514
Kovalev D, Heckler H, Polisski G, Koch F (1999) Optical properties of si nanocrystals. Phys Status
Solidi B-Basic Res 215(2):871932
Kumar P, Hofmann T, Knorr K, Huber P, Scheib P, Lemmens P (2008) Tuning the pore wall
morphology of mesoporous silicon from branchy to smooth, tubular by chemical treatment.
J Appl Phys 103(2):024303
mechanism of mesoporous silicon. Mater Sci Eng B 69:1122
Moretti L, De Stefano L, Rendina I (2007) Quantitative analysis of capillary condensation in
fractal-like porous silicon nanostructures. J Appl Phys 101(2):024309
Naumov S, Khokhlov A, Valiullin R, Karger J, Monson PA (2008) Understanding capillary
condensation and hysteresis in porous silicon: network effects within independent pores.
Phys Rev E 78(6):060601
Roman HE, Pavesi L (1996) Monte Carlo simulations of the recombination dynamics in porous
silicon. J Phys Condens Matter 28:5161
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985)
Reporting physisorption data for gas solid systems with special reference to the determination
of surface-area and porosity (recommendations 1984). Pure Appl Chem 57(4):603619
Svyakhovskiy SE, Maydykovsky AI, Murzina TV (2012) Mesoporous silicon photonic structures
with thousands of periods. J Appl Phys 112(1):013106
Thonissen M, Berger MG, Billat S, ArensFischer R, Kruger M, Luth H, Theiss W, Hillbrich S,
Grosse P, Lerondel G, Frotscher U (1997) Analysis of the depth homogeneity of p-PS by
reflectance measurements. Thin Solid Films 297(12):9296
Tondare VN, Gierhart BC, Howitt DG, Smith RL, Chen SJ, Collins SD (2008) An electron
microscopy investigation of the structure of porous silicon by oxide replication. Nanotechnology
19(22):225301
Wesolowski M (2002) Fractal-like model of porous silicon. Phys Rev B 66(20):205207
Microporous Silicon
Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Micropores in Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Properties of Microporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Potential New Application Areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
130
130
132
133
133
134
Abstract
Virtually all porous silicon structures studied to date via electrochemical

etching are mesoporous or macroporous, rather than microporous. Very high
surface area (540840 m2/g) porous silicon structures with high micropore
content have now been demonstrated by wafer anodization in very concentrated hydrofluoric acid, metal-assisted stain etching, galvanic etching, and
silica reduction. The smallest electrochemically generated pores to date are
probably supermicropores lying in the range of 12 nm diameter since they
do not exhibit molecular sieving over the 0.40.85 nm molecule size range.
Highly microporous silicon could be advantageous for a number of specific
applications such as hydrogen storage, gettering, explosives, and gas sensing,
but the low chemical stability of the material could pose challenges with its
industrial exploitation.
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_12
129
130
L. Canham
Introduction
In this handbook we adopt the IUPAC definition of micropores, namely, that this
label only refers to extremely small pores of diameter less than 2 nm. We now
know that with anodization (see handbook chapter Porous Silicon Formation by
Anodization), average pore size is lowered when using (a) lightly doped p-silicon,
(b) low current densities, and (c) highly concentrated (>40 wt%) hydrofluoric acid.
This last parameter has been particularly important in the literature with regard
micropore generation.
Bomchil et al. (1983) demonstrated in 1983, via X-ray tomography, that the
addition of a simple surfactant like ethanol to HF-based solutions produced anodized layers of much higher uniformity, due to lowering of the effects of hydrogen
gas generation. This was subsequently verified and adopted by most research
groups worldwide to this day. One consequence of this is that virtually all material
made by wafer anodization over the last 30 years is primarily mesoporous, not
wholly microporous. One has to search the early literature to find examples where
very concentrated (>40 wt%) hydrofluoric acid was used that generates the smallest
pores. Although the more recent literature contains many examples where authors
refer to fabrication of microporous silicon, an examination of their fabrication or
characterization data reveals this is somewhat a misnomer, according to the IUPAC
criteria above. In extreme cases, even macropores (>50 nm diameter) have been
referred to as micropores. Such studies are not referenced here although microporous silicon appears in their titles.
In this review we first examine the literature for strong evidence of micropores
(<2 nm width) and the smallest mesopores (25 nm) and then comment on the
attributes and challenges inherent with such material which has received much less
attention than macroporous and mesoporous forms of the semiconductor.
Micropores in Silicon
Figures 1 and 2 illustrate two key signatures of wholly microporous silicon: the
absence of any mesopores (>2 nm width) by high-resolution transmission electron
microscopy (see handbook chapter Microscopy of Porous Silicon) and the
absence of any hysteresis in a type I isotherm of nitrogen adsorption and desorption
in a material of very high surface area (see handbook chapter Gas Adsorption
Analysis of Porous Silicon).
Although the first Uhlir studies (1956) included work with 2448 % HF, it is
not clear whether or not they processed p-silicon with the most concentrated
electrolyte. Watanabe and Sakai were probably therefore the first to create
highly microporous silicon, albeit without realizing it (Watanabe and Sakai
1971). Other workers who conducted early studies on the properties of layers
anodized in p-wafers using highly concentrated HF included Unagami (1980) and
Koshida et al. (1985) who correctly referred to a microporous structure (Koshida
Microporous Silicon
131
Fig. 1 (a) TEM image and

inset diffraction pattern from
microporous silicon
fabricated by anodization of
p-wafers in concentrated
(50 %) aqueous
hydrofluoric acid
Fig. 2 (a) Typical isotherm

from mesoporous silicon with
hysteresis (b) isotherm from
microporous silicon
fabricated by anodization of
p-wafers in concentrated
(50 %) aqueous hydrofluoric
acid (Canham and Groszek
1992)
Amount adsorbed (103 mol)
0.3
0.2
0.1
mesoporous Si
0.2
0.1
microporous Si
0.2
0.4
0.6
0.8
1.0
Relative pressure (P/Po)
et al. 1986). The 1988 review of Bomchil et al. (1988) clarified the trends in poresize distribution with anodization parameters for a range of mesoporous layers.
They indicated the first gas adsorption evidence for some pores being below 2 nm in
specific cases but commented that the technique was no longer accurate in this poresize regime. Table 1 summarizes more recent studies where ultrasmall pore size
was quantified and the techniques used to estimate size. Note how, where measured,
the surface areas can have very high values (>800 m2/g).
132
L. Canham
Table 1 Estimates of micropore (<2 nm) and small mesopore (<5 nm) size
Fabrication
method
Anodization
Anodization
Anodization
Anodization
Anodization
Anodization
Details
p-Si
ETH-HF
5um layer
p-Si, 50%HF
200um
membrane
p-Si, 50 % HF
6um layer
p-Si, 55 % HF
150um
membrane
Not given
Anodization
n-Si and light

HF/ethanol
n-Si
Silica
reduction
Diatom
conversion
Stain
etching
p-Si, Fe(III)
catalyst
HF/H2SO4
p-Si
HF/acetic
acid
Anodization
Galvanic
etching
Pt cathode
HF/H2O2/
ethanol
Surface
area
(m2/g)
600
Pore
diameter
estimates
(nm)
<4.0
Gas adsorption
563
0.81.2
Sugiyama and
Nittono (1990)
Microcalorimetry
and gas
adsorption
Gas adsorption
812
1.02.0
Canham and
Groszek (1992)
783
3.0
Ruike
et al. (1996)
Water isotherms
(NMR)
Positron lifetime
spectroscopy
Not
given
Not
given
1.4
Mamykin
et al. (1998)
Biasini
et al. (2000)
Positron lifetime
spectroscopy
Gas adsorption
Not
given
541
1.41.5
HRTEM
Not
given
HRTEM
Not
given
~39
Gas adsorption
840
<3.0
Characterization
technique
Small angle
X-ray scattering
2.4
Wide
range
including
<2.0
~3.0
Reference
Goudeau
et al. (1989)
Cheung
et al. (2007)
Bao
et al. (2007)
Dudley and
Kolasinski
(2009)
Semai
et al. (2009;
Gael Gautier,
2013, Private
communication)
Becker
et al. (2011)
Properties of Microporous Silicon

Since microporous structures can have the highest surface areas and the highest
pore densities, they are the most sensitive to ambient and hence storage conditions.
Their chemical composition changes dramatically when stored in ambient air
(Canham et al. 1991). Thin layers are rapidly converted to stoichiometric silica
Microporous Silicon
133
at elevated temperatures (Watanabe and Sakai 1971) where even sub-ppm levels of
oxygen in argon gas will lead to significant oxygen content (Yamanaka et al. 1975).
When loaded with oxidation catalysts, they have very high chemical reactivity
(Becker 2011) and are under development for explosive use (see handbook chapter
Energetics with Porous Silicon). They have been utilized in bacterial culture
(Wainwright et al. 1999) and when in simulated body fluids can promote calcification, of relevance to orthopedic use (Canham 1995). Thick layers of moderate
porosity are also under study for RF device applications where high electrical
resistivity is desired (Gautier et al. 2008).
Potential New Application Areas

Highly microporous silicon will typically have larger surface areas than
mesoporous silicon. High surface areas can also be achieved at moderate porosities
(4060 %) where the mechanical strength of the matrix exceeds that of high
porosity mesoporous silicon. This could have benefits for those applications
that primarily utilize enlarged surface area, such as explosives (handbook chapter
Energetics with Porous Silicon), gettering (handbook chapter Porous
Silicon Gettering), or gas sensing (handbook chapter Porous Silicon Gas
Sensing and in particular Ref. (Gao et al. 2002) this chapter). Of particular
interest could be hydrogen storage uses since here, both ultrasmall pore size and
maximum surface areas should be advantageous with regard loading levels.
Nevertheless, against that attribute, the following potential disadvantages must
be considered:
Layer uniformity challenges with anodization

Difficulties in complete removal of etch residue products and drying
Moderate pore volumes
Limits to very small drug molecules that can be loaded for controlled release
Concluding Remarks
Very high surface area (540840 m2/g) porous silicon structures with high
micropore content have now been demonstrated by wafer anodization, metalassisted stain etching, galvanic etching, and silica reduction. The smallest
electrochemically generated pores to date are probably supermicropores lying in
the range of 12 nm diameter since they do not exhibit molecular sieving over the
0.430.85 nm molecule size range (Canham and Groszek 1992). Most applications currently utilize mesoporous rather than microporous silicon. Further
improvements in the surface area of both mesoporous and microporous silicon
are anticipated from improved drying techniques ( Drying Techniques Applied
to Porous Silicon).
134
L. Canham
References
Bao Z, Weatherspoon MR, Shian S, Cai Y, Graham PD, Allan SM, Ahmad G, Dickerson MB, Church
BC, Kang Z, Abernathy HW III, Summers CJ, Liu M, Sandhage KH (2007) Chemical reduction
of three-dimensional silica micro-assemblies into microporous silicon replicas. Nature 446:172
(2011) Galvanic porous silicon composites for high velocity nanoenergetics. Nano Lett 11
(2):803807
Biasini M, Ferro G, Monge MA, Di Francia G, La Ferrara V (2000) Study of the structure of
porous silicon via positron annihilation experiments. J Phys Condens Matter 12:59615970
Bomchil G, Herino R, Barla K, Pfister JC (1983) Pore size distributions in porous silicon studied
by adsorption isotherms. J Electrochem Soc 130(7):16111614
Bomchil G, Halimaoui A, Herino R (1988) Porous silicon: the material and its applications to SOI
technologies. Microelectron Eng 8:293310
Canham LT (1995) Bioactive silicon fabrication through nanoetching techniques. Adv Mater 7
(12):10331037
Canham LT, Groszek AJ (1992) Characterization of microporous silicon by flow calorimetry :
comparison with a hydrophobic silica molecular sieve. J Appl Phys 72(4):15581565
Canham LT, Houlton MR, Leong WY, Pickering C, Keen JM (1991) Atmospheric impregnation
of porous silicon. J Appl Phys 70(1):422431
Cheung CF, Nahid F, Cheng CC, Beling CD, Fung S, Ling CC, Djurisec AB, Pramanik C, Saha H,
Sarkar CK (2007) Optical and microstructural characterization of porous silicon using photoluminescence, SEM and positron annihilation spectroscopy. J Phys Cond Mat 19(48):486002
Dudley ME, Kolasinski KW (2009) Stain etching with Fe(III), V(V) and CE(IV) to form microporous silicon. Electrochem Solid State Lett 12(4):D22D26
Gao J, Gao T, Li YY, Sailor MJ (2002) Vapor sensors based on optical interferometry from
oxidised microporous silicon. Langmuir 18(6):22292233
Gautier G, Leduc P, Semai J, Ventura L (2008) Thick microporous silicon isolation layers for
integrated RF inductors. Phys Stat Sol C 5(12):36673670
Goudeau P, Naudon A, Bomchil G, Herino R (1989) X-ray small angle scattering analysis of
porous silicon layers. J Appl Phys 66(2):625628
Koshida N, Nagasu M, Sakusabe T, Kiuchi Y (1985) The current voltage characteristics of a
photoelectrochemical cell using p-type porous silicon. J Electrochem Soc 132(2):346349
Koshida N, Nagasu M, Echizenya K, Kiuchi Y (1986) Impedance spectra of p-type porous
Si-electrolyte interfaces. J Electrochem Soc 133(11):22832287
Mamykin AI, Moshnikov VA, Ilin AY (1998) Magnetic resonance spectroscopy of porous
quantum-size structures. Semiconductors 32(3):322324
Ruike M, Houzouji M, Motohashi A, Murase N, Kinoshita A, Kaneko K (1996) Pore structure of
porous silicon formed on a lightly doped crystal silicon. Langmuir 12:48284831
Semai J, Gautier G, Ventura L (2009) Study of thick microporous silicon layer from highly
resistive silicon. J Nanosci Nanotechnol 9(6):36523656
Sugiyama H, Nittono O (1990) Microstructure and lattice distortion of anodized porous silicon
layers. J Crystal Growth 103:156163
Uhlir A Jr (1956) Electrolytic shaping of germanium and silicon. Bell Syst Tech J 35:333347
Unagami T (1980) Formation mechanism of porous silicon layer by anodisation in HF solution. J
Wainwright M, Canham LT, Al-Wajeeh K, Reeves CL (1999) Morphological changes (including
filamentation) in Escherichia coli grown under starvation conditions on silicon wafers and
other surfaces. Lett Appl Microbiol 29:224227
Watanabe Y, Sakai T (1971) Application of a thick anode film to semiconductor devices. Rev
Electron Commun Labs (Japan) 19(78):899903
Yamanaka H, Sakamoto M, Hamano K (1975) Oxygen sensitivity of porous silicon by anodic
reaction. Jpn J Appl Phys 14(2):303304
Pore Volume (Porosity) in Porous Silicon

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pore Volume Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porosity, Pore Volume, and Bulk Density of Porous Silicon in Air . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications of Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
135
137
138
139
139
Abstract
The porosity (void fraction per unit volume) of silicon has been varied from less
than 1 % to as high as 97 % using electrochemical etching of solid silicon with
supercritical drying or silica aerogel reduction with supercritical drying. Fifteen
techniques are identified for quantifying porosity in specific physical forms, and
a conversion table is provided between porosity, pore volume (void content per
unit weight), and bulk density in air. Finally ten applications are given which
exploit medium to high (2595 %) porosity, or the ability to vary porosity
significantly within a given structure.
Introduction
The pore volume of a porous material or structure, its void content per unit weight
(cm3/g), is directly related to its porosity (void fraction per unit volume) via the density
of the remaining solid skeleton (Lowell and Shields 2004). It is a critical parameter for
applications such as drug delivery (see handbook chapter Drug Delivery with
Porous Silicon) where it often defines the maximum drug payload that can be
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_13
135
136
L. Canham
Fig. 1 Low- to ultrahigh porosity silicon structures: (a) <5 % macroporous wafer; (b) buried
porosity for layer transfer (Terheiden et al. 2011); (c) ~35 % porosity membrane for thermoelectrics (Tang et al. 2010); (d) a ~40 % macroporous photonic crystal waveguide (Muller et al. 2000);
(e) microfabricated ~60 % mesoporous microparticles for drug delivery (Chiappini et al. 2010); (f)
a ~70 % mesoporous nanowire for photocatalysis (Qu et al. 2010); (g) double-walled silicon
nanotubes (~80 % porosity) for battery anodes (Wu et al. 2012); (h) photoluminescent ~95 %
mesoporous aerocrystal (Canham et al. 1994)
delivered from a given structure. It also has a dramatic effect on mechanical properties
such as strength and hardness (handbook chapter Mechanical Properties of Porous
Silicon), thermal properties such as thermal conductivity (see handbook chapter
Thermal Isolation with Porous Silicon), and optical properties such as refractive
index (handbook chapter Refractive Index of Porous Silicon). Techniques available to quantify this property are first summarized; a conversion table between
porosity, pore volume, and bulk density for porous silicon is then provided. Finally,
application areas reviewed elsewhere in the handbook are selected where medium to
high pore volumes are utilized, with typical required porosity values estimated from the
literature. Figure 1 illustrates the variety of physical porous forms of silicon that require
pore volume analysis, with porosities ranging from about 595 %.
137
Pore Volume Measurement

Table 1 lists various established techniques available for quantifying pore volume
(porosity) in porous silicon layers, membranes, fibers, tubes, and particles.
Table 1 Standard techniques for quantifying pore volume in materials
Technique
Gravimetric
analysis
Gas adsorptiondesorption
Liquid sorption
DSC
(Differential
Scannig
Calorimetry)
thermoporometry
Ellipsometry
Electron
microscopy and
image processing
NMR
cryoporosimetry
Applicability
Microporous
or mesoporous
layers from
anodization
Mesoporous
powders
Basis of technique
Weight losses from
etching and complete
layer dissolution
Capillary
condensation of
nitrogen gas
Mesoporous or
macroporous
powders
Mesoporous
powders
Free-flowing powder
until liquid titration
reaches wet point
Pore liquid mass
fractions derived
from melt endotherm
peak intensities
Microporous
or mesoporous
layers or films
Mesoporous or
macroporous
layers
Mesoporous
flakes or
powders
Refractive index
scales with porosity
Surface pore
dimensions and
densities
Difference between
spin-spin relaxation
times of liquid/solid
in pores
Scattering contrast
between pores and
silicon skeleton
Scattering contrast
between pores and
silicon skeleton
General
review
(Lowell and
Shields 1991;
Lowell
et al. 2004)
(Sing
et al. 1985;
Groen
et al. 2003)
(McDaniel
and Hottovy
1980)
(Landry
2005)
Use with
porous
silicon
(Brumhead
et al. 1993)
(Herino
et al. 1987)
(Canham
2014)
(Riikonen
et al. 2011)
(Tompkins
and Irene
2005)
(Stevens
et al. 2009)
(Ludurczak
et al. 2009)
(Mitchell
et al. 2008)
(Khokhlov
et al. 2008)
(Calo and
Hall 2004)
(Kadar
et al. 2000)
(Schafer and
Keefer 1986)
(Goudeau
et al. 1989;
Mazumder
et al. 1998)
(Maehara
et al. 2000;
Chamard
et al. 2001)
(Chakravarty
et al. 2011)
Small-angle
neutron
scattering
Small-angle
X-ray scattering
Mesoporous
powders or
thick films
Mesoporous
powders or
thick films
Grazing
incidence smallangle X-ray
scattering
Mercury
porosimetry
Mesoporous
thin films
Critical reflectivity
angle dependence on
electron density
(Renaud
et al. 2009)
Macroporous
powders
Reversible intrusion
of mercury under
varying pressures
(Rouquerol
et al. 2012)
(Pettersson
et al. 1998)
138
L. Canham
More novel approaches developed to assess porosity in silicon include the use of
dye fluorescence (Plain et al. 2007), Rutherford backscattering spectroscopy (TorresCosta et al. 2005), optical interferometry (Lee et al. 2000; Foss et al. 2005; Gharbi
et al. 2012), and ultrasonics (Zharkii et al. 2003; Bustillo et al. 2014).
Porosity, Pore Volume, and Bulk Density of Porous Silicon in Air

Table 2 provides a conversion table for porosity and pore volume. The data is based
on the solid silicon skeleton having a true density of 2.33 gcm 3 and ambient air
having a density of 0.0012 gcm 3. Note how there is a very dramatic increase in
gravimetric pore volume with high porosities. A 70 % porosity layer has 1 ml/g of
pore volume available, but by 99 % porosity this has risen to 40 ml/g. Porous
amorphous silicon and silica will have slightly higher pore volumes, at a given
porosity, than those below for (poly)crystalline silicon, due to their lower skeleton
densities.
Table 2 Porosity, pore volume, and bulk density (silicon and air) values for crystalline silicon
Porosity (%)
0
10
Pore volume
0
0.05
(ml/g)
2.33 2.10
Bulk density
(g/cm3)
Porosity (%)
95
Pore volume (ml/g)
8.1
Bulk density (g/cm3)
0.12
20
0.11
30
0.18
40
0.29
50
0.43
60
0.65
70
1.0
80
1.7
90
3.8
1.86
1.63
1.40
1.16
0.93
0.70
0.47
0.23
96
10.2
0.094
97
13.7
0.071
98
20.5
0.048
99
40
0.025
99.5
77
0.013
99.9
283
0.004
Table 3 Utilization of porosity in silicon

Application area
covered in
handbook
Light emission
Layer transfer for

semiconductor
epitaxy and solar
cells
Microphotonics
Attribute of high porosity

High visible
luminescence efficiency
Lowered mechanical
strength
Refractive index contrast
Desired
porosity
values
>80 %
(as etched)
>40 %
(oxidized)
>50 %
(mesopores)
>20 %
(macropores)
3090 %
(mesopores)
Study examples
(Canham et al. 1994;
Gelloz et al. 2005; Chen
et al. 2012)
(Yonehara et al. 1994;
Terheiden et al. 2011)
(Muller et al. 2000; Nava

et al. 2009)
(continued)
139
Table 3 (continued)
Application area
covered in
handbook
Thermal isolation
Active delivery
Tissue engineering
Attribute of high porosity

Very low thermal
transport
High payload of active

with matrix
biodegradability
Tissue ingrowth and
vascularization with
matrix biodegradability
Lithium battery
anodes
Matrix accommodation
of lithiation-induced
expansion
Thermoelectrics
Reduction of thermal
conductivity while
retaining electrical
conduction
Large surface area with
broad visible absorption
Biomolecule access to
high surface areas
Photocatalysis
Biosensing
Desired
porosity
values
>80 %
(as etched)
>60 %
(oxidized)
>60 %
(mesopores)
>90 %
(macropores
in
composites)
>30 %
(mesopores)
>60 %
(macropores)
>50 %
(mesoporous
wire array)
>30 %
(macropores)
>50 %
(mesopores)
>50 %
(mesopores)
Study examples
(Boarino et al. 1999;
Nassiopoulu and Kaltsas
2000)
(Salonen et al. 2005;
Canham 2007; Chiappini
et al. 2010; Canham 2014)
(Coffer et al. 2005; Sun
et al. 2007)
(Cho 2010; Wu
et al. 2012; Ge et al. 2012)
(Tang et al. 2010; de Boor

et al. 2012)
(Qu et al. 2010)

(Deloiuse and Miller
2004)
Applications of Porosity
Table 3 provides ten examples of applications where medium to high porosity is
targeted, and guidelines as to likely minimum values are needed. To achieve
ultrahigh porosities (>90 %) in silicon via wet etching techniques, great care has
to be taken during drying (see handbook chapter Drying Techniques Applied to
Porous Silicon).
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Canham LT (2014) Porous silicon for oral hygiene and cosmetics. In: Handbook of Porous Silicon.
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Ultrathin Porous Silicon Films

Brahim Bessas
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation of Ultrathin PS Films for XRR Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
XRR Analyses of Ultrathin PS Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
143
145
147
149
Abstract
Investigations of the structure and morphology of ultrathin PS films are reviewed,

of relevance to the technological control of miniaturized PS-based devices. Several
characterization tools with high reliability and precision are available; however,
many of them are destructive or could affect the ultrathin PS structure. Grazing
incidence X-ray reflectivity (XRR) is a powerful tool to probe the structural and
morphological characteristics of ultrathin PS films. Homogeneity, thickness, surface and interface roughness, porosity, and density of ultrathin PS films were
accurately determined using XRR. Nonetheless, prior to XRR measurements,
ultrathin PS films should be submitted to complementary nondestructive morphological and optical examinations (thickness, roughness, oxidation, etc.).
Introduction
Since the discovery of the room temperature photoluminescence (PL) in 1990
(Canham 1990), porous silicon (PS) has raised a strong interest owing to its potential
applications in electronic and optoelectronic devices (see handbook chapter
Porous Silicon Application Survey). The physical properties and performance
B. Bessas (*)
Research and Technology Centre of Energy, Borj-Cedria Technopark, Hammam-Lif, Tunisia
e-mail: Brahim.bessais@crten.rnrt.tn
DOI 10.1007/978-3-319-05744-6_14
143
B. Bessas
144
Table 1 Methods used for the characterization of thin PS films
Technique
Gravimetry
SEM
TEM
AFM
SE
XPS
XRR
UVvisNIR
Parameters
Average porosity,
thickness
Thickness, pore
morphology
Pore and crystallite
size distribution
Surface roughness
Optical index,
absorption, porosity
gradient
Chemical
composition
Porosity, density,
thickness, interface
roughness
Thickness,
absorption
coefficient
Comments
Lower accuracy with
thin layers
Destructive
Destructive
Accuracy in tapping
mode
Nondestructive
Destructive at high
X-ray dose, formation
of Si oxides
Quasi-nondestructive,
possible reduction of
the porosity
Homogeneity, optical
absorption, aging, etc.
References
(Pickering et al. 1984;
Brumhead et al. 1993)
(Riley and Gerhardt 2000;
Dittrich et al. 1995)
(Berbezier and Halimaoui
1993; Gardelis et al. 2008)
(von Behren et al. 1995;
Striemer et al. 2007)
(Pettersen et al. 1998;
Wongmanerod et al. 2001)
(Hardeman et al. 1985; Lees
et al. 2003)
(Sama et al. 2001; Ennejah
et al. 2011)
(Pickering et al. 1984; von
Behren et al. 1995; Butturi
et al. 1997)
of these devices often crucially depend on their interfacial structures. Thereby,

characterization of the structure of ultrathin films became increasingly important.
With the continuing minimization of thin film devices, characterization techniques
with high reliability and precision are required (Isao and Boquan 1999).
Nanoengineered PS films have many advantages in lab-on-chip devices, separations/filtrations, and nanoelectromechanical and nanofluidic systems applications
(Whitby and Quirke 2007; Tong et al. 2004; Hinds et al. 2004). The handbook
chapter Porous Silicon for Microdevices and Microsystems focuses on such
uses. For most applications, the main important performance goals of membranelike PS films are high permeation rate and good selectivity, which are achieved by
high porosity, narrow pore size distribution, and small thickness (Kavalenka
et al. 2012). The thickness of the films is a crucial parameter that influences most
of the film properties; hence, most of technological applications require thin films of
precise and definite thickness. In this context, the control of the structure and
morphology of ultrathin PS films (porosity, crystallite sizes, homogeneity, etc.) is
of prime importance to achieve powerful miniaturized PS-based devices. In Table 1,
we summarize the main methods used for the characterization of ultrathin PS films.
The technique of grazing incidence X-ray reflectivity represents a quasinondestructive method for the determination of thicknesses less than 250 nm (with
of one or several ultrathin PS films), electronic densities,
a precision of about 13 A
and surface and interfacial roughnesses and porosities (Chamard et al. 2001). The
value of the porosity of the PS film is very sensitive to the preparation conditions
together with the employed determination method. XRR measurements are highly
145
successful when the investigated films are deposited on polished substrates

(a condition also needed for SE investigations) (Tompkins and Irene 2005; Ennejah
et al. 2011). Furthermore, XRR is a well-adapted technique for measurements of thin
PS films (Eymer et al. 1999; Keissing 1931), if one can visualize Keissing interferential fringes (Parratt 1954). The latter could only be observed if the PS film has a flat
and homogeneous thickness not exceeding 250300 nm and a surface roughness less
than 3 nm, which approximately corresponds to 1 % of the maximum allowed
thickness (Isao and Boquan 1999; Ennejah et al. 2011; Eymer et al. 1999). One may
guess that these conditions are not so simple to obtain with ultrathin PS films; this is
why sets of PS samples should be prepared in order to optimize the electrochemical
etching (EE) conditions (Guilinger et al. 1995; Ennejah et al. 2011; Eymer et al. 1999).
These special precautions could be satisfied by varying the anodization time at a
rather low current density (Ennejah et al. 2011). Accordingly, XRR can be considered as a powerful characterization method. In order to take benefit of the effectiveness of XRR, one needs to estimate the chemical species, the homogeneity, the
surface roughness, and the thickness of the PS films by performing infrared
spectroscopy, SE, AFM, and UVvisNIR characterizations. Therefore, care
should be taken to protect the ultrathin PS films against oxidation prior to XRR
investigations. The aim of this review is to focus on the early-stage formation
kinetic of EE-based ultrathin PS films using the glazing angle XRR.
Preparation of Ultrathin PS Films for XRR Analysis

Homogeneous ultrathin PS films may be prepared by electrochemical etching
(EE) of p-type monocrystalline Si wafers, in HF-based solutions during short
periods and optimized current densities allowing to get various thicknesses
(Ennejah et al. 2011; Guilinger et al. 1995) and an average porosity of about
5075 %. For a general review of this fabrication technique, see handbook chapter
Porous Silicon Formation by Anodization. In order to observe Keissing fringes,
the ultrathin PS thickness should be lower than 250 nm and the surface roughness as
low as 3 nm (Ennejah et al. 2011). An example consists of lowering the surface
reflectivity of pyramidal-textured Si solar cells by forming ultrathin nanoporous
films on the pyramidal facets (Kim et al. 2009; Fig. 1a) using the EE technique.
New ways of structuring rather uniform ultrathin nano-PS films having various pore
shapes consist of HNO3/HF vapor etching of silicon (Fig. 1b) or crystallizing a thin
amorphous silicon film (Kavalenka et al. 2012; Striemer et al. 2007; Saadoun
et al. 2002; Fig. 1c).
For PS films prepared from the EE method, one should optimize anodization
conditions and check and/or estimate the silicon oxide content (SiOx) in the PS
films before performing XRR characterization. In fact, freshly prepared PS films are
generally covered with SiH bonds; nevertheless formation of SiO bonds always
takes place at the early stages of PS formation (Ennejah et al. 2011).
On the other hand, one should have a rough idea on the homogeneity of the PS
films by checking their diffuse and specular reflectivity (Fig. 2a, b).
B. Bessas
146
Fig. 1 (a) EE-based nanoporous pyramidal plane applied in pyramidal-textured Si solar cells
(Kim et al. 2009). (b) SEM cross-sectional view of a gold-coated thin PS film prepared from
HNO3/HF vapor etching (Ben Jaballah et al. 2005). (c) Cross-sectional SEM image of porous
nanocrystalline (pnc) Si membrane imaged on the surface of a metalized silicon wafer revealing
the cylindrical nature of the pores (Kavalenka et al. 2012)
b 60
Specular Reflectivity (%)
Diffuse Reflectivity (%)
a
10s
40s
50s
7
6
5
4
3
400
600
800
1000
Wavelength (nm)
1200
10s
40s
50s
120s
50
40
30
20
10
400
600
800
1000
Wavelength (nm)
1200
Fig. 2 Variation of (a) diffuse and (b) specular optical reflectivity of ultrathin PS films with
anodization time (Ennejah et al. 2011)
One may notice that for anodization time ranging from 10 to 50 s, the diffuse
reflectivity is lower than the specular one. As anodization time (i.e., thickness)
increases, the interference fringes (Fig. 2b) become closer to each other indicating
at a first sight the formation of relatively smooth and homogeneous PS films.
147
To evaluate the surface roughness, AFM microscopy characterizations were

made on the same samples (Ennejah et al. 2011). By examining the AFM surface
topography of ultrathin PS films in tapping mode, Ennajeh et al. (2011) found
that the PS surfaces have a root-mean-square (rms) roughness not exceeding
1.5 nm (Ennejah et al. 2011), whatever the anodization time may be, indicating
an etching time independence of the surface roughness. In fact, short anodization
times do not allow deep etching of early formed surface structures, suggesting
an almost invariable roughness. For current densities not exceeding 5 mA/cm2
and etching times ranging from 10 to 1,200 s, the rms does not exceed
1.5 nm (Ennejah et al. 2011). Spectroscopic ellipsometry (SE) measurements of
thickness, optical index, and optical absorption require modeling the PS films. In
that case, the Bruggeman (1935) model may be adopted, if one considers the PS
film formed of two phases (e.g., silicon and vacuum) having different volume
percentages. The PS thickness evaluated from SE varies from tens of nanometers
to a few hundreds of nanometers, with a quasi-constant porosity value (Ennejah
et al. 2011).
XRR Analyses of Ultrathin PS Films

For X-rays, the matter refraction index is slightly lower than unity. The reflection of
the X-rays occurring at the interface separating two media could be estimated from
the SnellDescartes law, which reveals total reflection below a critical angle
depending on the electronic density of the material (Abramof et al. 2006). This
critical angle has a very small value in the grazing X-ray technique (Abramof
et al. 2006). The analysis of the reflected X-ray intensity and shape in the total
reflection region (i.e., angles smaller than the critical one) (Fig. 3a) provides
information on the surface structure from ten to several hundred angstroms deep.
One may point out two critical angles cPS and cSi related to reflection at the
interfaces air/PS and PS/silicon, respectively (Ennejah et al. 2011; Fewster 1996).
One may also notice that cPS is smaller than cSi due to lower density of the PS
films.
In the total reflection zone, the reflected X-ray intensity is sensitive to electron
density variation of the characterized material and is independent of the amorphous
or crystalline structure or the crystallites orientation at the surface (Chamard
et al. 2002). If the surface of the sample presents two or more homogeneous
media, the reflection curve shows peculiarities associated to the electronic property
of each media and to the different interface behaviors. For angles higher than the
critical one, the X-rays are absorbed by the material and the reflected intensity
drops abruptly. In the case of stratified homogeneous media having smooth boundary interfaces, one may observe reflected rays presenting Keissing fringes (Fig. 2b),
which give information about film thickness and density variation between media
and interface states. In the conditions of Ennejah et al. (2011), the Keissing fringes
vanish at anodization time exceeding 50 s (Fig. 3b). The porosity of the PS films can
be estimated from the relation (Buttard et al. 1998):
B. Bessas
148
107
cSi
cSP
106
10 s
40 s
100 s
105
0.1
0.2
0.3
0.4
0.5
Grazing incidence angle 2 ()
0.6
X-ray reflected Intensity (counts/s)
X-Ray reflected intensity (counts/s)
106
10
20
30
40
50
100
105
s
s
s
s
s
s
104
103
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
Grazing incidence angle 2 ()
Fig. 3 (a) XRR measurements on thin PS films etched for 10, 40, and 100 s in the total reflection
region, (b) XRR measurements of thin PS films in the X-ray penetration region (Ennejah
et al. 2011)
P%
h

i
1 cSP =cSi 2 100
Figure 4 shows the variation of porosity, thickness, and roughness, determined

from XRR patterns versus anodization time. In fact, pore initiation proceeds
spontaneously on smooth silicon substrate yielding 1010/cm2 tiny etch pits after
only a few seconds of anodization; many of these pits merge to form approximately
106/cm2 to 108/cm2 stable pores, which then continue to grow into the substrate
(Buttard et al. 1998; Zhang 1991), leading to a final stable porosity. The porosity of
ultrathin PS films, determined from Keissing fringes, grows almost linearly for
short anodization time (Fig. 4a); then it tends to a stable porosity value (Ennejah
et al. 2011). The thickness of EE-prepared ultrathin PS films (Fig. 4b), determined
from XRR, exhibits a linear growth for short and long anodization times; the
estimated values (Fig. 4b) are almost similar to that determined from SE or
electronic microscopy (Guilinger et al. 1995) and even gravimetry for rather thick
PS films (Guilinger et al. 1995). Riley and Gerhardt (2000) observed the same linear
thickness behavior for thin p-type PS (Fig. 4b), although a nonlinear growth was
depicted on n+-type PS films at short anodization times while using gravimetric
analysis (Brumhead et al. 1993). It seems to be obvious that in case of homogeneous
EE, the porosity of p-type PS films remains stable and etching is time independent,
while the thickness grows linearly within etching time (Bessas et al. 2000).
From XRR, one may evaluate the PS surface roughness and the PS/Si interface
roughness (Fig. 4c). The PS surface roughness fluctuates in the range of 0.41 nm
and is always less than unity; it tends to a constant value (equivalent to that
determined from AFM for a virgin silicon wafer) with increasing anodization
time (Guilinger et al. 1995; Ennejah et al. 2011), results in agreement with that
obtained from AFM and TEM analysis (Guilinger et al. 1995). The interface
roughness could be determined in the XRR specular geometry, where only the
direction perpendicular to the sample surface is investigated, allowing to probe the
interface state evolution associated to progressive pore nucleation.
149
b 200
Thickness (nm)
Porosity (%)
70
60
50
40
160
120
80
40
20
40
60
80
Anodization time (s)
Interface roughness (nm)
100
10
20
30
40
50
7
6
5
4
roughness at SP/Si interface
roughness at PS surface
3
1.0
0.5
10
20
30
40
50
Fig. 4 (a) Porosity, (b) thickness, and (c) interface roughness versus anodization time (Ennejah
et al. 2011)
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Berbezier I, Halimaoui A (1993) A microstructural study of porous silicon. J Appl Phys 74:5421
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Brumhead D, Canham LT, Seekings DM, Tufton PJ (1993) Gravimetric analysis of pore nucleation and propagation in anodised silicon. Electrochim Acta 38:191
Buttard D, Dolino G, Bellet D, Baumbach T, Rieutord F (1998) X-ray reflectivity investigation of
thin p-type porous silicon layers. Sol State Commun 109:1
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Butturi MA, Carotta MC, Martinellia G, Passaria L, Youssef GM, Chiorino A, Ghiotti G (1997)
Effects of ageing on porous silicon photoluminescence: correlation with FTIR and UV-vis
spectra. Solid State Commun 101:11
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Porous Silicon Multilayers and

Superlattices
Vivechana Agarwal
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Type of Multilayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Patterning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Functionalization and Stabilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Major Challenges/Problems in Fabricating Thick Multilayered Structures . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
153
154
157
157
158
159
160
Abstract
Electrochemical etching of silicon can generate porous silicon where porosity is

modulated with depth. The overall fabrication technique, experimental tips for
improving uniformity, typical porosity profiles, and methods of patterning and
stabilization are reviewed. Due to its ease of fabrication, such multilayers have
been extensively fabricated and applied in different fields, such as photonics,
phononics, sensing etc.
Introduction
After the pioneering work of G. Vincent (1994) in 1994, followed by M.G. Berger
et al. (1994) demonstrating the possible fabrication of porous silicon
(PS) superlattices, in the last few years, porous silicon multilayers have found
broad range of applications. For example, the formation of tunable
one-dimensional photonic devices such as Bragg mirrors, rugate filters,
V. Agarwal (*)
Centro de Investigacion en Ingenieria y Ciencias Aplicadads, Universidad Autonoma
del Estado de Morelos, Col. Chamilpa, Cuernavaca, Mexico
e-mail: vagarwal@uaem.mx
DOI 10.1007/978-3-319-05744-6_15
153
154
V. Agarwal
microcavities, and waveguides (see handbook chapter Porous Silicon Optical

Waveguides) and their use as optical bio- and chemical sensors (handbook
chapter Porous Silicon Gas Sensing), optoelectronics (handbook chapter
Electroluminescence of Porous Silicon), solar cells (handbook chapter
Porous Silicon and Solar Cells), etc. As an excellent example, in 2001,
G. Lammel (Lammel et al. 2001) demonstrated a PS multilayer-based MEMS
infrared gas spectrometer. In general, the main advantage of using porous silicon
for making multilayers is the cost-effective, easy, and fast fabrication of any
combination of layers with the required optical thicknesses to obtain the desired
optical properties. In the next sections the formation of the multilayered structure
and its classification based on the type of silicon wafer and pore morphology is
given. Additionally, patterning and stabilization of porous silicon multilayers is
followed by a brief overview of the major considerations while making thick
multilayers.
Fabrication
A number of methods have been used for fabricating PS multilayers (ML):
(i) constant current density on a periodically doped Si wafer (Frohnhoff and Berger
1994), (ii) variation of illumination density on uniformly doped n-type Si wafer
(Frohnhoff et al. 1995), (iii) variation of current density with a uniformly doped
silicon wafer (Vincent 1994; Berger et al. 1997) (some examples given in Table 1),
and (iv) glancing angle deposition technique (Kaminska et al. 2003; Robbie
et al. 2004). Variation of current density in an electrochemical etching an uniformly
doped silicon wafer is the most extensively used method, based on the fact that the
etching process is self-limiting (Smith and Collins 1992) and mainly occurs at the
pore tips, i.e., at the interface between the electrolyte and the silicon substrate,
without affecting the already formed porous layer. Hence, the PS multilayer is
formed by controlling the current density along the depth of the Si substrate (see
Fig. 1). In other words, for the formation of the first layer, a constant current density
provides the holes, and the dissolution reaction begins from the defects on the
surface of the Si wafer. The pores are formed and their walls are eroded until they
are emptied of holes. This passivates the already formed PS from further attack, and
the reaction proceeds at the tip of the pore, maintaining the entire etched Si skeleton.
The formation of the subsequent porous layers, by changing the current density,
is due to the overlap of the depletion regions formed on the pore walls in a Schottky
diode picture of the Si-electrolyte interface. Lehmann and Gosele (1991) proposed
the quantum model, in which the decrease of the carrier concentration in the porous
layer is related to an increased bandgap, which acts as a barrier for the hole
diffusion from the bulk Si to the pore walls.
On the other hand, for obtaining the multilayers of required optical properties,
the exact variation of etching rate and porosity (or refractive indices) as a
function of current density is needed (an example adapted from the reference
Porous Silicon Multilayers and Superlattices
155
Table 1 Some examples of different types of PS multilayer structures formed with the uniformly
doped silicon substrate (taking micro <10 nm, meso 1050 nm, and macro >50 nm)
Type of
structures
Microporous
Mesoporous
Meso- and
macroporous
Meso +
macro
Macroporous
Micro-,
meso-,
macroporous
Some fabrication
parameters
p or p- type, approx.
porosity range
5575 %, electrolyte:
HF + ethanol
p + or p++ with
resistivity <0.01
-cm; electrolyte,
HF + ethanol; porosity
range, 2585 %;
high-quality factor
microcavities
p++; high range of
porosities; electrolyte:
HF + ethanol
n or n++, 1050 nm
for mesoporous and
90150 nm for
macroporous layer
n or n++, electrolyte:
HF + CrO3, pore size
50200 nm;
low-quality factor
microcavities
0.010.02 -cm,
10300 mA/cm2,
3082 % porosity
Types of structures/
possible applications
Mirrors, microcavity,
rugate filter; used as
optical gas sensor due
to large surface area
Bragg,
omnidirectional, and
laser mirrors,
microcavities, rugate
filters, waveguides,
sensors, antireflection
coatings
Mirrors, filters, and
microcavities;
photonic applications
and macromolecule
sensing
Mirrors,
microcavities, sensing
application
Reference
Escorcia-Garcia
et al. (2009), Salem
et al. (2008)
Berger et al. (1997),
Ouyang et al. (2006),
Chan and Fauchet
(2001), Agarwal and
del Rio (2003), Kilian
et al. (2007b), Weiss
et al. (2005)
Estephan et al.
(2011), Orosco
et al. (2009), Becerra
and Agarwal (2009)
Ouyang et al.
(2005a), Muzina
et al. (2005)
Macromolecule
sensing, 2D and 3D
photonic crystals
Ouyang et al.
(2005b), Ghulinyan
et al. (2008), Murzina
et al. (2007)
Multilayers with vast

porosity range;
possible sensing and
photonic applications
Ge et al. (2013)
(Frohnhoff et al. 1995) is provided as Fig. 2). Although multilayer structures may
require thin layers, the error in porosity measurements for thin layers <200 nm
makes it unreliable. Hence, the thickness and refractive index (or approximate
porosity) of relatively thick monolayers are generally extracted from scanning
electron microscope and normal reflectance spectra/spectroscopic ellipsometry,
respectively. Apart from that several other remarks can be made:
1. High-resistivity (p-type) Si wafers lead to ML structure with smaller pore
dimensions and relatively less variation of porosity (Mulloni et al. 1999)
between 55 % and 75 % as compared to the highly doped (>0.01 -cm) silicon
wafer resulting in the formation of larger pore dimension (relatively big meso- or
macroporous as per IUPAC nomenclature) structure with the porosities ranging
between 35 % and 85 %, i.e., an increase in the doping concentration increases
the effective porosity range (Frohnhoff et al. 1995; Pavesi 1997).
156
V. Agarwal
Fig. 1 Schematic sketch on the formation of porous silicon multilayer structures. Upper part: The
variation of the current density as a function of the depth. Switching between two different current
densities, two different porosities are formed. Lower part: Typical PS multilayer structure
resulting from such current variations. Black and white regions represent high and low porosity
layers
a 3.5
p-PS
n(12000cm1)
3.0
p+-PS
2.5
2.0
1.5
b 1.0
Fig. 2 Dependence of (a)

refractive index and (b)
etching rate as a function of
current density for two
different resistivities of
p-type silicon wafer (Adapted
from Ref. Berger et al. 1997)
ETCH RATE (nm/s)
300
250
200
150
100
50
0
100
200
300
400
CURRENT DENSITY (mA/cm2)
500
157
2. Large variations in refractive indices are possible by varying the current density
or the concentration of electrolyte. An optimum level of HF concentration is
required to obtain the maximum range of the possible refractive index contrast, i.
e., maximum variation in porosity, which in turn is one of the factors responsible
for the fabrication of high-quality multilayers (Pavesi 1997).
3. Stress induced by high refractive index contrast has been reported to cause the
rupturing of the structure (Pavesi and Turan 2010). The stresses are often
capillary stresses caused by the evaporation of the electrolyte/rinsing solution.
Hence, the quality of the multilayer can be improved by improving drying
techniques (see handbook chapter Drying Techniques Applied to Porous
Silicon).
4. Etching rate is almost a linear function of current density for p-type substrate
(Frohnhoff et al. 1995; Mulloni et al. 1999) but nonlinear for n-type (Halimaoui
1997).
5. As etching rate depends on HF concentration, for designing an optical device
with thin porous silicon layers, low concentrations of HF are recommended due
to low etching rate.
6. Depending on the required application, the proper choice of the substrate
(type and resistivity) and the fabrication conditions can result in spongy
micro-, meso-, or macroporous (taking micro <10 nm, meso 1050 nm, and
macro >50 nm) multilayers (details given in the next section). Note that here the
term micropore differs from the IUPAC definition described and utilized in the
handbook chapter Microporous Silicon.
Type of Multilayers
Table 1 lists some examples of the different types of porous multilayers classified
on the basis of the pore dimensions for a given type (p- or n-) of silicon wafer. Some
typical images are shown in Fig. 3.
Patterning
In 1999 D. Hunkel et al. (Hunkel et al. 1999) proposed a method to produce MLs
with a lateral gradient by applying a potential parallel to the surface of the wafer.
Mark B.H. Breese et al. (Bresse and Mangaiyarkarasi 2007; Mangaiyarkarasi
et al. 2008) achieved 300 nm wide Bragg reflectors by irradiation of highly doped
p-type silicon with a focused beam of high-energy ions in a channeled alignment.
Some groups such as S. Um et al. (2013) have demonstrated the use of some similar
multilayers with lateral gradient (using conventional electrochemical method) as
chemical sensors.
158
V. Agarwal
Fig. 3 Cross-sectional SEM images of some typical multilayer structures: (a) p++ big
mesoporous, (b) n++ type macroporous (adapted from Ref. Ouyang et al. 2005b) thick
mesoporous (p++ type) (adapted from Ref. Lo and Murphy 2009), (d) p-type microporous
(pores <10 nm) microcavity (adapted from Ref. Escorcia-Garcia et al. 2009), (e) combination
of n-type meso- and macroporous layers (adapted from Ref. Ouyang et al. 2005a), (f) combination
of n-type macro-meso and microporous layers (adapted from Ref. Ge et al. 2013)
Functionalization and Stabilization

Due to the instability of porous silicon under atmospheric conditions, several
studies have been conducted to stabilize (Frohnhoff and Berger 1994; Canham
et al. 2000; Ghulinyan et al. 2008; Jalkanen et al. 2009) and derivatize porous
silicon multilayers. One of the common methods is to intentionally oxidize the
multilayers (Frohnhoff et al. 1995). However, the porous SiO2 structure remains
prone to degradation in aqueous media despite its functionalization with silanes as
all layers containing silicon-oxygen bonds are susceptible to hydrolysis at high pH
(higher than pH7) in general. A more stable surface functionalization was
achieved by the formation of silicon carbon bonds (Jalkanen et al. 2009; Kilian
et al. 2007a). Based on the low electronegativity of carbon, the nucleophilic attack
of silicon carbon bonds by water or hydroxide is hampered. Silicon-carbon bonds
are formed by hydrosilylation, chemical or electrochemical grafting techniques as
well as carbonization reactions. Not withstanding the obvious advantages of
porous silicon stabilized by silicon-carbon bonds, its application was neglected
for several years due to its tedious fabrication in oxygen excluding conditions
(inert atmosphere). (See handbook chapter Silicon-Carbon Bond Formation on
Porous Silicon.)
159
Major Challenges/Problems in Fabricating Thick

Multilayered Structures
Interfaces
The interface between the layers determines the quality of the porous silicon
multilayered structures. Detailed characterization of the interface quality of the
thin multilayered structures has been carried out by transmission electron microscopy (TEM) (Frohnhoff et al. 1995; Martn-Palma et al. 1998), X-ray diffraction
(Buttard et al. 1996), and Rutherford backscattering spectroscopy (Torres-Costa
et al. 2004). In contrast to the ML structures formed on p-type silicon wafer, the
interfaces between the layers formed with p++-type substrates have been found to
be sharp at the nanometric scale. The quality of the interface is found to deteriorate with an increase in the resistivity (Escorcia-Garcia et al. 2009). Apart from
the regeneration time of few seconds after each layer (Billat et al. 1997), a
decrease in the interface roughness is also reported with the application of pulsed
anodic etching (Escorcia-Garcia et al. 2009; James et al. 2009). Change in
viscosity (by low temperature fabrication or adding glycerol in the electrolyte)
and ultrasound has also been reported to flatten the interface homogeneity and
improve the optical quality of the multilayered photonic structure (Servidori
et al. 2001; Reece et al. 2002; Liu et al. 2003). As there is no need for external
lighting when etching p-type Si and the fairly low PS-cSi substrate interface
roughness obtained, most PSM structures are etched in p-type samples.
With lower resistivity samples, the interface roughness (microscopic) tends to
decrease, although macroscopic roughness (due to striations) tends to increase
(Setzu et al. 2000).
Depth Homogeneity
For thick multilayer structures, the variation of the HF concentration can cause a
porosity gradient along the depth. This effect is more prominent in n-type due to the
added effect of the decrease in the illumination intensity. The variation of the HF
concentration has been attributed to the problems due to the diffusion of the
electrolyte which has been explained with the help of Ficks law (Thonissen and
Berger 1997), i.e., the dissolution of silicon atoms is restricted by the mass transport
of the reactants through the pores and carrier transport in PSi layer : FHF DHF
(ctopcbottom/d), where FHF is the flux of the HF molecules, DHF the diffusion
coefficient of the molecules into the pores, and ctop and cbottom are the concentrations at the top and the bottom of the PSi layer of thickness d. Hence, several
methods (Escorcia-Garcia et al. 2009; Billat et al. 1997; James et al. 2009) have
been adopted to enhance the depth homogeneity. Depth resolved microspectroscopy of porous silicon multilayers has been studied by Manotas
et al. (Manotas et al. 1999) to obtain crystallite size and stress as a function of
depth. On the other hand, optical path gradients related to technical limitations of
the fabrication method are present when a very large multilayer structure is
160
V. Agarwal
considered (Ghulinyan et al. 2005). In spite of the above mentioned problems,

the formation of thick multilayered structures (Lo and Murphy 2009; Svyakhovskiy
et al. 2012; David Ariza-Flores et al. 2012) has been reported.
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Porous Silicon Membranes

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fabrication Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrochemical Etching: Anodization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Micromachining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Deposition/Annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
163
164
165
165
166
166
168
168
Abstract
Porosified silicon membranes of defined thicknesses were first studied in the 1990s
and have now been realized by electrochemical anodization, micromachining
techniques, and the annealing of ultrathin deposited films. The three fabrication
routes produce very different morphologies and levels of porosity. A variety of
applications have been explored for both macroporous and mesoporous membranes and these are also surveyed. Wholly microporous membranes in silicon,
where all pores have diameters less than 2 nm, have not been achieved to date.
Introduction
Membranes today are already widely used to extract potable water from the sea, to
concentrate or purify food and drug ingredients, and to separate gases (Strathman
2011). However, membrane engineering is possibly still in its infancy with regard to
certain materials like silicon. Solid silicon membranes are commercially available at
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_16
163
164
L. Canham
Fig. 1 Porous silicon membrane examples: (a) ultrathin membrane (Fang et al. 2010), (b)
membrane in microfluidic channel (Tjerkstra et al. 2000), (c) suspended micromachined membrane (Lammel and Renaud 2000), (d) membrane on silica support (Ghulinyan et al. 2003)
micron scale thickness and are found in a number of MEMS applications like
microvalves, micropumps, accelerometers, and microphones (Lindroos et al. 2010).
Solid silicon membranes of less than ten to several hundred nanometer thickness
(nanomembranes) are being researched for uses such as flexible electronics
(Rogers et al. 2011). Porosified silicon membranes first started to appear in the 1990s
(Kendall 1990; Kittisland et al. 1990; Drory et al. 1990; Searson et al. 1991) and have
subsequently received research study for varied reasons. This chapter summarizes the
most popular fabrication routes, some specific issues with characterizing them, and the
varied potential uses under investigation. Figure 1 illustrates some examples of
the types of membranes realized: free-standing structures, membranes within silicon
chips, and membranes transferred to and supported on substrates of another material.
Fabrication Techniques
There are now three top-down techniques developed to realize porous silicon
membranes from solid silicon: electrochemical etching (anodization),
micromachining, and thin film deposition/annealing. These techniques create
165
different pore morphologies and are suited to different membrane thicknesses and
porosity ranges. In this regard they are quite complementary.
Electrochemical Etching: Anodization

Porous silicon membranes have been realized electrochemically by four routes
(Agarwal et al. 2003; Angelucci et al. 2000; Bobo et al. 2012; Chao et al. 2000;
Chen et al. 2008; Chu et al. 2006; Cisneros et al. 2009; Cruz et al. 2005; Dubosc
et al. 2012; Fissell et al. 2009; Ghulinyan et al. 2003; Hajj-Hassan et al. 2011;
Hamzah et al. 2013; Hedrich et al. 2000; Kumar et al. 2014; Letant et al. 2003;
Mathwig et al. 2011; Matthias and Muller 2003; Michelotti et al. 2010; Muller et al.
2000; Ohkura et al. 2013; Pagonis et al. 2006; Pichonat et al. 2004; Saharil et al.
2013; Tantawi et al. 2013):
Anodization right through entire silicon wafers of standard thickness
Anodization right through thin solid silicon membranes
Anodization of part of the thickness of a wafer and then lift off by raising the
current density sharply for a few seconds
Pre-thinning of selected areas of wafers with subsequent anodization
Each approach has its merits and limitations. With very thick wafer anodization,
there can be a substantial porosity gradient with depth across the membrane; very
thin solid membranes while commercially available can be expensive at large size
and difficult to handle; the lift off technique introduces some asymmetry into the
membrane since a high current density pulse is applied to one side.
Anodized membrane thicknesses can cover a wide range (e.g., 1500 microns),
and porosities typically are 3080 % for mesoporous structures.
Micromachining
This approach, developed by Ferrari, Desai, Hansford, and coworkers, creates
porosity with highly defined mesopore diameters at low concentrations. The slitlike pores result from removal of a sacrificial silicon oxide layer of highly controlled thickness (tunable in the mesopore to macropore range). Mesopore diameter
is very accurately controlled (<5 % variation). The resulting membranes have
thicknesses in the range 0.55 micron, but the overall mesoporosity is very low
(~1 %). This provides excellent mechanical stability but at the cost of increased
likelihood of pore blockage in complex biological media. Such structures are also
expected to have similar biochemical properties to bulk crystalline silicon and
thus not be medically biodegradable like highly porous silicon (see handbook
chapter Biodegradability of Porous Silicon). More details on the morphology,
properties, and performance of such membranes are elsewhere in the handbook, in
the chapter Porous Silicon in Immunoisolation and Bio-filtration.
166
L. Canham
Fig. 2 Fabrication of mesoporous silicon membranes by thin layer deposition and thermal
treatment (Fang et al. 2010)
Deposition/Annealing
This approach, developed by Fauchet, Striemer, and coworkers, creates
mesoporosity via thermal anneal treatments of ultrathin (1050 nm) silicon films
(Fang et al. 2010). A typical process flow is shown schematically in Fig. 2.
For silicon films sandwiched between silica layers, porosities up to 15 % were
achieved. The potential in vitro and in vivo biomedical uses of such membranes are
reviewed in the handbook chapter Porous Silicon in Immunoisolation and
Bio-filtration. Very recently, higher levels of porosity have been achieved using
silicon nitride rather than oxide as the barrier layers (Qi et al. 2014).
Characterization
By removing bulk silicon, porous silicon can be studied in isolation, and in this
regard membranes are a valuable characterization tool for studying the effects of
porosity. Most of the early research (Kanemitsu et al. 1993; Vincent et al. 1993;
Klma et al. 1993; Ookubo et al. 1993; Xie et al. 1994; Feng et al. 1994; Hilnomaz
et al. 1994; Maly et al. 1994; Vadjikar et al. 1994; Sedlaclk et al. 1995;
Chan et al. 1995; Taliercio et al. 1995; Bustarret et al. 1995; Tanino et al. 1996;
Guha et al. 1997; OHalloran et al. 1998; Xu et al. 1999, 2000; Koyama and
Fauchet 2000) was concerned with elucidating the optoelectronic properties.
Mesoporous silicon membranes are however both mechanically fragile and have
167
Table 1 Potential uses of porous silicon membranes

Targeted
application
Gas sensors
Porosity type
Mesoporous
Fabrication
technique
Anodization
Membrane
thickness (microns)
70
Mesoporous
Anodization
Mesoporous
Micromachining
Macroporous
Anodization
50
Macroporous
Anodization
520
Macroporous
Mesoporous
Anodization
Anodization
350
40
Mesoporous
Anodization
1033
Macroporous
Anodization
Mesoporous
Anodization
70
Mesoporous
0.015
Mesoporous
Deposition/
annealing
Anodization
26
Optical
sensors
Drug delivery
Mesoporous
Anodization
30,64
Macroporous
Anodization
50
Photonic
biosensing
Mesoporous
Anodization
1.5
Humidity
sensors
Medical
implants
UV optical
filter
Microfluidic
reservoir
Micropump
Fuel cells
Chemical
sensors
Waveguide
sensors
Biofiltration
In vitro cell
culture
Energetics
Reference
example
Taliercio
et al. 1995
OHalloran
et al. 1998
Desai
et al. 2000
Avutsky
et al. 2003
Zheng
et al. 2005
Yao et al. 2006
Pichonat
et al. 2006
Garel
et al. 2007
Rong
et al. 2008
Velleman
et al. 2010
Agrawal
et al. 2010
Plummer
et al. 2011
Alvarez
et al. 2011
Chau and
Melvin 2012
Bocking
et al. 2012
low thermal conductivity and capacity. Thin porous silicon layers on wafers are
intimately attached to a heat sink; the corresponding membranes are not.
Care therefore needs to be taken when optically exciting membranes to avoid
thermal damage and to ensure that observed properties are not influenced by
increases in temperature (see handbook chapter Characterization Challenges
with Porous Silicon). Electrochemically etched membranes are also likely to have
spatial asymmetry in their structural (Milita et al. 2001; Pusep et al. 2009) and
hence optical (Pap et al. 2006; Alvarez et al. 2011; Palavicini et al. 2013),
thermal (Amato et al. 2000), mechanical (Drory et al. 1990), and electrical
(Dariani et al. 2010) properties, perpendicular and parallel to the plane of the
membrane.
168
L. Canham
Applications
Table 1 collates the varied potential applications that have been explored for porous
silicon membranes, both mesoporous and macroporous. Membrane thicknesses
vary from submicron to tens of microns to the full thicknesses of wafers (hundreds
of microns). Most studies have utilized anodization to realize the porosity. Notable
exceptions highlighted in Table 1 are the micromachining and deposition/anneal
techniques already mentioned.
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MACE Silicon Nanostructures

Ciro Chiappini
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Morphology of Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of Oxidizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of Substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of Other Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Etch Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Properties of MACE Porous Nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
172
173
174
176
179
180
181
182
184
Abstract
Metal-assisted chemical etching (MACE) of silicon is receiving much interest as

a controllable method of generating silicon nanostructures of varied forms,
including porous silicon. The various morphologies, etch chemistry variables
(e.g., metal catalysts, substrate type, electrolyte temperature), and potential
applications of the resulting nanostructures are reviewed.
Kim et al. (2011), Geyer et al. (2012), Chiappini et al. (2010), Chartier et al. (2008), Li and Bohn
(2000), Dudley and Kolasinski (2009), Peng et al. (2003, 2006), Yae et al. (2007) of particular
interest.
C. Chiappini (*)
Department of Materials, Imperial College London, Faculty of Engineering, London, UK
e-mail: ciro.chiappini@gmail.com
DOI 10.1007/978-3-319-05744-6_17
171
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C. Chiappini
Fig. 1 Overview of nanostructures synthesized by metal-assisted chemical etch. (a) Nanopores

with solid sidewalls (sNPs), from Lee et al. (2008); (b) nanopores with mesoporous sidewalls
(mNPs), from Tsujino et al. (2005); (c) solid nanowires (sNWs), from Chiappini et al. (2010); (d)
mesoporous nanowires (mNWs), from Chiappini et al. (2010); (e) porous nanowires over porous
silicon, from Chiappini et al. (2010); (f) porous silicon (pSi), from Chiappini et al. (2010)
Introduction
The formation of porous silicon by metal-assisted chemical etch (MACE) was discovered in 1997 when patterned aluminum on silicon rapidly induced selective formation
of porous silicon layers in stain-etch conditions (Dimova-Malinovska et al. 1997).
In a typical MACE process, a patterned metal deposited over a silicon substrate
catalyzes etch of silicon in its vicinities, when placed in an oxidizing solution of
hydrofluoric acid (HF). By anisotropically etching silicon in the vicinity of a metal
mask, MACE generates silicon structures dictated by metal patterning and etching
conditions: pores, nanowires, and porous silicon layers (Fig. 1). MACE combined
with lithographic patterning generates high aspect ratio silicon nanostructures of
tailored geometry (Kim et al. 2011a; Geyer et al. 2012; Chiappini et al. 2010; Wang
et al. 2012; Mikhael et al. 2011).
173
Under appropriate MACE conditions, porous silicon forms in the un-etched

silicon around the metal (Geyer et al. 2012; Chiappini et al. 2010; Tsujino and
Matsumura 2005; Chartier et al. 2008). Combining anisotropic etching and
porosification, MACE is a simple strategy to form high aspect ratio porous silicon
nanostructures. MACE is a top-down nanofabrication technique that allows finer
control than competing bottom-up strategies for growth of silicon nanowires.
MACE provides highly crystalline nanowires and grants control over their doping,
surface roughness, and porosity. MACE is a low-cost strategy, which works at
ambient temperature and pressure, to reproducibly generate wafer-scale porous
silicon as well as ordered arrays of oriented nanowires, nanorods, and vias
(see complementary handbook chapters Porous Silicon Formation by Metal
Nanoparticle-Assisted Etching, Porous Silicon Formation by Galvanic
Etching, and Porous Silicon Formation by Stain Etching).
There are good arguments to support that MACE and stain etching are two
tightly correlated manifestations of the same process. Both techniques rely on the
underlying principle that hole injection from an oxidizer in solution induces silicon
oxidation (Chartier et al. 2008; Kolasinski 2005; Li and Bohn 2000). The most
recent advances in stain etching show that oxidants containing metal ions induce a
faster and more reproducible etch that generates thick porous silicon films of higher
quality than the traditional etchants (Nahidi and Kolasinski 2006; Dudley and
Kolasinski 2009; Loni et al. 2011). On the other hand, MACE can form porous
and solid silicon nanowires in solutions containing only HF and metal ion oxidizing
salts without any pre-deposition of metal (Hochbaum et al. 2009; Peng et al. 2003).
This chapter aims to condense the current knowledge of MACE into a set of
empirical guidelines for the rational design of MACE nanostructures. The effects of
known MACE parameters on the resulting structure will be presented. Finally, a
summary of the known properties of MACE nanostructures will be outlined.
Morphology of Nanostructures
Metal-assisted chemical etch is employed to form a wide range of silicon structures,
including nanopores, i.e., pores of submicron size, with either solid sidewalls
(Dimova-Malinovska et al. 1997; Tsujino and Matsumura 2005, 2007; Chartier
et al. 2008) (sNP, Fig. 1a) or mesoporous sidewalls (Dimova-Malinovska
et al. 1997; Tsujino and Matsumura 2005, 2007; Chartier et al. 2008) (mNPs,
Fig. 1b), porous silicon layers (Dimova-Malinovska et al. 1997; Kim et al. 2011a;
Chiappini et al. 2010; Mikhael et al. 2011; Chartier et al. 2008; Voigt et al. 2011)
(pSi, Fig. 1c), solid nanowires (Chiappini et al. 2010; Chartier et al. 2008; Peng
et al. 2003; Huang et al. 2010a) (sNWs, Fig. 1d), mesoporous nanowires (Chiappini
et al. 2010; Chartier et al. 2008; Hochbaum et al. 2009; Chen et al. 2010a) (mNWs,
Fig. 1e), porous nanowires over porous silicon (Fig. 1f), and polished surfaces
(Chiappini et al. 2010; Chartier et al. 2008; Nahidi and Kolasinski 2006; Dudley
and Kolasinski 2009) (PS). The following sections will explore the effect of some
crucial MACE parameters on the resulting nanostructures.
174
C. Chiappini
Table 1 Common oxidizers for MACE, their associated cathode reaction, and the MACE
structures they have been employed to form
Oxidizer
H2O2
Cathode reaction
H2O2 + 2H+ ! 2H2O + 2h+
Structures
sNP, mNP,
pSi, sNW,
mNW, PS
2H+ ! Hg2 + 2h+
HNO3
HNO3 + 3H+ ! NO + 2H2O + 3h+
sNP, pSi
Metal
salt
(Mn +)
Mm + ! M(m n) + + nh+
Metal ions can be neutralized (M0)
and precipitated
pSi, sNW,
mNW
References
Tsujino and Matsumura
(2007), Megouda
et al. (2009), Zhang
et al. (2009)
Chartier et al. (2008), Li and
Bohn (2000), Peng
et al. (2006a)
Dimova-Malinovska
et al. (1997)
Nahidi and Kolasinski
(2006), Dudley and
Kolasinski (2009)
Effect of Oxidizers
The solution-metal-silicon system constitutes a microscopic electrochemical cell
that induces anodic silicon etch. For the most commonly employed oxidants H2O2
and HNO3, the proposed cathodic reactions provide free positive carriers to be
transferred to the silicon (Table 1).
In the anode reaction, the silicon consumes the positive carriers and is solubilized through oxidation. Several models for the anodic reactions have been proposed and are outlined in the handbook chapter Porous Silicon Formation by
Metal Nanoparticle-Assisted Etching.
A wide variety of metal salts can induce silicon porosification without the
addition of any other oxidizer, as their electrochemical potential is sufficiently
high to directly inject holes in the valence band of silicon. Those that have been
employed for MACE are listed in the following table alongside the nanostructures
they have been shown to produce (Table 2).
All oxidizers have a standard energy sufficient to inject holes into the valence
silicon, and the metal deposited on the silicon surface is not necessary for the
dissolution to occur. The metal acts as a catalyst facilitating charge transfer between
the silicon and the oxidizers in solution. As a consequence, etching occurs preferentially in the vicinity of the metal due to the higher concentration of free holes.
Hydrogen Peroxide
Hydrogen peroxide is by far the most commonly employed oxidizer in MACE.
Chartier et al. assume that the relative concentration of HF and H2O2 in a MACE
etch solution plays a similar role to Jps in anodic etch (Chartier et al. 2008). To this
extent, they define a useful parameter to correlate the relative concentrations of HF
and H2O2 in solution with the resulting silicon structures:
HF
HF H 2 O2
175
Table 2 Metal-based oxidizers employed in MACE and resulting MACE structures

Oxidizer
AgNO3
AgO
HAuCl4
KAuCl4
H2PtCl6
K2PtCl6
PdCl2
Na2S2O8
K2Cr2O7
KMnO4
NaMnO4
Fe(NO3)3
FeCl3
V2O5
CeF4
M(NO3)2
M Ni, Mn, Cu, Fe, Co, Cr, Mg
MACE
structures
pSi, sNW,
mNW
pSi, sNW,
mNW
NW, sNP,
mNP
References
Hochbaum et al. (2009), Peng et al. (2003),
Chen et al. (2010a), Zhang et al. (2009),
Peng et al. (2006a), Yae et al. (2003), Chen
et al. (2008, 2010b), Sivakov et al. (2009),
Zhu et al. (2011)
Kato and Adachi (2011)
Yae et al. (2005, 2007), Peng and Zhu
(2004, 2003)
sNP,
mNP, pSi
Peng et al. (2003), Yae et al. (2005)
sNP,
mNP, pSi
sNP,
mNP, pSi
sNP,
mNP, pSi
sNP,
mNP, pSi
sNP,
sNW,
mNW,
pSi
pSi
Yae et al. (2005)
pSi
pSi
sNP, pSi,
sNW,
mNW
Douani et al. (2008)

Peng et al. (2006b)
Nahidi and Kolasinski (2006), Dudley and

Kolasinski (2009), Loni et al. (2011)
Dudley and Kolasinski (2009)
Dudley and Kolasinski (2009)
Peng et al. (2003)
It was observed that structures transition from solid etches (sNPs, sNWs) to
mesoporous etches (mNPs, mNWs, pSi) to polished surfaces with decreasing , id
est with increasing relative concentration of H2O2 (Chiappini et al. 2010; Chartier
et al. 2008). Figure 2 plots a collection of 108 etch conditions sourced from
13 independent publications, where silicon substrates deposited with Ag from
AgNO3 solution in HF were etched in HF/H2O2/H2O solution at room temperature,
in the absence of any other solvent (Geyer et al. 2012; Chiappini et al. 2010; Tsujino
and Matsumura 2005; Chartier et al. 2008; Huang et al. 2010a; Zhang et al. 2008,
2009; Zhong et al. 2011; Wu et al. 2012a, b; Wang et al. 2011; Qu et al. 2010;
Sivakov et al. 2010). Etch time was not a considered parameter. Substrate-doping
type does not seem to play a significant role in the resulting structures. Albeit
substrates of different resistivity have different transition thresholds, decreasing
induces porosification first and polishing then. As the oxidizer concentration is
176
C. Chiappini
Solid p-type
Porous p-type
Polish p-type
Solid n-type
Porous n-type
100
90
80
70
r/%
60
50
40
30
20
10
0
0.0001
0.001
0.01
0.1
Substrate Resistivity /
10
Fig. 2 Phase diagram for the nanostructures resulting from MACE as a function of substrate
resitivity and the parameter. Collection of 108 experiments from 13 independent publications.
Solid indicates pores with either solid sidewalls or solid nanowires; porous indicates pores with
either mesoporous sidewalls, mesoporous nanowires, or porous silicon; polish indicates complete
surface polishing
ultimately responsible for the rate of hole injection, and thus of the anodic current, it
is expected that increasing oxidizer concentration would lead to more
porosification, larger pores with higher porosity, and eventually surface polishing.
The data available to estimate pore size and porosity is significantly scarcer but
supports the idea of larger pores and increasing porosity with decreasing
(Chiappini et al. 2010; Zhong et al. 2011; Wang et al. 2011; Qu et al. 2010).
By tuning the concentration of oxidant in solution over time, it is possible to
obtain mesoporous nanowires and nanopores with segments of different porosity
(Chiappini et al. 2010; Chartier et al. 2008; Kolasinski 2005), as well as
nanostructures with segments of different orientation, switching periodically from
100 to non-100 (zigzag) (Refer to sections Orientation and Etch Rate).
Effect of Metal
A wide range of transition metals can catalyze MACE. Noble metals are especially
favored for the formation of nanowires as well as for nanostructures with defined
cross sections since they better preserve their structure during the etch, as they do
not dissolve in HF. Non-noble transition metals have been mostly used to form sNP,
pSi, and polished surfaces. Metals can be deposited on Si by a variety of methods,
including electroless deposition (Peng et al. 2003; Peng and Zhu 2004;
177
Table 3 Morphology of metal deposition, associated deposition techniques, and resulting MACE
structures
Metal
morphology
Continuous
film
Patterned film
Discontinuous
film
Deposition
Sputtering
Evaporation
Electroplating
Electroless
Evaporation
Sputtering
Electroless
Evaporation
Sputtering
Electroless
Dendrites
Electroless
Nanoparticles
Electroless
From solution
Electroplating
MACE
structures
pSi
References
Dimova-Malinovska et al. (1997), Geyer
et al. (2012), Peng et al. (2003)
Tailored
structures
Kim et al. (2011a), Geyer et al. (2012),

Chiappini et al. (2010), Mikhael et al. (2011),
Balasundaram et al. (2012)
pSi,
sNW,
mNW,
PS
pSi,
sNW,
mNW,
PS
sNP,
mNP,
pSi, PS
Megouda et al. (2009), Peng and Zhu (2004),

Yae et al. 2007, Peng et al. (2006b)
Chiappini et al. (2010), Chartier et al. (2008),

Peng et al. (2003, 2006b), Peng and Zhu
(2004), (Sivakov)
Dimova-Malinovska et al. (1997), Tsujino and
Matsumura (2005), Chartier et al. (2008), Lee
et al. (2008), Yae et al. (2007)
Yae et al. 2007), electroplating (Yae et al. 2005) evaporation (Dimova-Malinovska

et al. 1997; Chiappini et al. 2010; Zhong et al. 2011; Weisse et al. 2012), sputtering,
focused ion beam-assisted deposition, and nanoparticle deposition from solution
(Lee et al. 2008; Harada et al. 2001). Each deposition strategy can generate specific
metal morphologies, which best suits specific MACE structures (Table 3).
Continuous metal films that extend over several tens of microns tend not to sink
into the silicon and are unable to form MACE nanostructures, at time impeding
MACE altogether as they prevent the silicon underneath from interacting with the
solution. In appropriate conditions, silicon porosification can occur underneath and
in the vicinity of extended metal films (Geyer et al. 2012).
A common strategy is to pattern metal films by nanosphere lithography
combined with metal evaporation to obtain nanoscale-size hexagonally
close-packed dot arrays (Mikhael et al. 2011). The arrays of dots then undergo
MACE to form solid or porous silicon nanopillars. This general strategy can be
extended to any lithographic technique to obtain porous silicon nanostructures of
tailored geometry (Kim et al. 2011a, b; Harada et al. 2001). Multiple layers of
different metals (e.g., Au/Ag) are employed to improve Ag stability in oxidizing
conditions and allow for extended etch of high aspect ratio structures
(Kim et al. 2011a).
MACE of tailored nanostructure occurs also by combining lithographic patterning with electroless deposition, with the assistance of a hard, HF-resistant mask,
such as polystyrene or low-stress silicon nitride (Chiappini et al. 2010;
Asoh et al. 2009).
178
C. Chiappini
Table 4 Metal salts precursors for electroless deposition and resulting metal morphology
Metal
Ag
Precursor
AgNO3
Au
HAuCl4
Pt
Pd
Cu
KAuCl4
H2PtCl6
K2PtCl6
PdCl2
Cu
(NO3)2
Morphology
Nanoparticles
Dendrites
Nanoparticles
Dendrites
Films
Nanoparticles
Films
Nanoparticles
Films
Nanoparticles
Films
References
Chiappini et al. (2010), Chartier et al. (2008),
Hochbaum et al. (2009), Peng et al. (2003, 2006a)
Chiappini et al. (2010), Megouda et al. (2009), Yae
et al. (2005), Peng and Zhu (2003)
Yae et al. (2003), Peng et al. (2005, 2006b)
Yae et al. (2005, 2007)
Peng et al. (2003, 2006b)
Discontinuous metal films produce thin silicon nanowires, which can be

mesoporous or solid (Peng et al. 2006b). They are also employed to form porous
silicon or electropolished surfaces (Peng and Zhu 2004).
Dendrites form during extended electroless deposition of Ag or Au and are the
most commonly employed strategy to form dense forests of aligned silicon
nanowires or nanoplatelets. Tuning MACE conditions it is possible to obtain pSi
or PS from dendrites (Chiappini et al. 2010).
Isolated metal nanoparticles yield nanopores, which can have solid or
mesoporous sidewalls. Similarly as for dendrites, the conditions can be tuned to
form pSi or PS (Tsujino and Matsumura 2005; Chartier et al. 2008; Lee et al. 2008;
Yae et al. 2007).
Electroless deposition (ELD) of noble metals on the silicon surface is widely
employed in MACE. By ELD metal ions from a precursor salt in a solution of HF
inject holes in the silicon valence band and as a result get reduced and nucleate on
the silicon surface. This process is by no means different than MACE, and in fact
during ELD, the substrate gets also etched. ELD is a very simple and versatile
strategy that yields a wide array of metal morphologies, albeit with more limited
control with respect to the alternatives. ELD of noble metals generates all morphologies ranging from isolated nanoparticles to continuous metal films, but with
limited control on nanoparticle size, arrangement, metal film thickness and uniformity, grain, and domain size. Not all electroless deposited metals can achieve all
structures (Table 4).
Deposition time and precursor concentration can control the resulting metal
morphology (Peng and Zhu 2004; Yae et al. 2007). Initially, metal nanoparticles
nucleate on the silicon surface. As time progresses, the nanoparticles grow in size
eventually becoming dendrites or metal films (initially discontinuous and then
continuous) (Chartier et al. 2008; Peng et al. 2003; Yae et al. 2003). The density
of nanoparticles depends on the metal employed, its concentration, and the state of
the silicon surface (Yae et al. 2007).
179
Table 5 Etch direction as a function of substrate orientation and etching rate

Etch direction
Substrate
orientation
(100)
(110)
(111)
<100>
<110>
<111>
Other
All but extremely high

etch rate
Low etch rate
Low etch rate
Extremely high
etch rate
High etch rate
X
X
High etch
rate
Zigzag etch
Zigzag or
<113> etch
Effect of Substrate
Doping
Within the variety of etch conditions explored in the literature, MACE has shown
little dependence on substrate-doping type (Fig. 2). n-type (30 occurrences) and
p-type (78 occurrences) silicon start porosifying and polishing at comparable values
of . The resulting porous structures for p- and n-type silicon are also similar. This
behavior is justified in contrast to what is observed for electrochemical etch; as for
MACE, the positive carriers necessary for the oxidation are supplied from the
solution and do not originate from the semiconductor.
Doping concentration instead plays an important role controlling the etch morphology (Chiappini et al. 2010; Mikhael et al. 2011; Zhong et al. 2011). For all
resistivities considered, both solid and mesoporous structures can arise for
Ag-deposited substrate etched in H2O2/HF (Fig. 2; Chiappini et al. 2010; Chen
et al. 2010a; Bai et al. 2012). Polishing could also be obtained for any substrate in
appropriate conditions (Chiappini et al. 2010). Limited data is available for other
metal catalysts, but it suggests a similar behavior at least for Au and Pt. Choosing
appropriate values of , with decreasing resistivity, the etch morphology can transition
from solid to mesoporous to polished. When forming porous structures, decreasing
substrate resistivity is correlated with increased surface area and average pore size.
Orientation
The available data suggests that at low etch rates, there is a preferential etch in the
<100> direction regardless of substrate orientation (Kim et al. 2011a; Huang
et al. 2010a; Chen et al. 2008, 2010b; Wu et al. 2012a; Sivakov et al. 2010). As
the etch rate increases in non-(100) substrates, the etch orients in the vertical
direction. In some instances, a progressive orientation occurs. This phenomenon
has been justified through the energy requirements for silicon backbond breaking,
in analogy to the descriptions of electrochemical etch and anisotropic silicon etch in
alkaline conditions. Lower etch rates are associated with lower hole injection rates,
which in turn induce a preferential etch in the <100> direction as only two
backbonds must be broken for the etch to progress. Kim et al. observed <110>
etch in (100) substrates for extremely high etch rates surpassing 1,500 nm/min (Kim
et al. 2011a) and suggested a correlation between etch rate and etch orientation. This
phenomenon was also interpreted in terms of backbond breaking energies (Table 5).
180
C. Chiappini
The etch rate, which determines orientation, is controlled by multiple parameters

during MACE and will be discussed in detail in section Etch Rate (Kim
et al. 2011a). Typically etch orientation is controlled by tuning the concentration
of oxidizer (H2O2) in solution or the temperature. In general, higher H2O2 concentrations and higher temperatures are conducive to higher etch rates.
By appropriately controlling the etch conditions, it is possible to obtain both
solid and mesoporous nanowires for all orientations. By alternating between
regimes of high and low etch rate during MACE, it is possible to form zigzag
pores or zigzag wires, both solid and mesoporous (Chen et al. 2010b; Wu
et al. 2012a; Sivakov et al. 2010). Addition of organic solvents also influences
the etch directionality. Addition of ethanol or methanol to the etch solution resulted
in slanted nanopillars, while 2-propanol and acetonitrile returned uniformly curved
nanopillars (Kim et al. 2012).
Effect of Other Parameters

Temperature
A few studies have investigated the role of temperature in MACE. Ultimately, the
effect of temperature appears to be the expected one of providing energy to the
system with the effect of accelerating its kinetics. Increasing temperature can
induce the transition from solid to porous structure (Chen et al. 2010a). Increasing
temperature also correlates with higher surface area and larger pores (Loni
et al. 2011). Temperatures higher than 50 C were necessary to obtain porous
nanowires from lightly doped n-type silicon in Ag-deposited, H2O2/HF etched
substrates (Chen et al. 2010a). However, p-type lightly doped porous silicon
nanowires have been achieved at room temperature by depositing either Ag or Au
(Chiappini et al. 2010; Bai et al. 2012).
It is possible to switch etching from the 100 direction to non-100 direction on
both 100 and non-100 substrates by increasing temperature (Kim et al. 2011a; Chen
et al. 2010b).
Electric Field
MACE has been combined with electrochemical etch to form localized porous
segments in nonporous nanowires and obtain nanowires of prescribed length by
cleavage at the porous sections (Kim et al. 2011b). A pulsed current is applied to
the substrate to induce periodic porosification. Direct contact to a patterned
continuous metal film is necessary to induce localized porosification. If the
backside of the wafer is contacted, the entire nanowire structure porosifies upon
current pulsing.
Alcohol
Ethanol is typically added to the electrolyte during anodic etch to reduce hydrogen bubble formation, improve pore wettability, and reduce and strain in the
resulting layer. Ethanol though is known to differentially affect the activity of
181
Table 6 Effect of etch parameters on etch rate

Parameter
Action
Decrease
Oxidizer
Si resistivity
Temperature
Increase conc. ~
constant HF
Increase conc. ~
constant H2O2
Ordered by
increasing etch rate
Increase
Increase
Illumination
Alcohol
Increase intensity
Increase conc.
HF
Metal
Effect on etch rate

Increase 100 < < 80
Decrease 80 <
Increase etch rate
References
Chartier et al. (2008)
Decrease etch rate
Kim et al. (2011a)
Ag Au < Pt < PtPd
Asoh et al. (2009)
Increase etch rate

Increase etch rate
Chiappini et al. (2010)

Chartier et al. (2008),
Zhong et al. (2011)
Huang et al. (2010b)
Increase etch rate

Decrease etch rate
fluoride ions which is posed to impact the etch outcome. Addition of ethanol to an
H2O2/HF etching solution induces a progressive change in morphology from
solid nanowires, to mesoporous nanowires, to porous silicon layers, and eventually to electropolished structures (Chiappini et al. 2010). Similarly, addition of
methanol increased the surface area of porous silicon microparticles synthesized
by MACE (Loni et al. 2011). This effect was attributed to foam reduction and
improved wetting but could also partially be due to the changes in the etch
process associated with alcohol addition. Ethanol was also shown to improve
film uniformity in metal-assisted stain etch, while the addition of a tertiary
alcohol in the same conditions resulted in a significant decrease in etch rate
(Nahidi and Kolasinski 2006).
Etch Rate
Etch rate is an important parameter in MACE not only because it determines the
depth of the etch but also because it directly affects the resulting nanostructures.
Increasing etch rate has been shown to induce a switch from etching in the <100>
direction to etching in the non-<100> direction, for substrates of (100), (110), and
(111) orientations (Kim et al. 2011a). Etch rate is tightly correlated with the
structure of the porous nanowires (Chiappini et al. 2010). When the etch rate is
slower than the rate of porosification, vertical nanowires with vertically aligned
mesopores form, often over a layer of porous silicon. When the etch rate is slower
than the porosification rate, mesopores are oriented from the sidewalls of the wire
toward their core, and partially porous structure can form. The following table
summarizes how various known parameters affect etch rate. The table disregards
extreme conditions (usually at very high etch rates or for very long etch times)
where tip shortening or polishing occurs that effectively reduces the length of the
resulting structure and complicates the estimate (Table 6).
182
C. Chiappini
Properties of MACE Porous Nanowires

Table 7 provides a brief summary of the investigated properties of porous
nanowires synthesized by MACE. For the applications listed, the most relevant
handbook chapters are Porous Silicon and Solar Cells, Porous Silicon and
Li-Ion Batteries, and Photoluminescence of Porous Silicon.
Table 7 Properties of porous nanowires synthesized by MACE and their field of applicability
Property
Reflectance
Transmittance
Wetting
In situ PL
Observation
Dense nanowire arrays show
0.013 % reflectance in the
300800 nm range
Applicability
Photovoltaics
Antireflective
coatings
Solar-weighted reflectance
(41.96 %). Decreases with
decreasing incidence angle
(60 0 ), increasing density
of wires, increasing etching
temperature, and increasing
HF concentration during etch
Thin films show increase of
high-angle scattering for
wavelengths >1 m
H-terminated wires
superhydrophobic (>135 )
Oxidized wires are
superhydrophilic (<5 )
Contact-angle dependence on
wire density, diameter, length
H-terminated 525 and
424 nm em
Photovoltaics
885 nm em H-terminated
Effect of
oxidation on PL
PL excitation
and emission
peaks
Blue shift of peak with

oxidation, with peak intensity
increase
Red shift of peak with
oxidation, similar intensity
560 nm emission with
470 nm excitation
442 nm excitation
References
Wang
et al. (2012), Sun
et al. (2011),
Najar
et al. (2012)
Yeo et al. (2013)
Photovoltaics
Kato
et al. (2013)
Surface coatings
Wang et al.
(2012)
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Zhu et al. (2011)
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Voigt
et al. (2011)
Zhu et al. (2011)
Voigt
et al. (2011)
Chen
et al. (2010a)
Qu et al. (2011)
(continued)
183
Table 7 (continued)
Property
Observation
590 nm emission
473 nm excitation
PL intensity
Multiple PL
sources
Transistor
fabrication
Conductivity
Conduction
mechanism
Energy storage
Photocurrent
generation
Toxin
degradation
Thermal
conductivity (k)
Inelastic
scattering
Substrate
quality
Increase PL intensity and

energy with increasing etch
duration
Increase PL intensity and
energy with increasing H2O2
during etch
Applicability
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Nanophotonics
Optoelectronics
Multicolor PL from porous

nano-barcodes
FET device fabricated from
8 to 13 -cm p-Si, on-off
current ratio 104, h 46
cm2/V, n 8.6 1013 cm3
Threefold increase in
conductance for mNW over
sNW for lightly doped NW
mNWs have greatly reduced
conductivity over sNW for
highly doped NW
Poole-Frenkel conduction
Biolabelling
Li storage capacity 2,172 mA

h g1
910 A/cm2 photocurrent at
0.2 V bias
Pt-loaded mNWs degrade
indigo carmine (87 %) and
4-nitrophenol (66 %) under
light
mNWs degrade methyl red
(89 %) under visible light
k decreases with increasing
porosity
Li batteries anodes
Ag-covered nanoneedles
provide enhanced Raman
signal
MACE improves
metallurgical silicon purity
from 99.7 % to 99.9 %
Electronics
References
Li and Bohn
(2000)
Zhang
et al. (2009)
Voigt
et al. (2011), Lin
et al. (2010)
Voigt
et al. (2011), Lin
et al. (2010),
Zhang
et al. (2013)
Chiappini
et al. (2010)
Zhang
et al. (2008)
Nanoelectronics
Chen
et al. (2010a)
Nanoelectronics
Zhang
et al. (2009)
Nanoelectronics
Weisse
et al. (2012)
Wang and Han
(2010)
Wu
et al. (2012b)
Qu et al. (2010)
Photoelectrochemistry
Photocatalysis
Photocatalysis
Wang
et al. (2011)
(Weisse et al)
Nanoelectronics
Nanophononics
Surface-enhanced
Raman scattering
Kiraly
et al. (2013)
Photovoltaics
Li et al. (2013)
184
C. Chiappini
References
Asoh H, Arai F, Ono S (2009) Effect of noble metal catalyst species on the morphology of
macroporous silicon formed by metal-assisted chemical etching. Electrochim Acta
54:51425148
Bai F et al. (2012) One-step synthesis of lightly doped porous silicon nanowires in HF/AgNO3/
H2O2 solution at room temperature. J Solid State Chem
Balasundaram K et al (2012) Porosity control in metal-assisted chemical etching of degenerately
doped silicon nanowires. Nanotechnology 23:305304
Chartier C, Bastide S, Levy-Clement C (2008) Metal-assisted chemical etching of silicon in
HFH2O2. Electrochim Acta 53:55095516
Chen C-Y, Wu C-S, Chou C-J, Yen T-J (2008) Morphological control of single-crystalline silicon
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Ester Segal and Maksym A. Krepker
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Design of PSi-Polymer Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fabrication Methods of PSi-Polymer Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Incorporation of a Preformed Polymer with PSi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Polymerization Within PSi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
A variety of PSi-polymer composites have been developed, from the perspectives of different polymers, different composite morphologies, and different
targeted applications.
The field is comprehensively reviewed, focusing on the different design and
synthesis strategies, together with a brief discussion of the emerging fields of
application.
E. Segal (*)
Department of Biotechnology and Food Engineering, The Russell Berrie Nanotechnology
Institute, Technion Israel Institute of Technology, Haifa, Israel
e-mail: esegal@tx.technion.ac.il
M.A. Krepker
Department of Biotechnology and Food Engineering, Technion Israel Institute of Technology,
Haifa, Israel
e-mail: maks@techunix.technion.ac.il
DOI 10.1007/978-3-319-05744-6_18
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E. Segal and M.A. Krepker
Introduction
The combination of polymers with nanostructured silicon scaffolds, in particular
porous Si (PSi), into a single composite system opens vast opportunities for
developing advanced functional materials. These composites display unique properties that are culminated by the characteristics of each building block, to allow the
design of highly tunable nanomaterials. Over the past decade, various PSi-polymer
composites were introduced and their application as sensors (chapter Porous
Silicon Optical Biosensors), actuators, optical devices (e.g., chapter Porous
Silicon Optical Waveguides), drug delivery systems (chapter Drug Delivery
with Porous Silicon), and tissue-engineered scaffolds (chapter Porous Silicon
and Tissue Engineering Scaffolds) was demonstrated.
In this chapter, we will describe the basic considerations in designing functional
PSi-polymer composites, synthesis strategies, and emerging applications of these
nanomaterials. Future prospects and challenges in both fabrication and implementation of PSi-polymer-based devices will be discussed.
Design of PSi-Polymer Composites

Porous Si-polymer composites may be designed in diverse configurations. Figure 1
schematically illustrates the most common structures: PSi infiltrated with a polymer, polymer-coated PSi, polymer-capped PSi, released PSi film supported by a
polymer, PSi particles encapsulated by a polymer, and composite microparticles.
Each of these structures possesses different properties, which can be further refined
by a proper choice of the polymer constituent and the PSi nanostructure.
The simplest composite structure is that of a polymer-infiltrated PSi substrate
(Fig. 1a), wherein the polymer fills the entire porous volume (Segal et al. 2007;
Massad-Ivanir et al. 2010; Perelman et al. 2010; Massad-Ivanir et al. 2012a;
Krepker and Segal 2013). The polymer is confined within the nanoscale pores,
and its interaction with the pore wall can be enhanced by covalent attachment
(Massad-Ivanir et al. 2012a; Bonanno and Delouise 2010; Bonanno and Segal
2011; Sciacca et al. 2011). To some extent, polymer-coated PSi (Fig. 1b) has a
similar design, where the polymer only forms a uniform layer onto the pore walls,
resulting in an open porous structure (Segal et al. 2009; McInnes et al. 2009).
Polymer-capped PSi is a more sophisticated architecture (Fig. 1c), in which the
polymer only forms a blocking layer on top of the PSi, leaving the greater fraction
of the porous volume unoccupied (Wu and Sailor 2009). The fabrication of these
composites is more challenging, as the degree of polymer penetration into the pores
needs to be precisely controlled. Figure 1d presents a polymeric replica from PSi.
These replicas are usually prepared from polymer-infiltrated PSi by selective
removal of the Si scaffold (Li et al. 2003; Park et al. 2007). The previously
described designs make use of intact PSi substrates. However, the following
PSi-polymer composite configurations require mechanical processing of the PSi.
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Polymer-capped PSi
D Polymeric replica
B Polymer-coated PSi
A Polymer infiltrated PSi

G Composite microparticles
E Freestanding PSi film
supported by polymer
F PSi particles encapsulated

in polymer matrix
Fig. 1 Common structures of PSi-polymer composites. Insets in A illustrate interfacial chemistry

where the polymer is not attached to PSi (right) and is covalently attached to the PSi surface
through different linkers. Schematics are not drawn to scale
A freestanding PSi film supported by polymer is presented in Fig. 1e. In this case,
separation of the porous layer from the bulk Si is typically achieved by
electropolishing (DeLouise et al. 2005). Further fracturing of these porous films
allows us to fabricate particulate composites (McInnes et al. 2012). The resulting
PSi micro-/nanoparticles can be embedded in a polymer matrix (Fig. 1f) or encapsulated individually by a polymer layer (Fig. 1g). The latter case is more synthetically challenging.
The diversity in the design of these composites highlights the possibility to select
a suitable configuration for tailoring specific mechanical, chemical, and optical
properties for a desired function. Rational selection of the polymer component, PSi
substrate nanostructure, and fabrication strategy are of utmost importance in tuning
the behavior of the resulting composite.
Fabrication Methods of PSi-Polymer Composites

There are many synthetic approaches for integrating polymers with PSi. Figure 2
summarizes the main methods that are practiced for the fabrication of PSi-polymer
composites. In general, these techniques can be divided into two main categories.
The first is incorporating a preformed polymer with the Si scaffold. The second
involves in situ polymerization of monomers within/on the PSi. Herein, we will
focus only on the main techniques for the fabrication of PSi-polymer composites.
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PSi-polymers composite
fabrication
PSi + Polymers
B Grafting to
Solution/melt casting
PSi + Monomers
E In-situ polymerization
Voltage
Dispersion
Electrospinning
F Grafting from
Fig. 2 Common practiced methods for the fabrication of PSi-polymer composites
Incorporation of a Preformed Polymer with PSi

Solution casting (Fig. 2a) is probably the simplest route for fabricating
PSi-polymer composites, and thus, it is widely implemented (Wu and Sailor
2009; Park et al. 2007; McInnes et al. 2012; Gao et al. 2008; Orosco et al. 2006;
Shang et al. 2011; De Stefano et al. 2009; Schwartz et al. 2006; Kim et al. 2008;
Koh et al. 2008; Sychev et al. 2009; Whitehead et al. 2008; Li et al. 2005). In this
case, a polymeric solution is prepared and cast onto the PSi. This procedure is
usually followed by a subsequent spin-coating step to remove excess solution and to
distribute the polymer evenly on the surface of PSi (Gao et al. 2008; Shang
et al. 2011; Schwartz et al. 2006). The extent of polymer solution penetration into
pores plays a vital role in determining the final structure of the composite. Generally, polymer infiltration into the porous scaffold depends on several key parameters: the molecular weight (MW) of the polymer, the solution viscosity and its
surface tension, pore dimensions and morphology, and the pore wall surface
chemistry. In addition, the small size of pores can trap air or other gases, inhibiting
the penetration of the polymer solution into the pores. In this case, degassing under
vacuum and PSi conditioning with the solvent is recommended. Overall, this
technique is relatively straightforward, as it does not involve complex synthetic
steps and specialized experimental setups. Moreover, the use of a preformed
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polymer, which its characteristics are already defined (e.g., MW and chain configuration), offers significant advantages in terms of the properties and behavior of the
final composite. Capping layer on PSi film (Wu and Sailor 2009; Gao et al. 2008;
Orosco et al. 2006; Shang et al. 2011), PSi infiltrated with polymers (McInnes
et al. 2012; De Stefano et al. 2009; Schwartz et al. 2006), polymer replicas of PSi
templates (Li et al. 2003; Park et al. 2007; Kim et al. 2008), and a freestanding PSi
film supported by a polymer (Koh et al. 2008; Sychev et al. 2009) are the most
common designs of PSi-polymer composites prepared by solution or melt casting.
Another simple technique for preparation of PSi-polymer composites is by
dispersing PSi particles within a molten polymer or a polymeric solution
(Fig. 2c). Further processing of these dispersions is required in order to form
coatings (Svrcek et al. 2009), monoliths (McInnes et al. 2012; Mukherjee
et al. 2006), and fibers (Fan et al. 2011; Kashanian et al. 2010).
Fibrous PSi-polymer systems can be fabricated by electrospinning (Fig. 2d)
which is an established method for the production of large area networks of
thin flexible fibers. In this case, the PSi-polymer dispersion or melt is squeezed
through a nozzle, to which a strong electrical field is applied. The applied
voltage causes a cone-shaped deformation of the drop of polymer solution/melt
and a jet is formed. As the spurt makes its way to the counter electrode, the melt
solidifies or the solvent evaporates and a polymer fiber is formed (Greiner and
Wendorff 2007). The resulting properties of electro-spun fibers are controlled by
the process parameters, e.g., electrical conductivity, electrode separation and
geometry, temperature, concentration, and the polymer characteristics. Coffer
et al. (Fan et al. 2011; Kashanian et al. 2010; Fan et al. 2009) have applied this
technique to produce electro-spun fibers of PSi particles encapsulated within a
polycaprolactone matrix.
Grafting involves covalent attachment of the polymer to a surface. Grafting
provides a versatile tool for surface modification and functionalization in a highly
controllable manner. Two main grafting categories can be identified. The first is
termed grafting to, in which a preformed polymer is attached to the surface. In the
second approach grafting from, polymerization is initiated from the substrate
surface by the attachment of initiating groups (Minko 2008). The latter method will
be discussed in the following section, dealing with polymerization techniques.
In the grafting to method (Fig. 2b), end-functionalized polymer chains are
reacted with complementary functional groups located on the PSi surface to form
tethered polymer chains (Minko 2008). The versatile chemistry of Si/SiO2 allows
functionalization of the PSi surface with a wide repertoire of reactive groups
(Buriak 2002; Ciampi et al. 2008; Kilian et al. 2009a; Alvarez et al. 2009;
Jarvis et al. 2012). Some of the most common PSi functionalization routes are
presented in Fig. 3.
The advantage of the grafting to method is that the end-functionalized polymers
with a predetermined configuration (e.g., MW and functional groups) are employed
for grafting, and, as a result, well-defined layers can be readily obtained. It should be
mentioned that a disadvantage of this method is the limited grafting density that can
be achieved (Zdyrko et al. 2006). Thus, this technique was implemented for grafting
192
Fig. 3 Commonly practiced

surface chemistries for the
functionalization of PSi.
These end groups can be
reacted with a wide variety of
polymers
poly(n-isopropylamide) (polyNIPAM) (Segal et al. 2009), chitosan (Sciacca

et al. 2011), and gelatin (Kilian et al. 2009b). Grafting to is typically used for
fabricating polymer-coated PSi surfaces and nanostructures (see Fig. 1b).
Polymerization Within PSi

In many cases, when using high-MW polymers, these macromolecules are size
excluded from the nanoscale pores, or their efficient infiltration into the PSi
nanostructure is impaired. Thus, to circumvent these issues, in situ polymerization
of low-MW monomers (or oligomers) within the PSi scaffold can be applied (Segal
et al. 2007; Massad-Ivanir et al. 2010; Perelman et al. 2010; Krepker and Segal
2013; Massad-Ivanir et al. 2012b; El-Zohary et al. 2013). The PSi nanostructure is
commonly filled with a prepolymer solution, which may contain a composition of a
solvent, monomers, cross-linking agents, initiators, and catalysts. When the polymerization reaction is initiated, the polymer is formed inside the pores of PSi,
resulting in a uniform and high pore filling. In certain cases, polymerization can be
initiated from the PSi surface, generally termed as a grafting from technique, or
the growing polymer chains can be tethered to the pore walls.
There are many different polymerization routes that have been employed for the
fabrication of PSi-polymer composites, including free-radical polymerization (FRP),
photopolymerization (Segal et al. 2007; Massad-Ivanir et al. 2010; Perelman
et al. 2010; Krepker and Segal 2013; Massad-Ivanir et al. 2012b), atom transfer radical
polymerization (ATRP) (Vasani et al. 2011; Yang and Choi 2010; Pace et al. 2013),
ring-opening polymerization (McInnes et al. 2006, 2009, 2012; Yoon et al. 2003), and
electro-polymerization (Belhousse et al. 2010; Jin et al. 2009; Chiboub et al. 2010;
Fukami et al. 2009; Harraz et al. 2008; Betty 2009; Urbach et al. 2007a, b; Nahor
et al. 2011; Badeva et al. 2012; Dian et al. 2013). Polymerization method has a
profound effect on the resulting PSi-polymer composite structure and its properties.
For example, FRP typically results in time invariant degrees of polymerization and a
high polydispersity index (a wide MW distribution). ATRP, on the other hand, allows
for achieving a controllable molecular weight and low polydispersity, as the polymer
193
chains preserve their ability to grow for a long time and their degree of termination or
chain transfer is very low (Braunecker and Matyjaszewski 2007).
When grafting from approach is applied for polymer synthesis, an appropriate
initiator is commonly immobilized onto the pore walls followed by polymer chains
growth via different possible mechanisms (Jarvis et al. 2012; Vasani et al. 2011;
Xu et al. 2004; Chen et al. 2009). The main advantage of the grafting from methods
is the possibility to form polymer layers of high density in comparison to the
grafting to approach.
It should be emphasized that in situ polymerization within nanostructures is a
complex process in which nano-confinement conditions may affect the polymerization kinetics and the resulting properties of the polymer (Massad-Ivanir
et al. 2012a; Alcoutlabi and Gregory 2005; Keten et al. 2010; Kruk et al. 2008;
Liang et al. 2000; Uemura et al. 2010; Gorman et al. 2008). Recent studies have
shown that the imprisonment of hydrogels in PSi nanoscale pores induces significant changes in the confined polymer properties, e.g., volume phase transition
(VPT) kinetics, compared to those observed for the bulk free polymers (Segal
et al. 2007; Massad-Ivanir et al. 2010; Perelman et al. 2010; Bonanno and Segal
2011). Moreover, significant differences between the thermal degradation behaviors of the confined polymers, poly(acrylamide), and polyNIPAM and neat polymer
and thin polymer films deposited onto planar Si surfaces were observed. The
confined polymers have inferior thermal stability than the neat polymers. These
findings indicate that the in situ polymerization and the polymer confinement
conditions have a profound effect on the nanostructure and resulting behavior of
the polymeric phase (Massad-Ivanir et al. 2012a).
We expect that investigation and characterization of the properties of different
polymeric systems confined within nanostructured porous Si hosts will allow to
finely tune the polymer properties by controlling the confinement conditions and
interfacial interactions between the polymer and the host material. This will expand
the possibility for rational design of new PSi-polymer nanomaterials with tailored
properties and functions.
Applications
As PSi-polymer composites exhibit unique properties that are culminated by the
characteristics of each building block, they can be rationally designed to display
highly tunable properties, e.g., mechanical, chemical, optical, and electrical. Over
the past decade, these attractive nanocomposites have been studied as platforms for
designing different devices. Applications of these composites range from drug
delivery systems, sensors, and actuators to optoelectronics and photovoltaics.
A recent review (Bonanno and Segal 2011) provides an updated overview on the
biomedical applications of these materials, highlighting the construction of smart
drug delivery systems (Wu and Sailor 2009; Vasani et al. 2011; Godin et al. 2011),
improved label-free optical biosensors (Massad-Ivanir et al. 2010; Massad-Ivanir
et al. 2012b; Holthausen et al. 2012), or sensors (Bonanno and Delouise 2010) for
194
point-of-care applications such as temperature sensors to monitor wound healing

(Pace et al. 2012), lab-on-chip systems (Chen et al. 2009), and tissue engineering
scaffolds (Coffer et al. 2005). In addition to the vast biological applications,
PSi-polymer composites are being investigated as chemical sensors for different
targets (Belhousse et al. 2010; Jin et al. 2009; Wang et al. 2012; Levitsky
et al. 2007; Pang-Leen and Levitsky 2011), optoelectronics devices, photovoltaics
(Svrcek et al. 2009; Badeva et al. 2012; Halliday et al. 1996; Mishra et al. 2008;
Nguyen et al. 2003a, b; Gongalsky et al. 2012), and energy storage (Ge et al. 2012).
Thus, the versatility of polymers in combination with the unique properties of PSi
offers a wealth of opportunities for the design of new functional materials for a
range of applications. We have yet to see the widespread translation of these
composite-based devices into commercial application, and only the future will
reveal the true impact of these materials.
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Part II
Properties

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porosity-Based Structural Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Surface-Based Chemical Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Composite-Based Property Tuning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Property Ranges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
202
202
203
203
204
205
Abstract
Data and literature are collated that emphasize the high tunability of porous
silicon properties, either via manipulation of its structural parameters, via the
chemistry of the large internal surface area, or via impregnation of other
materials. An overview of quantitative data on more than 30 properties is
tabulated and compared to those of nonporous silicon. Where available,
the range of values reported to date is given. The properties showing the
widest tunability to date include the visible photoluminescence (optical
bandgap), mechanical stiffness, thermal conductivity, optical refractive
index, electrical resistivity, biodegradability kinetics, optical reflectivity, and
surface wettability.
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_19
201
202
L. Canham
Introduction
Introducing nanoscale and microscale porosity into a material can be utilized to tune
a wide variety of selected properties. At the nanoscale, and with a semiconductor like
silicon, one is in a regime where quantum confinement effects become important, and
many properties vary dramatically with skeleton size distribution. The purpose of this
short introductory review to the properties section of the handbook is to highlight the
different approaches to tuning the various properties (see Fig. 1) and give a tabulated
overview of most property values reported to date (see Table 2).
The majority of, but not all, properties listed in that table have dedicated reviews
elsewhere in the handbook for those readers interested in much more detail on
specific properties.
Porosity-Based Structural Parameters

Many properties have been investigated as a function of porosity (pore volume) but
this parameter alone is a simplification of the overall morphology. Certain properties will scale better with internal surface area, others with skeleton size distribution, yet others with pore diameter distribution. Gas diffusion and liquid diffusion
through porous silicon, for example, are primarily dependent on pore diameter and
interconnectivity. Visible photoluminescence depends primarily on skeleton size
distribution in combination with surface chemistry.
With electrochemically etched porous silicon structures, quantum size effects
are only important in microporous and mesoporous silicon. Macroporous silicon
can for many properties be modeled as bulk silicon with voids therein, provided
the macropores therein do not contain mesoporosity, for example.
PORE IMPREGNATION
Eg. Polymer, metal,
ceramic
Fig. 1 The three approaches

to tuning properties of porous
silicon. In some cases two
approaches have been used in
conjunction, but rarely all
three
STRUCTURAL
PARAMETERS
Eg. Porosity, skeleton
size, surface area
SURFACE CHEMISTRY
Eg. Si-O, Si-C, Si-N bonding
203
Examples of properties that can be tuned over a wide range by structural

parameters alone include many thermal, optical, mechanical, and emissive ones.
Surface-Based Chemical Parameters

For materials with high surface area, dramatic effects can also be observed by
manipulating surface chemistry with a fixed structural morphology. The importance
of surface chemistry generally rises with increasing porosity, increasing pore
density, and decreasing average pore size. Table 1 illustrates the dramatic increase
in surface atom contributions to properties for the three classes of silicon material,
each with a fixed porosity of 50 % and cylindrical pores arranged in an idealized
uniform array. If we could fabricate, for example, completely microporous silicon
with 1 nm wide pores (see handbook chapter Microporous Silicon), almost one
in every three silicon atoms would have pore wall surface bonding arrangements.
Examples of properties tuned significantly via primarily surface chemistry
manipulation include physiochemical ones like zeta potential and isoelectric
point. Surface wettability is a good example where both structural and surface
chemical parameters have been optimized in order to achieve superhydrophobicity with mesoporous and macroporous silicon (Cao et al. 2006;
Ressine et al. 2008).
Composite-Based Property Tuning

Nanoscale porosification has been shown capable of introducing new functionality
to silicon; examples are its visible luminescence and its medical biodegradability
(Canham 1997). There are however other properties where nanostructuring alone
has not dramatically changed silicon performance; one notable example is its
magnetic properties. In this case tunability can still be achieved by impregnation
of appropriate magnetic materials (Granitzer and Rumpf 2010). Via the impregnation route, radically different tunable properties are achievable in macroporous
silicon as well (Murzina et al. 2007; Perez et al. 2012) and thus all three classes of
material (see also handbook chapter Processing of Macroporous Silicon). The
formation of novel nanocomposites on-chip and in nanoparticle form is likely to
be increasingly explored and should have a profound effect on mechanical properties, for example.
Table 1 Pore size scaling in the importance of surface chemistry with structural parameters
Material
class
Macroporous
Mesoporous
Microporous
Porosity
(%)
50
50
50
Pore
diameter
1 m
10 nm
1 nm
Pore density
(mm 2)
5 105
5 109
5 1011
Surface area
(m2/g)
1.7
170
1,700
Surface/bulk Si
atom ratio
0.0003
0.03
0.3
204
L. Canham
Property Ranges
Table 2 presents an overview of the property tunability reported to date for
mesoporous silicon (Yu et al. 2000). In every case values are compared with
those of nonporous crystalline (Hull 1999), rather than amorphous silicon
(Fritzsche 1989). Most of these properties are dealt with in more detail individually
in the accompanying handbook chapters.
Table 2 The tunable properties of mesoporous silicon. Data were extracted from the references
listed below in combination with many other reviews of this handbook. Missing entries for either
silicon or mesoporous silicon refer to instances where the author is unclear as to an appropriate
range from the literature studied
Class of
property
Structural
Property
Silicon
Mesoporous silicon
Porosity
Density
Pore size (diameter)
Surface area
Lattice symmetry
Lattice constant
Not applicable
2.33 g
Not applicable
Not applicable
Diamond
0.543 nm
2095 %
0.121.9 g cm
250 nm
100800 m2 g
Diamond
0.540.59 nm
Youngs Modulus
Hardness
160 GPa
11.5 GPa
1100 GPa
0.210 GPa (layers)
0.051 GPa (polymer
composite)
Yield strength
Fracture toughness
7 GPa
0.6 MPa.m1/2
Bandgap
Infrared refractive index
Color
1.1 eV
3.5
Gray
Reflectivity (5001,000
nm)
1035 %
Resistivity
Electron mobility
Hole mobility
Dielectric constant
10 2103 cm
1,350 cm2V 1 s
480 cm2V 1 s 1
11.5
Conductivity
Melting point
Specific heat
Diffusivity
150 Wm 1 K
1,414 C
0.7 Jg 1 K 1
0.8 cm2 s 1
Mechanical
14 MPa. m1/2
Optical
1.13.2 eV
1.13.0
All colors (layers)
Brown-yellow
(particles)
0.110 %
Electrical
1
1031012 cm
0.130 cm2V 1 s
2-6 cm2V 1 s 1
28
Thermal
1
0.0320 Wm 1 K
8001,414 C
(continued)
205
Table 2 (continued)
Class of
property
Magnetic
Property
Silicon
Mesoporous silicon
Diamagnetic susceptibility
1.2 10 6
(n+ Si)
Not applicable
<1 10
1,0001,200 nm
4001,300 nm
Ferromagnetic coercivity
280500 Oe
(Ni nanocomposite)
Emissive
Photoluminescence
(PL) wavelength
PL efficiency (visible)
10
EL efficiency (visible)
10
Isoelectric point
pH 1.62.5 (native
oxide)
-(4570) mV (native
oxide)
596
0.010.23 (films)
0.010.60 (suspensions)
0.010.1
Physiochemical
Zeta potential (pH7)

Surface wettability
(contact angle)
pH 1.67.7 (oxidized/
derivatized)
<0.5o167
Biochemical
Medical biodegradability
(duration)
Energetic
Burning rate
Not applicable
Months (implants)
Days (microparticles)
Hours (nanoparticles)
1500 m s 1
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Zhang Q, Gu M (2005) Rheological properties and gelcasting of concentrated aqueous silicon
suspension. Mater Sci Eng A339:351357
Thermal Properties of Porous Silicon

Nobuyoshi Koshida
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Constants of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Related Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
207
208
210
211
Abstract
Mesoporous silicon has tunable thermal properties that can be radically different
from those of nonporous silicon. Published data on the major thermal constants
and the techniques of measurement are reviewed and values compared to those
of other materials. The combination of very low thermal conductivity and heat
capacity of highly porous silicon has led to a number of specific applications that
exploit these thermal properties.
Introduction
The major thermal constants of solids are the thermal conductivity (W/mK) and the
heat capacity per unit volume, C (J/m3K). Related thermal parameters are the thermal
p
diffusivity D /C (m2/s) and the thermal effusivity e C (Ws1/2/m2K). As a
p
dynamic factor, the thermal penetration length L (m), given by
2=C , is
important from a viewpoint of the practical use, where is the angular frequency
of a thermal oscillation at the solid surface. The thermal properties of
single crystalline silicon (c-Si) are characterized by a very high (148 W/mK)
N. Koshida (*)
Tokyo University of Agriculture and Technology, Tokyo, Japan
e-mail: koshida@cc.tuat.ac.jp
DOI 10.1007/978-3-319-05744-6_20
207
208
N. Koshida
and a relatively low C (1.66 MJ/m3K) (Hull 1999). In addition, a significantly small
thermal expansion coefficient and a sufficiently high melting point are compatible
with the device applications.
Thermal Constants of Porous Silicon

In porous silicon (PS), is dramatically decreased as suggested from thermal flow
measurements (Drost et al. 1995). For characterizing the thermal parameter in
nanostructures like PS, two major ways have been employed to generate a probing
signal of the thermal fluctuation: electrical input and noncontact optical incidence.
The most useful method in the former case is so called the 3 method (Cahill 1990),
in which the third-harmonic component of the alternating thermal oscillation with a
certain frequency is selectively detected by a phase-sensitive measurement.
In the case of the 3 measurements for PS (Gesele et al. 1997; Kihara
et al. 2005), the test sample is composed of a patterned thin metal film, a PS
layer, and c-Si substrate. A narrow thin metal wire (e.g., 25 m and 3 mm in
width and length, respectively) was formed on the PS layer by photolithographic
patterning of a deposited thin metal film and used as both a heater and thermometer.
An oscillating electrical current of frequency is supplied to the metal wire using a
signal generator. The produced Joule heating causes a surface temperature oscillation T with a frequency of 2. This temperature fluctuation produces a small
change in the resistance of the metal wire with a certain thermal coefficient.
Consequently, the terminal voltage generated in the metal wire includes the thirdharmonic component of 3. Thus, the information about the surface temperature
oscillation can be obtained from the detection of a small voltage signal.
The actual experimental system uses a bridge circuit and a lock-in amplifier, and
the T values are measured as a function of frequency. The theoretical value of T
is given by the solution of the diffusion equation for a radial heat flow from the
surface electrode. At low frequencies in which the thermal penetration depth is
much larger than the PS layer thickness, T is the summation of two components:
one from the PS layer, TPS, and the other from the c-Si substrate, TS. The TPS
value depends on the thermal conductivity of the PS layer and the experimental
parameters. Since the TS value is obtained from the known thermal parameters of
c-Si, value of the PS layer can be determined from the analysis of the measured
T. At high frequencies, on the other hand, the thermal penetration depth is smaller
than the PS layer thickness, and then the contribution of the substrate to T is
negligible. Under this situation, the experimental T data simply relate to the
D value that is given as /C. So the C value of the PS layer can be deduced from
measured at low frequencies. Owing to the insensitivity to errors from black-body
radiation, this method makes it possible to determine the thermal constants more
precisely rather than the method based on simple thermal flow measurements.
Another method is based on the noncontact optical probing of PS samples. One
approach utilizes the optical absorption and the subsequent photoinduced acoustic
effect (McDonald and Wetsel 1978; Almond and Patel 1996). When the photo-
Thermal Conductivity a (W/mK)
209
Metals
(Al, Cu, Ag, W, Au)
c - Si
100
Semiconductors
10
Oxidized PS
Quartz glass
Water
Polyethylene
PS
0.1
Rubber
Air
0.01
Heat Capacity per unit Volume C (MJ/m3K)
Fig. 1 Plots of the typical measured thermal conductivity of PS and other materials versus their
corresponding heat capacity per unit volume. The most important determining factor for the
thermal parameters of PS is the porosity. An extremely big contrast is induced in the thermal
properties between PS and c-Si, especially in the high-porosity case
acoustic emission amplitude and its phase are measured for the sample as a function
of chopping frequency, a kink appears in the frequency response at which
the thermal diffusion length is equal to the sample thickness. From this critical
frequency, the e and values of different PS samples were determined in ambient
air at room temperature (Cruz-Orea et al. 1996; Calderon et al. 1997; Benedetto
et al. 1997; Obraztsov et al. 1997; Bernini et al. 1999; Shen and Toyoda 2003). To
detect the thermal wave propagation based on the optical methods, micro-Raman
spectroscopy (Lysenko et al. 1999) and transient heating by a laser pump
pulse (Bernini et al. 2001) have also been conducted. By using self-standing PS
membranes (Maccagnani et al. 1999), the accuracy of these measurements
was improved (Bernini et al. 2005; Wolf and Brendel 2006). The periodic
microporous freestanding PS thin film is also useful for measuring the in-plane
thermal conductivity by a steady-state method (Song and Chen 2004).
Recently, the characteristic phonon transport in nanostructures was analyzed by
molecular dynamics simulations (Fang and Pilon 2011) in relation to the scaling
laws for the thermal conductivity in nanodot array (Fang et al. 2012) and by
hydrodynamic approach (Alvarez et al. 2010) for investigating the influence of
PS porosity and pore size on the reduction in the thermal conductivity.
Figure 1 shows -C mapping of various materials. In metals, the contribution of
high-density free electrons to is dominant over that of lattice vibrations, while
the situation is reversed in semiconductors. In c-Si with purely covalent bonds,
particularly, the lattice contribution is enhanced due to the completely neutral lattice
point. This exceptionally high thermal conductivity of c-Si disappears in PS, and
then the C value is significantly decreased. For the porosity of 40 % and 70 %, typical
experimental values are 1.2 and 0.2 W/mK, respectively (Gesele et al. 1997).
210
N. Koshida
Table 1 Techniques for quantifying the thermal constants of PS and the respective experimental
values
Method
Thermal
flow
Electrical
(3)
Optical
Porosity
(%)
40
Thermal
conductivity
(W/mK)
1.2
64
71
79
89
55
Oxidized
80
0.20
0.14
0.05
0.03
1.1
1.9
0.025
62
74
50
0.9
0.3
0.9
48
66
30
8.7
5.1
0.230.37
Volumetric heat capacity

(MJ/m3K)
0.18
0.65
0.5 (estimated from

thermal diffusivity)
0.96
0.45
References
Drost
et al. (1995)
Gesele
et al. (1997)
Kihara
et al. (2005)
Obraztsov
et al. (1997)
Lysenko
et al. (1999)
Bernini
et al. (2005)
Wolf and
Brendel (2006)
Fang and Pilon
(2011)
The corresponding C values fall within 0.40.2 MJ/m3K (Kihara et al. 2005). As a
consequence, the thermal effusivity of PS is over 30 times lower than that of c-Si.
The measured thermal diffusivity D of a 50 %-porosity PS sample at room temperature is ~0.01 cm2/s (Bernini et al. 2005). This value, consistent with the result of a
theoretical analysis, is two orders of magnitude lower than that of c-Si. When
oxidized, both and C values tend to become higher than those of as-prepared PS
(Kihara et al. 2005). In the PS samples with an extremely high porosity (8090 %),
values fall to 0.050.03 W/mK (Gesele et al. 1997) that is over three orders of
magnitude lower than that in c-Si.
Related Applications
Typical experimental values of these thermal properties are listed in Table 1.
Coexistence of low and low C in PS is a very attractive feature as the thermal
insulating material (see handbook chapter Thermal Isolation with Porous Silicon).
Most conventional materials do not meet this requirement: Though silica, polymers,
and rubbers have relatively low thermal conductivities, it is difficult to lower their
C values. The exceptional one is silica aerogel powder and its mixture with carbon
black whose and C values are significantly reduced, especially at low temperatures
due to its extremely low density (Fricke et al. 1989; Rettelbach et al. 1995).
211
The abovementioned specific thermal property underpins many potential application areas: thermal isolation (Lysenko et al. 2002), thermally induced broadband
sound emission (Shinoda et al. 1999; Koshida et al. 2013; Okabe et al. 2013),
thermoelectric conversion (Lee et al. 2008a), photothermal therapy (Lee
et al. 2008b; Lee et al. 2012), local heating leading to black-body radiation
(Costa et al. 1998), use in Si micro-cooling devices (Valalaki and Nassiopoulou,
2013) and sintering (Kovivchak and Davletkildeev 2009; Timoshenko et al. 2000;
Koyama and Fauchet 2000). These applications and processing issues are reviewed
in the handbook chapters Porous Silicon for Microdevices and Microsystems,
Thermal Isolation with Porous Silicon, Porous Silicon in Photodynamic
and Photothermal Therapy, and Sintering of Porous Silicon.
References
Almond DP, Patel PM (1996) Photothermal science and techniques. Chapman & Hall, London
Alvarez FX, Jou D, Sellitto A (2010) Pore-size dependence of the thermal conductivity of porous
silicon: a phonon hydrodynamic approach. App Phys Lett 97:033103/1-3
Benedetto G, Boarino L, Spagnolo R (1997) Evaluation of thermal conductivity of porous silicon
layers by a photoacoustic method. Appl Phys A 64:155159
Bernini U, Maddalena P, Massera E, Ramaglia A (1999) Photo-acoustic characterization of porous
silicon samples. J Appl Opt A Pure Appl Opt 168:210213
Bernini U, Lettieri S, Maddalena P, Vitiello R, Francia GD (2001) Evaluation of the thermal
conductivity of porous silicon layers by an optical pump-probe method. J Phys Condens Matter
13:11411150
Bernini U, Bernini R, Maddalena P, Massera E, Rucco P (2005) Determination of thermal diffusivity
of suspended porous silicon films by thermal lens technique. Appl Phys A 81:399404
Brozel M (1999) Thermal properties, Chap 4. In: Hull R (ed) Properties of crystalline silicon. The
Institution of Electrical Engineering, London, pp 149171
Cahill DG (1990) Thermal conductivity measurement from 30750 K: the 3 method. Rev Sci
Instrum 61:802808
Calderon A, Alvardo-Gil JJ, Gurevich YG, Cruz-orea A, Delgadillo I, Vargas M, Miranda LC
(1997) Photothermal characterization of electrochemical etching processed n-type porous
silicon. Phys Rev Lett 79:50225025
Costa J, Roura P, Morante JR, Bertran E (1998) Blackbody emission under laser excitation of
silicon nanopowder produced by plasma-enhanced chemical-vapor deposition. J Appl Phys
83:78797885
Cruz-Orea A, Delgadillo I, Vargas H, Gudino-Martnez A, Marn E, Vzquez-Lopez C,
Calderon A, Alvarado-Gil JJ (1996) Photoacoustic thermal characterization of spark-processed
Drost A, Steiner P, Moser H, Lang V (1995) Thermal conductivity of porous silicon. Sens Mater
7:111120
Fang J, Pilon L (2011) Scaling laws for thermal conductivity of crystalline nanoporous silicon
based on molecular dynamics simulations. J Appl Phys 110:064305/1-10
Fang J, Kang CB, Huang Y, Tolbert SH, Pilon L (2012) Thermal conductivity of ordered
mesoporous nanocrystalline silicon thin films made from magnesium reduction of polymertemplated silica. J Phys Chem C 116:1292612933
Fricke J, Hummer E, Morper H-J, Scheuerpflug P (1989) Thermal properties of silica aerogels.
Revue de Phys Appl Colloque C4 24:8797
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Gesele G, Linsmeier J, Drach V, Friche J, Arens-Fischer R (1997) Temperature-dependent thermal

conductivity of porous silicon. J Phys D 30:29112916
Kihara T, Harada T, Koshida N (2005) Precise thermal characterization of confined nanocrystalline silicon by a 3 method. Jpn J Appl Phys 44:40844087
Koshida N, Hippo D, Mori M, Yanazawa H, Shinoda H, Shimada T (2013) Characteristics of
thermally induced acoustic emission from nanoporous silicon device under full digital operation. Appl Phys Lett 102:123504
Kovivchak VS, Davletkildeev NA (2009) Melting of porous silicon under the action of a
nanosecond pulsed high-power ion beam. Tech Phys Lett 35:446448
Koyama H, Fauchet PM (2000) Laser-induced thermal effects on the optical properties of freestanding porous silicon films. J Appl Phys 87:17881794
Lee J-H, Galli GA, Grossman JC (2008a) Nanoporous Si as an efficient thermoelectric material.
Nano Lett 8:37503754
Lee C, Kim H, Hong C, Kim M, Hong SS, Lee DH, Lee WI (2008b) Porous silicon as an agent for
cancer thermotherapy based on near-infrared light irradiation. J Mater Chem 18:47904795
Lee C, Hong C, Lee J, Son M, Hong SS (2012) Comparison of oxidized porous silicon with bare
porous silicon as a photothermal agent for cancer cell destruction based on in vitro cell test
results. Lasers Med Sci 27:10011008
Lysenko V, Perichon S, Remaki B, Barbier D, Champagnon B (1999) Thermal conductivity of
thick meso-porous silicon layers by micro-Raman scattering. J Appl Phys 86:68416846
Lysenko V, Perichon S, Remaki B, Barbier D (2002) Thermal isolation in microsystems with
porous silicon. Sens Actuators A Phys 99:1324
Maccagnani P, Angelucci R, Pozzi P, Dori L, Parisini A, Bianconi M, Benedetto G (1999) Thick
porous silicon thermo-insulating membranes. Sens Mater 11:131147
McDonald FA, Wetsel GC jr (1978) Generalized theory of the photoacoustic effect. J Appl Phys
49:23132322
Obraztsov AN, Okushi H, Watanabe H, Timoshenko VY (1997) Optical absorption in porous
silicon studied by photoacoustic spectroscopy. Phys Stat Sol (B) 203:565569
Okabe S, Nagasawa M, Kihara T, Kato M, Harada T, Koshida N, Mogi K, Kikusui T (2013) Pup
odor and ultrasonic vocalizations synergistically stimulate maternal attention in mice. Behav
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Rettelbach T, Sauberlich J, Korder S, Fricke J (1995) Thermal conductivity of silica aerogel
powders at temperatures from 10 to 275K. J Non-Cryst Solids 186:278284
Shen Q, Toyoda T (2003) Dependence of thermal conductivity of porous silicon on porosity
characterized by photoacoustic technique. Rev Sci Instr 74:601603
Shinoda H, Nakajima T, Ueno K, Koshida N (1999) Thermally induced ultrasonic emission from
porous silicon. Nature 400:853855
Song D, Chen G (2004) Thermal conductivity of periodic microporous silicon films. Appl Phys
Lett 84:687689
Timoshenko VY, Dittrich T, Sieber L, Rappich J, Kamenev BV, Kashkarov PK (2000) Laserinduced melting of porous silicon. Phys Stat Sol (A) 182:325330
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513(12):385390
Mechanical Properties of Porous Silicon

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Youngs Modulus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Yield Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fracture Toughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Anisotropy of Mechanical Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mechanical Properties of Nanoscale Solid Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Relevance of Mechanical Properties to Emerging Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding Remark . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
214
214
215
216
217
217
218
218
218
219
Abstract
Introducing nanoscale porosity into silicon dramatically lowers its stiffness and
hardness in a tunable manner over a wide range. Available data is collated on
Youngs modulus and Vickers hardness as a function of porosity and layer
morphology. There is little quantitative data on fracture toughness and strength,
but theoretical work predicts that optimized nanocomposites could be very
mechanically durable. The exceptional plasticity recorded for individual silicon
nanowires is yet to be demonstrated in mesoporous silicon. A number of
application areas are highlighted that rely heavily on the mechanical properties
of porous silicon.
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_21
213
214
L. Canham
Introduction
The remarkable mechanical properties of silicon underpin its role in MEMS
(Peterson 1982). The single crystal pure material is relatively hard, very brittle,
but exceptionally strong, with a yield strength that exceeds that of stainless steel.
When we porosify a material, we can dramatically change mechanical properties,
often in a tunable manner (Gibson and Ashby 1997; Rice 1998).
The mechanical properties of mesoporous silicon have so far received
nothing like the intense scrutiny that its structural, luminescent, thermal, and
optical properties have (see, e.g., the handbook chapters Microscopy of Porous
Silicon, Photoluminescence of Porous Silicon, Thermal Properties
of Porous Silicon, and Refractive Index of Porous Silicon). Following the
very first studies (Barla et al. 1984; Drory et al. 1990), there have been continued
but infrequent assessments (Da Fonesca et al. 1995; Fang et al. 2008; Rahmoun
et al. 2009; Aliev et al. 2011). Nonetheless, there is a growing realization that robust
porous silicon device and system performance will ultimately rely on achieving the
appropriate mechanical properties, in conjunction with the novel functionality
achieved through nanostructuring.
In this short review, we survey the literature data available on yield strength,
Youngs modulus, hardness, and fracture toughness. Comparisons are made with
bulk nonporous silicon and occasionally other materials. Emerging application
areas where the mechanical properties have primary importance are mentioned.
Finally, we identify specific mechanical properties where data is scarce and comment on perceived valuable areas for further research.
Youngs Modulus
The Youngs modulus of a material, sometimes called the modulus of elasticity,
quantifies its stiffness. Nonporous crystalline silicon has a value around 160 GPa,
higher than, for example, the metals aluminum, titanium, and copper, but much
lower than ceramics such as silicon carbide and diamond.
There are now a number of studies conducted on Youngs modulus as a
function of porosity in silicon, and the agreement between differing measurement
techniques is generally good for similar material (see Fig. 1 from Magoariec
et al. 2009).
Table 1 lists typical values for different types of porous silicon.
The higher the porosity, for similar pore size distributions and skeleton morphology, the lower the Youngs modulus. At the highest levels of mesoporosity
(with small pore size) studied, it can be reduced to values around 1 GPa,
even lower than that of polymers like nylon and polystyrene. For primarily
macroporous silicon, the reduction in stiffness versus porosity is less dramatic
(Wang et al. 2011).
215
140
X-Ray diffraction
Acoustic measurements
Nanoindentation
Brillouin scattering
Theoretical prediction
Young modulus (GPa)
120
100
80
60
40
20
0.1
0.2
0.3
0.4
0.5
0.6
Porosity
0.7
0.8
0.9
Fig. 1 Tunability of Youngs modulus of mesoporous silicon (Magoariec and Danescu 2009)
Table 1 Youngs modulus of porous silicon layersa over a range of porosities (3490 %), pore
size (meso-, macro), and silicon substrate types (p , p+, n+)
Method
Porous Sia
Nanoindentation
Meso- (p+) 36 %
60 %
80 %
90 %
Meso- (p+) 70 %
Meso- (p ) 80 %
Meso- (p+) 79 %
Meso- (n ) varied
Meso- (p+, p ) varied
Macro- 34 %
Macro- 48 %
Strain analysis
Acoustic microscopy
Nanoindentation
Nanoindentation
Nanoindentation
Calculated
Youngs modulus
Value (GPa)
50.9
18.8
5.5
0.87
1.5
1.25
10.4
5.552
327
72.1
45.2
References
Bellet et al. (1996)
Populaire et al. (2003)

Doghmane et al. (2006)
Fang et al. (2009)
Oisten et al. (2009)
Charitidis et al. (2011)
Wang et al. (2011)
Yield Strength
The yield strength of a material is the maximum stress it can withstand while being
stretched or compressed without breaking. Silicon has very high yield strengths
(7 GPa for single crystal and 1.5 GPa for polycrystalline). There is virtually no
216
L. Canham
quantitative data available to date on either the tensile or compressive strength of

porous silicon as a function of porosity. This is a valuable area for much further
research.
One study (Klyshko et al. 2008) created a meniscus-shaped porous silicon
structure in order to investigate tensile strength. A nonlinear decrease of strength
with increasing porosity was observed. A mesoporous layer (p + Si) of 50 %
porosity, for example, was reported to have less than 30 % of the strength of
bulk Si, but the control tensile strength was not given and so the accuracy of the
experimental approach is difficult to verify. Another study on porous silicon
derived from n-type wafers (Wang et al. 2011) gave remarkably low compression
strengths (in the range 0.250.35 GPa) at an estimated 34 % porosity. Here there
are concerns from the microscopy data that the layers underwent significant
degradation during air drying (see handbook chapter Drying Techniques
Applied to Porous Silicon) and wet surface modification treatments, prior to
mechanical testing.
Finally, a detailed study of mesoporous films generated by galvanic effects
(see handbook chapter Porous Silicon Formation by Galvanic Etching)
also reports a dramatic reduction in tensile strength as a function of etch time for
micromachined polycrystalline silicon (Miller et al. 2008). Porosity, estimated from
the morphology of layers, was in the range 2070 %. They commented that
nanoscale porosity alone (measured pore diameters were 515 nm) should change
Youngs modulus, but not strength, and attributed decreased strength to cracks
from etched as-fabricated defects and grain boundaries. Indeed, for corroded
single crystal structures, the tensile strength was decreased or increased,
depending on the etchant used. Mechanical failure analysis led to strength
changes being rationalized according to either a fracture mechanics or stress
concentration approach, depending on the surface wetting characteristics of the
etch chemistry.
Hardness
The hardness of a material quantifies its resistance to permanent shape changes
induced by applied mechanical forces such as friction or indentation by a sharp
object. Scratch resistance is often measured on the Moh 110 scale and indentation
hardness on the Vickers scale. Single crystal nonporous silicon has a Moh scale
hardness of 6 (for comparison, diamond is 10, quartz is 7, calcium carbonate is
3, talc is 1). It has a Vickers hardness of 11.5 GPa. There have now been a few
studies of the indentation hardness of porous silicon, with typical values for
different types of porous silicon listed in Table 2.
Clearly, like Youngs modulus, hardness decreases rapidly with increasing
porosity. Polymer-porous silicon composites (see handbook chapters Polymer Porous Silicon Composites and Porous Silicon and Conductive Polymer
Nanostructures Via Templating) are likely to have very low hardness but potentially high fracture toughness (see next section).
217
Table 2 Indentation hardness of porous silicon layersa over a range of porosities (3084 %) and
morphologies and the effects of impregnation and oxidation
Study objective
Porosity
dependence of
hardness
Porous Sia
Meso- (p+)
Effects of polymer
impregnation
Meso- (p+) and

heavily oxidized
Effects of oxidation
Meso- (p+)
Morphology
dependence of
hardness
Meso- (p+
vs. p )
Vickers hardness
value (GPa)
30 %
8.8
60 %
5.8
84 %
0.75
Dramatically lower in polymer
nanocomposite
0.050.15
6079% Significant increases
upon 300C oxidation
p+
1.42.4
References
Duttagupta
et al. (1997)
Ni
et al. (2005)
Fang
et al. (2009)
Charitidis
et al. (2011)
0.20.3
Fracture Toughness
Fracture toughness quantifies the resistance of a material to fracture when it
develops a crack. Ceramics like alumina and silicon carbide have a low fracture
toughness (35 MPa.m1/2) and are brittle; ductile metals in contrast have high
values (e.g., 1550 MPa.m1/2). Single crystal silicon has a fracture toughness of
only 0.6 MPa.m1/2 and so, like silica, is a very brittle material.
Very little data exists on the fracture toughness of porous silicon. However two
studies suggest that optimized nanocomposites (see hand book chapter Polymer Porous Silicon Composites) could exhibit much higher toughness than nonporous
silicon. An experimental study reported that the inclusion of poly-phenylene
vinylene polymers into oxidized mesoporous silicon could yield toughness values
more than five times higher than that of their bulk silicon control (Ni et al. 2005).
The maximum value reported for a polymer-impregnated mesoporous film on a
wafer was 4.2 MPa.m1/2. A particularly interesting theoretical study (Garcia
et al. 2010) proposed that the nanoscale porosity of silica in diatoms was responsible
for their remarkable toughness. Their calculations for idealized mesoporous silicon
predict a toughness that is extremely high for skeleton thicknesses in the range
12 nm and specific morphologies. This should be contrasted with the incredibly low
fracture toughness of ultrahigh porosity silica aerogels which can have measured
values as low as 0.0008 MPa.m1/2 (Phalippou et al. 1989).
Anisotropy of Mechanical Behavior

The directionality of electrochemical etching can give rise to strong spatial anisotropy
in the mechanical properties of mesoporous silicon (Populaire et al. 2003), as found for
other properties (see handbook chapters Optical Birefringence of Porous Silicon
218
L. Canham
and Electrical Transport in Porous Silicon). In a moderately oxidized 70 %

porosity layer generated from p + Si substrates, for example, the Youngs modulus
was estimated to be 0.44 GPa parallel to the predominant mesopore direction, but 1.5
GPa perpendicular to it (Populaire et al. 2003). We would expect less spatial mechanical anisotropy in mesoporous structures from p- substrates which have a more spongelike morphology (Charitidis et al. 2011). In sintered porous silicon (Martini et al. 2012),
much of this mechanical anisotropy is also lost. Nonetheless, this is another important
area for future research since many of the particulate porous silicon forms being
developed could have anisotropic porosity and hence mechanical properties.
Mechanical Properties of Nanoscale Solid Silicon

It is worth mentioning some specific mechanical phenomena reported for nanoscale
solid silicon, since these are the building blocks of porous silicon and clearly have
relevance. Silicon nanowires, for example, start to have significant changes in elastic
modulus below about 100 nm diameter (Sohn et al. 2010). At diameters below 60 nm,
they show significant plastic deformation before fracture, through the emission of
dislocations, amorphization, and necking (Han et al. 2007). Indeed, exceptional
plasticity has been recorded for stretched model bridge structures with elongations
of up to 20 times the original length prior to fracture (Ishida et al. 2011). Solid silicon
nanospheres also have higher hardness than microspheres (Gerberich et al. 2003).
Finally, it has been demonstrated with silicon nanobeams that mechanical properties
are sensitive to silicon surface chemistry: derivatized structures showed higher
strength and durability than hydride-terminated ones (Alan et al. 2006). Some data
exists on the effects of thermal oxidation for porous silicon (see Table 2) but none on
the effects of derivatization on mechanical properties, known to improve the
stability of numerous other properties (see handbook chapters Silicon-Carbon
Bond Formation on Porous Silicon and Chemical Reactivity and Surface
Chemistry of Porous Silicon). This would also be worth investigation.
Relevance of Mechanical Properties to Emerging Applications

Finally, Table 3 gives a number of diverse applications, reviewed in detail elsewhere in this handbook, where the mechanical properties are either the primary
factor in determining material suitability or play an important supporting role in
desired functionality.
Concluding Remark
This review has highlighted that there is currently significant data on the
stiffness and hardness of mesoporous silicon, but more data is needed on strength
and toughness. Remarkable mechanical properties have been seen with individual
219
Table 3 High relevance of mechanical properties of porous silicon to selected applications

Application
area
Acoustics
Drug
delivery
Lithium
batteries
Solar cells
Biofiltration
Tissue
engineering
Oral
hygiene
Aspect
Multilayer
acoustic reflectors
Maximizing drug
payload
Cycling stability
of anode
Layer transfer
Filtration
membranes
Use as a
biodegradable
scaffold
Use as a gentle
toothpaste
abrasive
Challenge
High reflectivity in thin
structures
Capillary forces during drug
loading
Accommodating lithiation
induced volume expansions
Facile fracture with low
interface roughness
Differential pressures across
membrane
Changing mechanical
properties during
biodegradation
Remove pellicle without
abrading tooth enamel
Desired mechanical
properties
Wide tunability of
acoustic velocity
Sufficient strength to
avoid matrix collapse
Ductility and high
fracture toughness
Low strength to
facilitate fracture
High strength yet high
permeability
Matched to those of
tissue being replaced
Low hardness but high
strength
silicon nanowires, such as exceptional plasticity. Clearly, the mechanical

properties of porous silicon deserve more scrutiny and optimization, especially
for important application areas such as lithium batteries, where porosity
engineering and morphology optimization is critical to avoid silicon anode fracture
during cycling.
References
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Fang Z, Hu M, Zhang W, Zhang X, Yang H (2008) Thermal conductivity and nanoindentation
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220
L. Canham
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techniques. Thin Solid Films 517(9):29302935
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deformability. Comput Mater Sci 48:303309
Gerberich WW et al (2003) Superhard silicon nanospheres. J Mech Phys Solids 51(6):979992
Gibson LJ, Ashby MF (1997) Cellular solids: structure and properties, 2nd edn. Cambridge
University Press, Cambridge, UK
Han X, Zheng K, Zhang YF, Zhang X, Zhang Z, Wang ZL (2007) Low temperature in situ largestrain plasticity of silicon nanowires. Adv Mater 19(16):21122118
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Solidi 6(7):16801684
Martini R et al (2012) Mechanical properties of sintered mesoporous silicon: a numerical model.
Miller DC, Boyce BL, Kotula PG, Stoldt CR (2008) Connections between morphological and
mechanical evolution during galvanic corrosion of micromachined polycrystalline and monocrystalline silicon. J Appl Phys 103:123518
Ni H et al (2005) Nanoscale structural and mechanical characterization of bamboo-like polymer/
silicon nanocomposite films. Nanotechnology 16:17461753
Oisten MK et al (2009) A Youngs modulus study of n- and p-type porous silicon. Phys Stat Solidi
A 206(6):12781281
Peterson KE (1982) Silicon as a mechanical material. Proc IEEE 70(5):420
Phalippou J et al (1989) Fracture toughness of silica aerogels. Revue De Phys Appl C4
(24):191196
Populaire CH et al (2003) On mechanical properties of nanostructured mesoporous silicon. Appl
Phys Lett 83:1370
Rahmoun K et al (2009) A multilayer model for describing hardness variations of aged porous
silicon low-dielectric constant thin films. Thin Solid Films 518:213221
Rice RW (ed) (1998) Porosity of ceramics. Marcel Dekker, New York
Sohn YS et al (2010) Mechanical properties of silicon nanowires. Nanoscale Res Lett 5:211216
Wang F et al (2011) Conciliating surface superhydrophobicities and mechanical strength of porous
silicon films. Appl Surf Sci 257:27522755
Mesopore Diffusion Within Porous Silicon

Jorg Karger and Rustem Valiullin
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diffusion in the Capillary-Condensed Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Surface Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diffusion as a Function of Phase State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Macroscopic Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
222
222
224
225
227
228
Abstract
In many applications exploiting mesoporous silicon (PSi), their performance

may be controlled by the rate of diffusive propagation of the confined molecules.
The pulsed field gradient technique of nuclear magnetic resonance provides the
most direct access to molecular diffusion. The different factors determining the
diffusivities in PSi are reviewed. In particular, diffusivities in liquid state are
shown to be most strongly affected by mesoscale disorder. Atomistic disorder is
shown to control surface diffusion in applications in which PSi is brought into
contact with gas phases at low vapor pressures. Correlations between the compositions of phases coexisting within the pore space, namely, liquid and gaseous,
and liquid and solid ones, respectively, are briefly discussed.
J. Karger (*) R. Valiullin

e-mail: kaerger@physik.uni-leipzig.de
DOI 10.1007/978-3-319-05744-6_22
221
222
J. Karger and R. Valiullin
Introduction
Molecular transport is an important process playing a key role in various applications
exploiting porous silicon, such as gas sensing or biomedicine (Schechter et al. 1995;
Kovalev and Fujii 2005; Prestidge et al. 2007). In these particular cases, the substances of interest (chemicals, rare elements, pharmaceuticals, biomolecules) have to
be transported into or out of inner pore spaces within the PSi particles. The effective
transport rate may, hence, determine the time lag of, e.g., the optical response and the
intensity of this response after having brought the PSi into contact with the gas
atmosphere containing the chemicals to be sensed. Similarly, molecular transport can
strongly affect the release rate of pharmaceuticals from the PSi material to which
they are confined upon getting into contact with a particular environment in the
human body (see handbook chapter Drug Delivery with Porous Silicon).
Among the methods of studying molecular diffusion in porous media, and in
porous silicon in particular (see Table 1), the pulsed field gradient technique of NMR
spectroscopy (PFG NMR) is of particular relevance (Callaghan 2011). As a noninvasive method, it allows the observation of molecular migration without interfering
with the internal processes. The technique is based on the creation of an initial
nuclear coherence and following its loss due to the molecular displacements in an
applied magnetic field gradient. Thus, the characteristics of molecular motion under
equilibrium conditions may be followed in a broad timescale, from milliseconds to
seconds. In the most relevant cases, however, transport in porous materials occurs
under (quasi)-equilibrium conditions, rendering the diffusive dynamics being the
decisive mode for molecular transport. Exactly for these reasons, this mini-review
will mostly focus on diffusion studies using PFG NMR applied to highly anisotropic
mesoporous silicon with tubular pore morphology prepared from anodization of
p + silicon wafers (Lehmann et al. 2000). Such anisotropy is evident, for example,
in its optical constants (see handbook chapter Optical Birefringence of Porous
Silicon), electrical current flow ( Electrical Transport in Porous Silicon), and
mechanical behavior ( Mechanical Properties of Porous Silicon).
Complementary to PFG NMR is quasi-elastic neutron scattering (QENS) (Jobic
and Theodorou 2007), which has a unique potential to monitor molecular displacements over the range of nanometers. However, among the various features, brought
about by the procedure of PSi fabrication, it is in particular the intrinsic mesoscalic
disorder which plays a crucial role in determining the material properties. These
inhomogeneities may lead to additional transport resistances which remain
unobservable with molecular displacements in the nanometer range as accessible
by QENS but are effective for the long-range displacements followed by PFG NMR.
Diffusion in the Capillary-Condensed Liquid

Under the condition of spatial confinement, two mechanisms may give rise to a
slowing down of the rate of molecular rearrangements. These are (i) surface
interaction of the confined species with the PSi pore walls and (ii) purely geometric
223
Table 1 A survey of the experimental method applied to study molecular transport in porous
silicon
Method
PFG NMR
Neutron
scattering
Gas
permeation
Permeability
measurements
Optical
interferometry
and
refractometry
Liquid or adsorbed phases

(study ref. numbers)
Valiullin et al. (2004,
2005a), Valiullin and
Khokhlov (2006),
Kondrashova et al. (2011)
Hofmann et al. (2012),
Kusmin et al. (2010)
Gas phase (study ref.

numbers)
Valiullin et al. (2004)
Measuring
principle
Equilibrium
conditions
Gaburro et al. (2001),

Lysenko et al. (2004),
Gruener and Huber (2008),
Kavalenka et al. (2012), Li
et al. (2013)
Nonequilibrium
conditions
Ileri et al. (2012), Desai

et al. (1999), Velleman
et al. (2010), de Smet
et al. (2002)
Mares and Weiss (2011),
Acquaroli et al. (2011),
Anglin et al. (2004), Wu
and Sailor (2013)
effects accounted for by the tortuosity factor. Their relative contributions can most
easily be separated by probing molecular diffusivities on length scales shorter and
much longer than the pore size. Recently, the former type of measurement has been
performed by using QENS with n-hexane as guest molecule within PSi with an
average pore diameter of 6 nm (Hofmann et al. 2012). Following molecular
displacements over a length scale of up to 0.65 nm, the diffusivities were obtained
to be smaller than the bulk diffusivities by not more than 30 %. This rather
moderate slowing down can be easily attributed to the existence of a less mobile
layer of n-hexane near the pore walls.
A totally different picture emerges from measurements by using PFG NMR. In
this case, the molecular trajectories are traced on a length scale above hundreds of
nanometers, notably exceeding the pore dimension. The data of Table 2 show that
the diffusivities in PSi with comparable pore diameters, as considered in the QENS
study, measured in the direction parallel to the channel axes are found to be few
times slower than the bulk diffusivity. This fact indicates that, in addition to
moderate surface effects, molecular diffusion over long distances is strongly
affected by heterogeneities in the pore structure.
The origin of these effects of heterogeneity may be quite different. First of all, it
is well established that mesoporous silicon possesses a substantial degree of
disorder, which is associated with the atomistic disorder of the pore walls and a
strong variation of its pore diameter along the pore axis (Wallacher et al. 2004;
Guegan et al. 2006; Naumov et al. 2008a, 2009; Dvoyashkin et al. 2008; Cerclier
et al. 2012). This variation may give rise to constrictions which act as additional
224
Table 2 Self-diffusivities D|| ( 1010 m2/s) in channel direction of different liquids in

mesoporous silicon of different average pore diameters measured using PFG NMR at 25 C.
The last column shows the bulk diffusivities
Average pore size
Water
Nitrobenzene
Cyclohexane
n-Eicosane
5.6 nm
5.2
1.2
3.2
0.26
6.6 nm
2.5
6.2
0.76
8.0 nm
3.3
7.6
0.95
10.4 nm
3.8
9.0
1.2
Bulk
23.0
6.9
14.2
transport resistances, blocking long-range diffusion in axial direction (Petersen

1958; Burada et al. 2009; Berezhkovskii et al. 2007). Such an explanation would
additionally be supported by the strong decrease in the effective diffusivities
observed with decreasing average pore diameter.
Further on, the occurrence of side channels, accompanied by the formation of
dead-end pores and intersections between the individual channels and, hence, an
increase in tortuosity, may also lead to decreasing long-range diffusivities
(Cussler 2009). Indeed, the emergence of such intersections with increasing
etching current and, therefore, porosity for the materials quoted in this study has
experimentally been proven by investigating diffusion anisotropy in PSi (Naumov
et al. 2008a). Thus, the ratio D||/D between the diffusivities measured in the
directions parallel and perpendicular to the channel axes was found to be >104 in
PSi with a pore diameter of 6 nm, showing that any significant contribution of
channel intersections to overall transport could be ruled out, while in PSi with
channels broadened to 9 nm, this ratio was found to drop to 50. This indicates that
mass transfer perpendicular to the channel direction is now notably facilitated
which testifies the existence of a substantial number of intersections between the
different channels.
Surface Diffusion
In contrast with the situation with capillary condensation so far considered, under
the conditions of low-pressure atmospheres in contact with PSi, surface diffusion
can become the key mechanism of mass transfer. Upon hitting the PSi surface, gas
molecules may get physisorbed. If the heat of desorption exceeds substantially the
activation energy required for molecular hops along the surface, molecular translation in the channel direction will mainly proceed by such hops. This process is
referred to as surface diffusion (Gomer 1990). Its different aspects have thoroughly
been addressed experimentally using atom microscopy and optics and using computer simulation approaches (Renisch et al. 1999; Ala-Nissila et al. 2002). The
experimental techniques mentioned are limited, however, to operate with flat
surfaces. It has recently been demonstrated that, benefitting from the option of
accommodating up to 1018 nuclear spins on the large inner surface of mesoporous
silicon, PFG NMR may serve as an excellent tool for probing surface diffusion in
PSi (Valiullin et al. 2005a; Dvoyashkin et al. 2009).
225
Fig. 1 Arrhenius plot of

surface diffusivities for nheptane in porous silicon with
an average pore diameter of
5.6 nm for different surface
coverages c (Dvoyashkin
et al. 2009)
In striking contrast to adatom diffusion on flat metal surfaces, the surface

diffusivity of organic molecules in PSi was found to increase with increasing
surface coverage. Moreover, it was found that the apparent activation energy for
diffusion decreases with increasing surface loading (see Fig. 1). These two facts are
to be associated with strong surface heterogeneities in geometry and/or chemical
nature. These heterogeneities give rise to a complex landscape in the site energies
and, correspondingly, a notable distribution in the residence (or hopping) times. At
a given surface coverage, molecules will therefore tend to occupy vacant sites with
the lowest site energies available (corresponding to the longest residence times).
This phenomenon may be used to tune molecular transport through porous silicon
by surface modification (see handbook chapter Silicon-Carbon Bond Formation
on Porous Silicon) (Velleman et al. 2010).
Diffusion as a Function of Phase State

With emerging potential applications of nanostructured porous silicon as, e.g., optical
switches (Barthelemy et al. 2007) or drug delivery containers (Prestidge et al. 2007),
the knowledge of correlations between diffusive transport of confined guests and
their phase state is of practical relevance. The occurrence of such correlations has
recently been demonstrated for both gasliquid and solidliquid coexistences of
fluids in the pore spaces of mesoporous silicon (Dvoyashkin et al. 2008; Valiullin
et al. 2004; Kondrashova et al. 2011). Due to strong confinement effects and intrinsic
geometric disorder, the phase state, namely, the phase composition, of confined fluids
is typically found to be smeared out over a sufficiently broad range of the external
conditions. Because transport mechanisms in different phases can be different, like in
gaseous and liquid phases, or one phase can form impermeable regions for molecular
transport, like the crystalline phase formed upon freezing, under otherwise identical
conditions, transport can also be most significantly affected by a change in the phase
226
Fig. 2 Effective diffusivities

of cyclohexane in PSi with an
average pore diameter of
10 nm as a function of the
relative gas pressure z at room
temperature (Valiullin
et al. 2005b)
composition. Understanding their relationships may thus become most useful in

optimizing the relevant processes in potential applications.
For gasliquid equilibria in pores, transport may include combinations of surface
diffusion, diffusion in multilayers adsorbed on the pore walls, diffusion in capillarycondensed phase, and Knudsen diffusion in the gaseous phase. At very low external
gas pressures, corresponding to sub-monolayer surface coverages, surface diffusion
is typically the rate-determining transport mechanism for most organic liquids at
moderate and low temperatures. Upon further increase of the external gas pressure,
multilayers of guest molecules are formed on the pore walls. Due to the increased
density of the gaseous phase and a weaker guestguest interaction (compared with
the guestpore wall interaction), the desorptionadsorption events, intermittent
with Knudsen flights in the pore interior, may substantially contribute to the
overall mass transfer, as demonstrated by Fig. 2, and cannot be neglected anymore.
Notably for inert gases, which are weakly adsorbed on the pore walls, Knudsen
diffusion can be the major transport mode. In this regime, the diffusivities are
proportional to one third of the product of the average thermal velocity and average
pore diameter (Pollard and Present 1948). It has recently been discussed that the
irregular pore shape in PSi may also affect the resulting effective diffusivities in the
Knudsen regime (Gruener and Huber 2008).
At even higher vapor pressures, the molecular pathways are further complicated
by the inclusion of diffusive transport through domains of capillary-condensed liquid.
Notably, these domains are formed at gas pressures well below the saturation
pressure, exemplifying confinement effects upon phase transitions. The impact of
these domains on the diffusion properties of the fluid is twofold. First of all, their
presence decreases the relative volume available for the gaseous phase, typically
leading to a corresponding decrease of the effective diffusivity. In addition, there is
experimental evidence that geometrical features of the spatial distribution of these
domains do also play a decisive role. Indeed, in line with adsorption hysteresis,
hysteresis is as well observed in the diffusivities, exhibiting quite different scenarios
for the processes of emptying and filling of the pore space (Naumov et al. 2008b).
227
Fig. 3 Effective diffusivities

of nitrobenzene in
mesoporous silicon with an
intentionally created random
variation of the pore diameter
from 6 to 12 nm measured
upon warming (Kondrashova
et al. 2011)
Figure 3 shows effective diffusivities of guest molecules measured at different

temperatures, corresponding to different compositions of the frozen and liquid
phases in the pores. The measurements have been performed starting from low
temperatures, at which the liquid was in the frozen state. At these temperatures,
diffusion takes place along a nonfrozen surface film of a few monolayers between
the pore wall and the frozen core. Upon heating, a progressive melting of the frozen
domains, starting from the pores with smallest dimensions as predicted by the
GibbsThomson equation (Jackson and McKenna 1990), does occur. Thus, more
and more free space becomes available for diffusion, leading to increasing effective
diffusivities with an apparent activation energy notably different from that of the
bulk liquid. It is worth mentioning that different distributions of the frozen domains,
which are attained during either freezing or melting, may result in different
diffusivities at identical phase compositions due to different tortuosities
(Dvoyashkin et al. 2008).
Macroscopic Transport
With the microscopic diffusivities as accessed using PFG NMR, the exchange rates
between the molecular ensembles confined to PSi particles and surrounding them in
the environment can be easily modeled (Carslaw and Jaeger 1946). To do this, the
size of PSi particles, their shape, and the internal pore space anisotropy have to be
known. Thus, for mesoporous silicon with channel-like pore geometry and a
thickness L of the porous film, the average lifetime of molecules within the porous
film may be found as L2/12D, where D is the intraparticle diffusivity. If the
relevant structural parameters are not known, the average exchange rates may be
assessed experimentally using PFG NMR. The respective approach is known as
tracer desorption technique (Karger et al. 2012). Its application can be based on the
difference in the diffusivities in the pores and in the surrounding space, allowing to
identify the relative fraction p of molecules in the overall NMR signal which,
228
during a fixed observation time t, have never left the intrapore space (Valiullin
et al. 2009). This quantity is directly relevant for drug delivery and reflects the
release rates of pharmaceuticals from the encapsulating body. Depending on physicochemical conditions, including size of molecular species, solvent properties,
surface chemistry, etc., they may vary from inverse seconds, for small molecules, to
inverse hours, for larger polymeric species. The option of PSi microstructuring and
surface modification may be used to effectively tune the release rates by affecting
the intrapore diffusion (Velleman et al. 2010; Kondrashova et al. 2011; Wu and
Sailor 2013).
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Refractive Index of Porous Silicon

Honglae Sohn
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Data Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fresh Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxidized Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Multilayer Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
232
232
236
238
240
242
Abstract
The optical properties of porous silicon layer described as a mixture of air, silicon,
and silicon dioxide are determined by the thickness, porosity, refractive index, and
the shape and size of pores. Refractive index of porous silicon is reviewed in this
chapter. Full theoretical solutions can be provided by different effective medium
approximation methods such as MaxwellGarnetts, Looyengas, or
Bruggemans. In the case of semiempirical approaches, the refractive indices
are measured using spectroscopic ellipsometry, and then, the model parameters,
such as the layer thickness and calculated effective dielectric function, are
adjusted to fit the spectra. Various methods based on optical transmission and
reflection measurements are used to calculate the refractive index data for both
fresh and oxidized porous silicon using the envelope, MaxwellGarnett, and
Goodman method. The coherent transfer matrix technique and Heavens theory
were used to determine the complex refractive index of porous silicon for the
reflectance of an absorbing layer on an absorbing substrate. An ab initio quantum
mechanical study of the effects of oxidation process in porous silicon using an
interconnected supercell structure and its complex refractive index was compared
H. Sohn (*)
Department of Chemistry, Chosun University, Gwangju, Republic of Korea
e-mail: hsohn@chosun.ac.kr
DOI 10.1007/978-3-319-05744-6_25
231
232
H. Sohn
with experimental data obtained from spectroscopic ellipsometry. The spectroscopic ellipsometry evaluation of a porous silicon multilayer was reported for the
preparation of porous silicon multilayer stacks. The effects of oxidation on the
Bragg reflector parameters and the variations in the refractive index and thickness
after oxidation were reported.
Introduction
Porous silicon materials are described as a mixture of air, silicon, and, in some
cases, silicon dioxide. The optical properties of a porous silicon layer are determined by the thickness, porosity, refractive index, and the shape and size of pores
and are obtained from both experimental- and model-based approaches. Porous
silicon is a very attractive material for refractive index fabrication because of the
ease in changing its refractive index. Many studies have been made on one- and
two-dimensional refractive index lattice structures. The refractive index is a complex function of wavelength, i.e., n() n() ik(), where k is the extinction
coefficient and determines how light waves propagate inside a material (Jackson
1975). The square of the refractive index is the dielectric function: () n()2,
which contributes to Maxwells equations.
The refractive index depends on the propagation of light as well as the reflected
and transmitted fractions of incident waves on an interface. The Fresnel coefficients
for reflection and transmission are given by the refractive indices of the two
adjacent materials. For many applications of porous silicon in optics or optoelectronics, it is necessary to know the exact refractive index (see, e.g., chapters
Porous Silicon Photonic Crystals Porous Silicon Optical Waveguides
Porous Silicon Diffraction Gratings Porous Silicon Optical Biosensors).
Herein, the methods to obtain the refractive index from various types of porous
silicon are discussed.
Data Evaluation
Porous silicon can be specified as an effective medium, whose optical properties
depend on the relative volumes of silicon and pore-filling medium. Full theoretical
solutions can be provided by different effective medium approximation methods
such as MaxwellGarnetts, Looyengas, or Bruggemans (Arrand 1997). Effective
medium theory describes the effective refractive index, neff, of porous silicon as a
function of the complex refractive index of silicon, nSi, and that of the pore-filling
material, nair 1, for air. The porosity P and the topology of the porous structure
will also affect neff (Theiss et al. 1995).
The most frequently used effective medium models are the Bruggeman approximation (Bruggeman 1935), the Looyenga formula (Looyenga 1965), and the
MaxwellGarnett mixing rule (Garnett 1904). The Bruggeman approximation is
given by

Fig. 1 Refractive index of
bulk silicon (solid line: real
part; dashed: imaginary part)
(Data from Aspnes and
Studna 1983)
233
8
Refractive index
7
6
5
4
3
2
1
0
1
Energy [eV]
1 n 2eff
n 2 n 2eff
1 P 2Si
0
2
1 2neff
n Si 2n2eff
(1)
It is adequate for irregularly shaped particles with low porosities and shows good
agreement with experimental data for as-etched meso-porous silicon (Snow
et al. 1999; Pap et al. 2006). The Looyenga model is suitable for high porosities
(Zettner et al. 1998) and is given by
2=3
n eff 1 Pn3eff P
(2)
The MaxwellGarnett formula describes isolated silicon particles embedded in a

vacuum matrix and is given by
1 n 2eff
n 2Si 1
0
1

P
n 2Si 2
2 n 2eff
(3)
Both Bruggeman and Looyenga exhibit an increased refractive index compared

to the MaxwellGarnett formula, due to the interconnection of the silicon network
(Theiss 1997; Theiss and Hilbrich 1997). For a porosity P of 30 % and a wavelength
between 300 and 1,500 nm, the calculation deviates only 3 % from the Bruggeman
formula and 10 % from the Looyenga model, whereas the deviation from the
MaxwellGarnett model is 74 % (Wolf et al. 2008).
Figure 1 shows the refractive index of bulk silicon. The application of different
effective medium theories leads to different results. Figure 2 shows the comparison
of the dependency of refractive index on porosity, determined by different effective
medium approaches. A value of 3.4 for the infrared bulk value has been taken for
234
H. Sohn
Fig. 2 Refractive index (real

part) versus porosity, given by
some effective medium
approaches (Data from Theiss
and Hilbrich 1997)
3.5
Mixing rule
Lower bound (Maxwell Garnett)
Looyenga
Bruggeman
Upper bound
Refr. index
3.0
2.5
2.0
1.5
1.0
0
20
60
40
Porosity [%]
80
100
the solid pore wall phase. The refractive index of porous silicon is expected to be
lower than that of silicon, as porous silicon is a two-phase composite, being a
mixture of air and solid phase (Theiss and Hilbrich 1997).
The optical properties are determined experimentally from the transmission or
reflection spectra using, for example, the envelope method or the Fresnels equation
(Manifacier et al. 1976; Laghla and Sched 1997). The traditional method to
determine the refractive index of porous silicon takes into account that the pore
size is much smaller than the wavelength of visible light. Porous silicon behaves
then as a continuous material. However, porous silicon is more complex due to a
large distribution of pores sizes. A simple method to determine the refractive index
of a material is to observe the interference fringes. The refractive index can be
calculated directly from the frequency difference of neighboring interference maxima of minima, when the layer thickness d is determined independently. However,
these procedures are limited when the materials have strong optical absorption or
scattering effects. In the case of semiempirical approaches, the refractive indices
are measured using spectroscopic ellipsometry, and then, the model parameters,
such as the layer thickness and calculated effective dielectric function, are adjusted
to fit the spectra (Theiss 1997; Theiss and Hilbrich 1997; Jellison and Modine
1994). The optical parameters using the transfer matrix method were varied to find
the best fit to the measured spectra (He and Cada 1992). Equation 4 can be used to
measure the real part of the refractive index of porous silicon through the interference fringes of the transmittance (T), or reflectance (R), spectra (Theiss et al. 1995;
Bruggeman 1935).
n
1
2d1=2 1=1
(4)
235
1 and 2 are the wavelength values of two successive maxima or minima of the
spectra, and the thickness (d) is measured independently. The use of Eq. 4 has
several restrictions; it can only be applied in the infrared region where n is approximately constant and neglects absorption. It cannot be used from the visible to UV
region where strong absorption exists. For an absorbing and slightly absorbing thin
film, the refractive index is a complex function and may be obtained by spectroscopic ellipsometry from its optical transmittance and reflectance spectra
(Bisi et al. 2000).
Table 1 lists the information for the type of porous silicon structure, porosity,
method and model, and spectral range.
Table 1 Information on the refractive index for various types of porous silicon
Porous
silicon
structure
Single layer
Porosity
(%)
2362
Single layer
75
Freestanding
4060
Single layer,
freestanding
3080
Freestanding
40
Single layer,
freestanding
6087
Single layer
1550
Oxidized
3463
Oxidized
1080
Oxidized
40
Data
information
Refractive
index versus
porosity
Refractive
index versus
wavelength
Refractive
index versus
wavelength
Refractive
index versus
porosity
Refractive
index versus
wavelength
Refractive
index versus
wavelength
Refractive
index versus
porosity
Refractive
index versus
porosity and
oxidation
degree
Refractive
index versus
porosity
Refractive
index versus
wavelength
Method/model
Fresnel, leastsquares fit
Spectral
range
(nm)
632.8
Reference
Krzyzanowska
et al. (1999)
Direct
measurement
500770
Strashnikova
(2002)
Envelope/
Bruggeman
7001700
Pap
et al. (2006)
Goodman/
Bruggeman
Khardani
et al. (2007)
KM theory/
Lambertian
5001500
Wolf
et al. (2008)
Heavens
3002,500
Arenas
et al. (2010)
Semi-analytical/
Bruggeman
632.8
Bazaru
et al. (2010)
Bruggeman leastsquares fit
632.8
Astrova
et al. (1999),
Astrova and
Tolmachev
(2000)
Pan
et al. (2005)
250850
Cisneros
et al. (2007)
Serialparallel
model
Fresnel, ab initio
(continued)
236
H. Sohn
Table 1 (continued)
Porous
silicon
structure
DBR
Porosity
(%)
3590
DBR
3590
DBR
3590
Gradient
63
Data
information
Refractive
index versus
applied
current
Refractive
index versus
wavelength
and applied
current
Refractive
index versus
wavelength
and applied
current
Refractive
index versus
wavelength
and applied
current
Method/model
Bruggeman
Spectral
range
(nm)
400800
Reference
Volk
et al. (2003)
Genetic
algorithm
400800
Torres-Costa
et al. (2004)
Fresnel
400900
Nava
et al. (2009)
KramersKronig
analysis
400850
Shokrollahi
et al. (2012)
Fresh Porous Silicon

Fresh etched porous silicon is described as a mixture of air and silicon. Various
methods based on optical transmission and reflection measurements are used to
calculate the refractive index data for porous silicon layers. The refractive index can
be determined by multiple-angle-of-incidence ellipsometry. Ellipsometry allows
very accurate determination of the optical constants. The multiple-angle-of-incidence ellipsometry study was investigated to evaluate the refraction indices, as well
as the porous silicon layer thickness values for samples of different porosities, from
23 % to 62 % (Krzyzanowska et al. 1999). From the ellipsometric measurements of
the incidence angle with the Fresnel complex refection coefficients, the transmitted
light intensity increases with increased porosity, and the refractive index decreases.
The refractive index in the violet spectral range, where strong absorption exists, is
obtained from the direct measurement of the change in phase of the transmitted
wave (Strashnikova 2002).
The optical parameters from reflection measurements on freestanding samples
indicated that optical scattering at the airporous silicon interface is the principal
reason for the loss of transmitted light intensity and for the inaccurate results
obtained by the envelope method. The porous silicon showed poor transparency
at shorter wavelengths ( < 800 nm), due to strong optical absorption in silicon.
Therefore, the experimentally determined refractive index is always larger than that
predicted by Bruggemans method. The mean of the relative difference between
2.4
2.2
Refractive index
Fig. 3 Refractive index

versus porosity for
nanoporous silicon obtained
from experiment () and the
prediction of the effective
medium theory for
nanoporous silicon () (Data
from Khardani et al. 2007)
237
2.0
1.8
1.6
1.4
1.2
30
40
50
60
Porosity (%)
70
80
3.0
2.8
2.6
Refractive index
2.4
2.2
2.0
1.8
1.6
1.4
1.2
30
40
50
60
70
80
Porosity (%)
Fig. 4 Refractive index versus porosity for freestanding meso-porous silicon obtained from
experiment () and the prediction of the effective medium theory () (Data from Khardani
et al. 2007)
experimental and theoretical values is 9.1 % with a standard deviation of 4.4 % (Pap
et al. 2006). The effective refractive indices of silicon-supported and freestanding
porous silicon layers were evaluated from the transmission spectra by applying the
Goodman method (Khardani et al. 2007). Good agreement between theory and
experiment was found in the case of silicon-supported meso-porous silicon for
all porosities (Fig. 3). However, for freestanding meso-porous silicon (Fig. 4),
238
H. Sohn
the Bruggeman effective medium theory fits the experimental results only for
porosities ranging between 50 % and 70 % (Khardani et al. 2007).
The coherent transfer matrix technique was used to calculate the specular reflection and transmission of porous silicon. In the wavelength range from 500 to 1,500
nm, the refractive index of porous silicon obtained using effective medium theory
and Mie scattering is 1935 % below the value for bulk silicon. Except for the
MaxwellGarnett formula, the measured values agree with the predictions of the
effective medium models for 500 < <1,000 nm. For wavelengths above 1,000 nm,
three models (Bruggeman, Looyenga, and the linear interpolation) overestimate the
refractive index, and the measured data are closer to the predictions of the
MaxwellGarnett mixing rule. In the visible range, the refractive index of porous
silicon agrees with the Looyenga, Bruggeman, and simple linear model, whereas in
the IR, the MaxwellGarnett formula gives a better match (Wolf et al. 2008).
Heavens (Arenas et al. 2010) has established analytical relations between transmittance and reflectance spectra to obtain the complex refractive index and thickness of thin films as functions of wavelength. Based on the Heavens theory, the
complex refractive index of porous silicon on a crystalline silicon substrate at
different wavelengths was determined for the reflectance of an absorbing layer on
an absorbing substrate. The real refractive index values of the porous silicon
samples decrease as their porosity increases. The use of interference fringes gives
similar values of n, only for the near infrared region. The strong absorption of
porous silicon in UVVIS leads to a major deviation (Arenas et al. 2010). The
experimental values of neff using a Fresnel-type relation between reflectivity and
effective linear refractive index were compared with the theoretical predictions
using a semi-analytical formula and the Bruggeman model in the range of 1550 %
porosity (Bazaru et al. 2010).
Oxidized Porous Silicon

The use of porous silicon, based on the ability to change the optical constants n and
k with porosity P, is very promising. However, porous silicon, especially highporosity porous silicon, is an unstable material and its properties change during
storage and operation due to oxidation. Thermal oxidation is an established method
of passivating freshly etched porous silicon (see chapter Oxidation of
Macroporous Silicon). Therefore, the relationship between the refractive index,
porosity, and oxidation degree is important to know. This relationship has been
calculated in the framework of the three-component Bruggeman effective medium
model (silicon, SiO2, and pores). The oxidation and composition (porosity and SiO2
content) of porous silicon films were measured by ellipsometry at a single wavelength. The aim was to investigate the variation of optical constants and thickness,
as functions of subsequent heat treatment. The refractive index and porosity in
relation to the oxidation degree in the framework of the Bruggeman effective
medium model and the determination method for the porous silicon composition
have been reported (Astrova et al. 1999; Astrova and Tolmachev 2000). Calculated
60%
70%
239
pin
90%
80%
100
Oxidation degree of silicon carcass s,%
pin = 50%
80
60
40%
Si + SiO2
30%
40
20%
20
0
1.0
1.5
2.0
2.5
3.0
Refractive index n
Fig. 5 Calculated curves characterizing the relation between the refractive index of oxidized
porous silicon and the degree of oxidation of the silicon base layer, 632.8 nm. The Si + SiO2
curve corresponds to a film in which no voids are left after oxidation; Pin is the initial porosity of
the unoxidized film (Data from Astrova et al. 1999)
curves relating the degree of oxidation of the silicon base layer to the refractive
index at 632.8 nm for films with various initial porosities are shown in Fig. 5.
Figure 6 shows how the porosity of the layer varies as n decreases because of
oxidation. The refractive index, optical thickness, and extinction coefficient of
porous silicon films decrease monotonically, but film thickness increases as the
degree of oxidation of the silicon base layer increases. The composition of the films
are determined from the measured refractive index at 632.8 nm, by means of
curves calculated on the basis of the three-component Bruggeman model for layers
with different initial porosities. Porous silicon with Pin > 56 % remains porous even
after 100 % oxidation of the silicon, and those with lower Pin become poreless at a
particular value of oxidation degree and form another two-component system:
SiSiO2. As oxidation proceeds, the refractive index and optical thickness of the
film decreases gradually, whereas the film thickness increases (Astrova and
Tolmachev 2000). The dependence of the relative thickness of the porous silicon
layer d/d0 on the degree of oxidation of the silicon base layer is reported (Astrova
et al. 1999; Astrova and Tolmachev 2000).
240
H. Sohn
100
80
Si + V
Porosity p, %
60
40
20
SiO2 + V
0
1.0
1.5
2.0
Refractive index n
2.5
3.0
Fig. 6 The porosity versus the refractive index of oxidized porous silicon, calculated for
various initial porosities pin of the unoxidized film, 632.8 nm. The dot-dashed curves
representing Si + V (porous silicon) and SiO2 + V (porous oxide) bound the region of values
having physical significance; Pin is determined from the point of intersection of the p-n curve with
the Si + V curve (Data from Astrova and Tolmachev 2000)
The refractive index and thickness, as well as the optical constants of the
photoluminescent porous silicon, were determined by measuring the dependence
on the angle of incidence of the reflected light intensity measured for three wavelengths of the visible spectral region (Makara et al. 1999). The relative thickness of
the porous silicon layer, d/d0 1.33, on the degree of oxidation of the silicon base
layer is due to the 98 % oxidation of the silicon base layer in columnar structure of
porous silicon (Astrova and Tolmachev 2000). A serialparallel model for the
porosity and oxidation dependence of dielectrics for porous silicon has thus been
reported. Predictions agree with experimental results, which enable us to measure the
extent of oxidation (Pan et al. 2005). An ab initio quantum mechanical study of the
effects of oxidation process in porous silicon using an interconnected supercell
structure and its complex refractive index was also reported and compared with
experimental data obtained from spectroscopic ellipsometry (Cisneros et al. 2007).
Multilayer Porous Silicon

There has been growing interest in the development of efficient control for the
preparation of porous silicon multilayer stacks (see chapter Porous Silicon
Multilayers and Superlattices). As porous silicon porosity is a function of the

100
90
3.0
Porosity (%)
80
70
2.5
60
PS
Fig. 7 Porosity and

refractive index (at 600 nm)
of porous silicon versus
current density. The samples
produced with the electrolyte
composition of hydrofluoric
acid, ethanol, and glycerin in
a ratio of 3:7:1 give a
refractive index contrast
around 1.3/2.8 at 600 nm
(Data from Nava et al. 2009)
241
50
2.0
40
30
1.5
20
10
0
10
15
20
25
30
2
(mA/cm )
35
40
45
1.0
current density, different refractive indexes of porous silicon layers can be built up,
one after another, on a silicon substrate in the vertical direction by alternating the
applied current densities during the electrochemical etching. The refractive index
contrast between the dielectric materials plays a crucial role on the photonic
properties. The quality of porous silicon multilayers in photonics can be improved
if the refractive index contrast between layers is increased. The bandgap widening
of porous silicon due to quantum confinement effects leads to a decrease of the
extinction coefficient k, making porous silicon transparent in the infrared region.
Berger et al. proved the feasibility of fabrication of high reflectivity porous silicon
mirrors, Bragg reflectors, and rugate filters (Berger et al. 1997). The Bragg reflector
is characterized by its central wavelength 0 (at normal incidence) and by the
reflection bandwidth which is determined mainly by the index contrast. Interference
filters in the IR have been demonstrated with good spectral behavior due to the low
absorption of porous silicon in this wavelength range. To achieve the same degree
of performance in the visible range, the layers of higher porosity are required to
further reduce the value of k, thus blue-shifting the absorption edge. The spectroscopic ellipsometry evaluation of a porous silicon multilayer was reported for the
process design and control for the preparation of porous silicon multilayer stacks
(Volk et al. 2003). A genetic algorithm has been used to precisely determine the
complex refractive index and thickness of thin films from their reflectance spectra
in the visible wavelength range (Torres-Costa et al. 2004). An experimental study
for the effect of the applied current density and the electrolyte composition on the
refractive index contrast of porous silicon multilayers produced at low current was
reported for increasing the refractive index contrast in a multilayer in the visible
range (Nava et al. 2009). In Fig. 7, the refractive index at 600 nm and the porosity
are shown as a function of the current density. There is a sharp drop in the porosity
for current densities below 5 mA/cm that allows to increase the refractive index.
However, the estimated porosities are relatively larger than the expected values for
the corresponding refractive indexes, probably due to inhomogeneities in the border
of the samples (Nava et al. 2009).
242
H. Sohn
The effects of oxidation on the Bragg reflector parameters and the variations in
the refractive index and thickness after oxidation were investigated. An oxidized
porous silicon Bragg reflector, centered at 1,550 nm, was formed by anticipating the
shift of central wavelength during oxidation. As the refractive index values of
porous silicon layers decrease strongly after oxidation, the index contrast decreases.
The reflection bandwidth also decreases after oxidation of the optical structure
(Charrier et al. 2012). The refractive index for a gradient-porosity porous silicon
which is equal to the effective index of a multilayer is also investigated (Shokrollahi
et al. 2012).
References
Arenas MC, Hu H, Nava R, Del Ro JA (2010) Determination of the complex refractive index of
porous silicon layers on crystalline silicon substrates. Int J Mod Phys B 24:48354850
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Minoru Fujii and Joachim Diener
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Structural and Refractive Index Anisotropy of (110) Porous Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Phase-Sensitive Detection of Adsorbed Atoms and Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Polarizing Elements Made from (110) Porous Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxidized (110) Porous Si (Porous Silica) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
245
246
248
249
250
251
251
Abstract
Electrochemically etched porous silicon can exhibit pronounced optical anisotropy even though bulk silicon is basically optically isotropic. The origin of this
effect, the most significant parameters, and potential applications in sensing and
micro-optic devices are reviewed.
Introduction
Bulk Si having a high symmetric diamond-type crystal structure is basically
optically isotropic. An alignment of pores, in porous Si preferentially in [100]
directions, induces optical anisotropy. However, even with porous Si having structural sizes smaller than the wavelength of light, the related effects are easily
M. Fujii
Department of Electrical and Electronic Engineering, Graduate School of Engineering, Kobe
University, Kobe, Japan
e-mail: fujii@eedept.kobe-u.ac.jp
J. Diener (*)
Physik-Department, Technische Universitat M
unchen, Garching, Germany
e-mail: jdiener@ph.tum.de
DOI 10.1007/978-3-319-05744-6_26
245
246
M. Fujii and J. Diener
observable in preferred geometries. For porous Si prepared from a (100)-oriented Si

wafer, pores and the nanocrystals forming the nanowire skeleton are preferentially
aligned/elongated normal to the wafer surface. Anisotropy of the refractive index,
i.e., birefringence, appears when light is incident upon a cleaved edge of the porous
Si layer (Kovalev et al. 1995; Mihalcescu et al. 1997), while it is optically
symmetric when light is incident perpendicular to the surface. By changing the
orientation of the etched Si wafer, an in-plane anisotropy of the refractive index can
be realized, for instance, by producing porous Si from lower symmetry Si surfaces,
e.g., (110) and (211) surfaces (Kovalev et al. 2000; Sarbey et al. 2000; Kunzner
et al. 2001, 2005; Kuznetsova et al. 2002; Koyama 2004; Golovan et al. 2007).
In this chapter, we will start with the microscopic structure of (110) porous Si and
the relation between the degree of the refractive index anisotropy and the
most significant preparation parameters, known to be crucial for the structural
morphology of porous Si. Potential applications of birefringent porous Si
like phase-sensitive detection of dielectric media (especially adsorbed atoms and
molecules) or polarizing elements made from (110) porous Si are discussed.
Finally, we turn to birefringent porous silica made by the oxidation of birefringent
porous Si, since a controlled change of the refractive index of the nanowire skeleton
offers an additional degree of freedom.
Structural and Refractive Index Anisotropy of (110) Porous Si

Figure 1a shows a cross-sectional TEM image of (110) porous Si observed from the

112 direction (Ishikura et al. 2008). The direction of the etching current is from
the top to the bottom. Because of preferential growth and consequently orientation
of pores to [100] directions, the preferential direction of the remaining Si skeleton
nanowires deviate from that of the etching current. Figure 1b shows a plan-view
TEM image of (110) porous Si. The projection of the Si nanowires on the (110)

surface appears as their in-plane alignment along the 110 direction (Shichi
et al. 2012). This preferential alignment is the origin of the in-plane refractive
index anisotropy.
Figure 2a shows a polar plot of the refractive index value of (110) mesoporous Si
as a function of the polarization direction of the incident light at 633 nm. In Fig. 2b,
refractive
indices
with the polarization direction of incident light parallel to the

n110 and [001] (n[001]) directions, respectively, and the difference n
110
n110 n001 are shown as a function of the etching current density (Ishikura
et al. 2008; Nishida et al. 2010). n rises with increasing etching current density,
indicating an overall morphological change with a more pronounced dielectric
shape/alignment effect at higher current densities. n also depends strongly on
typical sizes of the nanowire skeleton and the wavelength of light, as summarized in
Fig. 2c (K
unzner et al. 2001; Diener et al. 2007). This anisotropy of the refractive
index of (110) porous Si can be calculated and described within the framework of
several different models (Kuznetsova et al. 2002; Bonder and Wang 2005, 2006;
247
90
2.0
1.8
1.6
1.4
1.2
1.0
1.2
1.4
1.6
1.8
2.0
60
120
30
150
[110]
180
[001]
Refractive index
Refractive index
2.0
0.16
1.8
0.14
0.12
1.6
0.10
1.4
E
E
330
210
1.2
240

Fig. 1 (a) Cross-sectional TEM image of a (110) porous Si wafer observed from the 112
direction (Ishikura et al. 2008). (b) Plan-view TEM image of (110) porous Si and the electron
diffraction pattern (Shichi et al. 2012)
20
300
40
[110]
[001]
60
0.08
70
80
Current density (mA/cm2)
270
c
size 10-50 nm
0.1
size 6-8 nm
0.01
size 2-3 nm
500
1000
1500
2000
Wavelength (nm)
Fig. 2 (a) Polar plot of the refractive index value of a (110) mesoporous Si as a function of the
polarization direction of incident light at 633 nm. (b) Refractive indices at 633 nmof a (110)
mesoporous Si when the polarization direction of incident light is parallel to the 112 and [001]
directions. The difference of the refractive index values (n) between the two polarization
directions are shown on the right axis (Ishikura et al. 2008). (c) n of (110) porous Si with
different sizes of nanowire skeletons as a function of wavelength of light (K
unzner et al. 2001)
Kochergin et al. 2004, 2005; Ruda and Shik 2011) and is basically understood.
Consistently the structural anisotropy of (110) porous Si also affects the dielectric
properties in general, like the optical absorption coefficient and nonlinear susceptibility (Zabotnov et al. 2005; Timoshenko et al. 2003; Soboleva et al. 2005;
Efimova et al. 2007a, b).
248
Phase-Sensitive Detection of Adsorbed Atoms and Molecules

When linearly polarized light, whose polarization direction is rotated 45 from the

optical axes ( 110 and [001]), is normally incident to (110) porous Si, the relative
phase () of the electric field vectors on the optical axes shifts 2nd/, where d is the
thickness of the layer and is the wavelength (see Fig. 3a) (Shichi et al. 2011; Gross
et al. 2001; Kovalev et al. 2001). Figure 3b shows the ratio of the intensities of
transmitted light being polarized parallel and perpendicular to the polarization direction of incident light (Gross et al. 2001; Kovalev et al. 2001). The maxima (minima)
correspond to odd (even) orders of phase shift. The phase shift is very sensitive to
the refractive index of the dielectric medium in the pores (Gross et al. 2001; Kovalev
et al. 2001; Diener et al. 2003; Kunzner et al. 2003). The differential character of this
method allows monitoring of adsorptive condensation in nanopores and adsorbate
detection thresholds as low as 1010 g (Gross et al. 2001). This compares favorably
with several other methods including calorimetry, gravimetry, and volumetry, which
can be employed to study volume fractions of condensed fluids, but with a sensitivity
of the order of 106 g (Gross et al. 2001). Thus, monitoring this phase shift is a
promising method for high-sensitivity optical detection of dielectric media, especially
atoms and molecules incorporating the pores in normal incidence. Phase-sensitive
optical detection is of course also possible in (100) porous Si, however, when it is
tilted from the direction of incident light (Alvarez et al. 2012; Liu et al. 2002;
Beom-hoan et al. 2003; Oton et al. 2003; lvarez et al. 2011).
[110]
a
lo
Light
source
135
ll
Detector
45
Polarizer
45
[001]
Sample
Analyzer
102
Fig. 3 (a) sketch of the

crystallographic orientation
of (110) porous Si and the
polarization directions of the
incident and transmitted light
(Shichi et al. 2011). (b)
Intensity ratio of the linearly
polarized components of light
transmitted through a (110)
porous Si
I | / I ||
101
100
101
102
1000
1500
Wavelength (nm)
2000
249
Polarizing Elements Made from (110) Porous Si

The simplest polarizing elements made from (110) porous Si are wave plates
(retarders), which control the polarization state of light (Fig. 4a) (Kovalev
et al. 2000). Extending to (110) porous Si multilayers polarization-sensitive Bragg
reflectors (Diener et al. 2001, 2002, 2003; Ghulinyan et al. 2003), microcavities
(Diener et al. 2002, 2004; Saarinen et al. 2008) and polarizers (Diener et al. 2002,
Intensity of the transmitted

light (arb. units)
0.5
330
1.0
30
330
300
60
0.5
240
1.0
300
90
0.0 270
60
90
270
240
120
150
210
120
210
180
180
150
E|| [001]
Refractive index
30
E|| [110]
1.8
1.6
1.4
1.2
10
15
20
25
30
35
Thickness (m)
Transmittance (%)
100
80
60
40
20
0
500
1000
1500
Wavelength (nm)
2000
Fig. 4 (a) Polar plots of the intensity of linearly polarized incident (dashed lines) and transmitted
(solid lines) light as a function of the angle of the analyzer. (left) /4, (right) /2 retardation
conditions (Kovalev et al. 2000). (b) Refractive index profiles and transmittance spectra of a
polarization-sensitive rugate filter (Ishikura et al. 2008)
250
2004; Saarinen et al. 2008) can be realized by the modulation of the porosity and thus
the overall refractive index in depth directions. If the etching current is modulated
gradually, a so-called rugate filter characterized by a continuous sinusoidal refractive
index variation in the direction perpendicular to the film plane can be achieved.
Rugate filters provide advantages of suppressed higher-order harmonics and side
lobes if a proper apodization is applied to the index profile and index-matching layers
are added on the surfaces. Figure 4b shows an example of refractive index profiles and
transmittance spectra of a polarization-sensitive rugate filter. The wavelength of the
stop bands depends on the polarization direction (Ishikura et al. 2008). All these
multilayers can be realized with a high degree of freedom in a well-controlled manner.
Oxidized (110) Porous Si (Porous Silica)

So far we addressed the specifics of the etching process of porous Si and basic,
mainly geometric, issues relevant to the topic. A potential limitation of the system
at visible wavelengths emerges from the dielectric properties of the material
Fig. 5 (a) Plan-view TEM images of (a) as-prepared and oxidized (900 C) (110) porous
Si. Insets are electron diffraction patterns (Shichi et al. 2011). (b) Oxidation temperature dependence of n of porous Si (@800 nm) and porous silica (@400 nm) (Shichi et al. 2011)
251
forming the nanowire skeleton, i.e., self-absorption. However, oxidation of

porous Si results in porous silica, which can have transparency to the deep
ultraviolet region. Figures 5a, and 5b compare plan-view TEM images of (110)
porous Si and the corresponding (110) porous silica after oxidation at 900 C
(Shichi et al. 2011).
Due to the increase of the skeleton volume by oxidation, pores become smaller.
However, structural anisotropy is still evident in the TEM image (Shichi et al. 2011;
Golovan et al. 2006). Figure 5c shows n as a function of oxidation temperature.
Above 800 C, Si nanowire skeletons are completely oxidized, and thus, n
becomes more than one order of magnitude smaller than that of porous
Si. Birefringence disappears when porous Si is oxidized around 1,000 C. n of
porous silica is small but sufficient for true-zero-order wave plates in the deep
ultraviolet region (Shichi et al. 2011, 2013).
Summary
Self-orienting and self-limiting specifics of the etching process of porous Si,
combined with straightforward geometrical approaches, opens a unique way of
three-dimensional nanostructuring of silicon by wet chemistry. It is possible to gain
control of the structural and consequently dielectric properties of Si both parallel
and perpendicular to the wafer surface. In that sense, nanostructuring, here anisotropic dielectric nanostructuring, of semiconductors is an alternative approach to
create artificial materials. In this case, a Si-based material being sensitive to the
polarization state of light, with bulk Si being basically optically isotropic, could be
realized. With structural sizes smaller than the wavelength of light, a
quasiuniform distribution/alignment/elongation of pores and nanocrystals (for
porous silica, the dielectric material) forming the nano-skeleton is sufficient for
optical applications. It is a system which is rather easy to handle and to control.
Moreover, it can serve as basis for other novel metamaterials, for instance, by
controlled manipulation of the nano-skeleton of (110) porous Si by oxidation.
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Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mesoporous Silicon Layers, Multilayers, and Photonic Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mesoporous Silicon Membranes and Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Black Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Color Matching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
256
256
257
259
260
261
Abstract
The visual color of a material is often not important for many applications but
can be crucial for those that involve consumer acceptance and branded products.
Solid silicon is gray, but porous silicon can have varied colors depending on its
physical form and pore contents. Silicon chip-based layers can exhibit vivid
colors, tunable across the visible spectrum through their lowered refractive index
and optical interference with the underlying bulk silicon. Highly columnar
morphologies, referred to as black silicon, include highly porous forms.
Even white silicon is possible via photonic crystals. Polydisperse mesoporous
silicon microparticle powders are typically dark brown through light tan,
depending on bandgap widening, particle size, and the level of oxidation,
which is useful for matching skin tone in cosmetic products, but disadvantageous
with various foodstuffs, beverages, and oral care products. The color of such
powders can be better tuned chemically by the impregnation of specific food
nutrients that themselves have vivid colors. Some such natural pigments can
themselves benefit with improved fading resistance as a result of UV protection
via oxidized porous silicon impregnation.
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_27
255
256
L. Canham
Introduction
The color of the semiconductor in your computer chip or the color of your
implanted biomaterial or pharmaceutical tablet is of little consequence. The color
of your toothpaste, face cream, beverage, or food is another matter. Consumers are
used to the manufactured brands of brilliant white toothpaste with blue, red, or
green stripes. Brown is not a popular color for bathroom products (see the handbook
review Porous Silicon for Oral Hygiene and Cosmetics). There are brown and
even black popular foodstuffs think of bread, peanuts, cereals, chocolate, coffee,
and marmite (see handbook chapter Porous Silicon and Functional Foods).
However, these are in the minority, and once again the consumer associates specific
foods with specific colors.
In this review we detail how the color of mesoporous silicon can be tuned, like
many other properties (see handbook chapter Tunable Properties of Porous
Silicon). This has been achieved by both control of the physical structure of silicon
at the nanoscale and chemical means. The physical color of porous silicon films,
membrane flakes, and photonic crystals is much more easily tuned than those of
milled microparticle powders. The latter display various shades of brown, rather
than the gray of solid silicon, and this has to date been an obstacle for applications
in certain high-volume consumer products.
Mesoporous Silicon Layers, Multilayers, and Photonic Crystals

The very first studies of mesoporous silicon noted the different colors of anodized
and so-called stain films (Uhlir 1956; Turner 1958; Archer 1960). Uhlir referred to
his surfaces as having a matte black, brown or red deposit (Uhlir 1956). Turner
commented that several orders of interference colors can be seen as the film
thickens (Turner 1958). The first use of such colored silicon in the late 1950s
was in p-n junction delineation (Iles and Coppen 1958; Whoriskey 1958; Robbins
1962). Porous silicon, with its lower refractive index than solid silicon, induces
optical interference effects as etched films on wafers. A colorimetric analysis for
layer thicknesses below 500 nm, at quantified porosities, showed that interference
color directly related to the optical thickness of anodized single-layer structures
(Lazarouk et al. 1997). Figure 1 shows examples for stain-etched p + wafers. The
visual color of a given layer can be further changed by plasmonic effects of
deposited metal nanoparticles (Lublow et al. 2012) or through controlled oxidation
of the silicon skeleton.
Many natural organisms have evolved to optimize their visual appearance using
layers of modulated refractive index so-called structural color (Xu and Gao 2013).
They can have not only very vivid colors but also change their color in response to
external stimuli. Increasingly, we are learning to utilize such biomimetic designs
in synthetic structures to achieve specific functionalities such as colorimetric
sensors (Wang and Zhang 2013). The color palettes achieved via porous silicon
photonic crystals are impressive and include white (see Fig. 1 and Mangaiyarkarasi
257
Fig. 1 Varied physical colors from ultrathin single layers of stain-etched mesoporous silicon
(LHS- A. Loni unpublished 2009) and anodized mesoporous silicon photonic crystals (RHS
Gooding Group Univ. New South Wales, Australia http://www.rsc.org/Publishing/ChemTech/
Volume/ 2009/02/biosensors.asp)
et al. 2008). For detail on the optics, the reader is referred to the reviews of
Wehrspoon and Schilling (2003), Sailor (2012), Pacholski (2013), and Agarwal
(photonic crystal review in this handbook).
Of particular interest from a sensing perspective is that the color of such
structures can vary reversibly, or non-reversibly, with substances entering and
leaving the mesopores, as first demonstrated by Arwin and co-workers (Bjorkland
1996). Figure 2 shows the reversible effect of a volatile solvent like ethanol entering
the pores. In this regard, mesoporous silicon can truly be described as a silicon
chameleon, not only for its tunable color of electroluminescence under bias
(Canham 1993) but also its changing color upon pore filling (Fig. 2), analyte
binding, or chemical reaction (Bonanno and DeLoiuse 2010).
Multilayers of mesoporous silicon of modulated porosity, when detached from
the wafer, have the typical appearance of metal-based glitter or even gold leaf
(Fig. 3) and yet are pure silicon. Unlike conventional glitter, they can be loaded for
sustained release of actives like fragrance, thereby having a dual cosmetic role (see
handbook chapter Porous Silicon for Oral Hygiene and Cosmetics).
Mesoporous Silicon Membranes and Powders

To achieve reasonable quantities (e.g., 1001 kg) of porous silicon powder, thick
(e.g., 100200 m) mesoporous membranes can be detached from large-diameter
wafers using the electrochemical lift-off technique (see handbook chapters
Porous Silicon Formation by Anodization and Porous Silicon Membranes)
and converted to powders via mechanical means (see handbook chapter Milling
of Porous Silicon Microparticles). Both the membranes and powders are typically
brown in color (see Fig. 4). For powders with irregular acicular-shaped microparticles, the color is now dominated by optical absorption and scattering, rather than
interference. The brown hue gets lighter; the higher the porosity, the smaller the
particle size and the higher the oxide content.
258
L. Canham
Fig. 2 Reversible color changes due to ethanol wetting (LHS) and evaporation from mesopores
(RHS)
Fig. 3 Golden silicon flakes.

Mesoporous multilayer
structures removed from the
substrate after anodization
Fig. 4 Physical colors of dark gray solid silicon powder and brown porous silicon powders. The
brown hue of mesoporous silicon is tunable via porosity, microparticle size, and oxide content
(Loni A (2008) Unpublished data. Intrinsiq Materials Ltd)
Large batches of multicolor porous silicon powders with defined particle size
distributions (e.g., d50 in the range of 125 m) have not been achieved via
structural color. Instead more progress has been made using pigment impregnation. Figure 5 shows examples of the three primary colors achieved using foodgrade additives. Of particular interest are hydrophobic and light-sensitive nutrients
such as lycopene and beta-carotene that have vivid colors. They can impart a
desired hue to mesoporous structures (Canham et al. 2010), in return be UV
protected (Canham and Aston 2012; Pavlikov et al. 2012), and potentially have
their bioavailability improved as well when ingested (Canham 2007).
259
Fig. 5 Varied chemical

colors from mesoporous
silicon powders, oxidized
(800 C 3 h air) and then
impregnated with nutrients or
food additives (Canham LT
(2009) Unpublished data.
Intrinsiq Materials Ltd UK).
The light brown color was
tuned to red using carmine,
yellow using curcumin, and
blue using a commercial food
dye formulation (E133,
E122). Solvent loading was
used with 12 wt% pigment
Control over silicon particle shape, porosity, and polydispersity could provide
structural control of color of powders in the future. Of relevance here are the
so-called silicon colloids made by bottom-up routes. Porous silicon microspheres
of 0.55.5 m diameter scattered yellow, orange, and red colors when under white
light illumination (Fenollosa et al. 2010).
Black Silicon
Porous silicon films of one particular color have recently shown potential in a
number of specific application areas. The so-called black silicon has been etched
into a morphology that almost completely suppresses optical reflectivity over a very
broad spectral range (Koynov et al. 2006). Its visual appearance however does not
directly impact most of the uses currently under development.
The first optically black silicon structures were probably made by anodization as
early as the 19501960s. Koltun studied films generated at lower current densities
than Uhlir and Turner (Uhlir 1956; Turner 1958; Koltun 1964). He described their
persistent black color being due to a high degree of dispersion of silicon.
Interestingly, he also recorded reflectivity from his photocells, but focused on
the infrared rather than the visible range (Koltun 1964).
Sometimes also referred to as silicon nanograss because of its columnar
morphology, black silicon also became an unwanted by-product of reactive ion
etching (Jansen et al. 1995) but has subsequently been deliberately realized using
pulsed laser ablation and metal-assisted etching (Her et al. 1998; Koynov
et al. 2006; Chen et al. 2011). It is now being widely investigated for its
260
L. Canham
Fig. 6 Color matching: porous silicon and instant coffee for burst aroma release. The jar on the left
contains a commercial instant coffee/mesoporous silicon blend after boiling water addition. The jar
on the right shows the mesoporous silicon component trapped in the meniscus of boiling water
low reflectivity in solar cell applications (Ma et al. 2006; Branz et al. 2009;
Yuan et al. 2009; Koynov et al. 2011; Oh et al. 2012): photodetectors
(Su et al. 2013) and photoelectrodes (Ao et al. 2012). Other potential uses are in
microsystems (Roumanie et al. 2008), sensing (Gervinskas et al. 2013), its tunable
wetting (Dorrer and Ruhe 2007; Zhang et al. 2013), and its antibacterial properties
(Ivanova et al. 2013).
Color Matching
Manipulation of color in silicon-based devices and nanostructures can be for a
myriad of technical reasons (Cao et al. 2010; Doan and Sailor 1992; Seo et al. 2011;
Kuznetsov et al. 2012). Highlighted here are very different applications where the
intrinsic color of porous silicon is important for consumer acceptance.
The example chosen in Fig. 6 is from the beverage industry (see handbook
chapter Porous Silicon and Functional Foods). Instant coffee is an example
of a beverage, which in both dried powder and liquid form has the same color as
mesoporous silicon powder. Six properties of mesoporous silicon are important
here for it to be utilized: its ability to entrap coffee aroma under ambient storage
and thermally release it into the headspace above boiling water, its ability to stay
afloat on boiling water due to its hydrophobicity and low density, its taste and
mouthfeel, its low oral toxicity, and, last but not least, its low cost and an appropriate color.
261
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Sanjay K. Ram
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrical Transport Characteristics and Mechanisms: General Overview . . . . . . . . . . . . . . . . . . .
Contact Phenomena in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Characteristics of Current Versus Voltage (IV) Behavior in Porous Silicon Diode . . . . . . . . .
Temperature-Dependent Conduction Behavior in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Anisotropy in Electrical Transport of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conductivity Versus Porosity in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effective Medium Theory Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Percolation Theory Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Attempts on Classification of Electrical Properties of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
264
264
265
268
270
272
273
273
275
275
276
277
Abstract
The future development of porous silicon (PS)-based optoelectronic devices

depends on a proper understanding of electrical transport properties of the PS
material. Electrical transport in PS is influenced not only by each step of processing
and fabrication methods but also by the properties of the initial base substrate. This
chapter endeavors to chronologically document how the knowledge base on the
nature of carrier transport in PS and the factors governing the electrical properties
has evolved over the past years. The topics covered include the proposed electrical
transport models including those based on effective medium theories, studies on
contacts, studies on physical factors influencing electrical transport, anisotropy in
electrical transport, and attempts to classify the PS material.
S.K. Ram (*)
Department of Physics and Astronomy, Aarhus University, Aarhus C, Denmark
Interdisciplinary Nanoscience Center iNANO, Aarhus University, Aarhus C, Denmark
e-mail: sanjayk.ram@phys.au.dk; sanjayk.ram@gmail.com
DOI 10.1007/978-3-319-05744-6_28
263
264
S.K. Ram
Introduction
An important attraction of porous silicon (PS) has been its customizable morphology which can be tailored to change its optoelectronic properties to suit the required
application. In case of luminescence, an important property of PS, morphology can
be modified to tune the intensity and the peak position of luminescence over a wide
range of wavelengths (Marsh 2002). However, the versatile microstructural nature
of porous silicon that imparts to it these exciting possibilities is also the main
hindrance in the studies of its electrical properties.
The inhomogeneous microstructure of PS impedes the comparability between
studies of different laboratories (Foll et al. 2002; Bisi et al. 2000). Even within a
sample of the material, the complex and inhomogeneous microstructure and crystallites (Islam et al. 2001, 2005) can result in lack of uniformity in the observed
electrical properties (Dutta et al. 2002). In the past decades, electrical transport
properties of PS have been found to be dependent not only on its microstructure
(Kocka et al. 1996a) but also on several factors like the base c-Si selection (Zimin
and Bragin 2004), anodization method (Dutta et al. 2002), metal contact formation
(Simons et al. 1995; Martin-Palma et al. 2002), annealing (Zimin and Komarov
1998), electrical measurement method (Boarino et al. 2009), etc. In addition, the
electrical properties are strongly influenced by external factors such as ambient
atmosphere (Zhang et al. 1995) and residual electrolyte (Parkutik 1996). Thus, the
understanding of the transport properties of carriers through such a disordered
system is challenging.
The early research on the electrical transport properties of porous silicon carried
out in the 1980s revealed that the resistivity of the porous silicon layer was a few
orders of magnitude higher than the original substrate (Beale et al. 1985). While
quantum confinement model has been successfully used to explain the luminescence properties of PS, applying it to explain the transport properties of PS has been
difficult and less unequivocal. In this chapter, we present an overview of the
electrical properties of porous silicon based on the literature published in the last
three decades.
Electrical Transport Characteristics and Mechanisms:

General Overview
The earliest reports on the electrical properties of PS were about the high electrical
resistivity in this material. Electrical resistivity in PS is 5 orders of magnitude
higher than in intrinsic Si due to the depletion of free carriers. One reason behind
the depletion is the widening of energy gap due to quantum confinement and
decreased thermal generation of free carriers. The depletion of free carriers can
also occur due to their trapping, which occurs during the preparation of PS either
because the binding energy of dopant impurities are increased or because of the
formation of surface states. Even after etching, the concentration of dopants
remains unchanged, although the dopants are in neutral state (Bisi et al. 2000).
265
The electrical conductivity of PS can be dependent on voltage and/or temperature. The commonly observed thermally activated temperature dependence of DC
conductivity behavior in PS is expressed by a relation:
T 0 expEa =kB T ,
(1)
where activation energy (Ea) and conductivity prefactor ( 0) are material property
used to explain transport mechanism. In most reports, the value of Ea has been
found to be 0.5 eV. This value is half of the energy of the bandgap deduced by
luminescence and also comparable to the Ea in intrinsic Si 0.5 eV, suggesting that
mechanisms other than quantum confinement are in play as well. All these indicate
the disordered nature of the PS skeleton and its local crystalline structure as they are
expected to have strong geometrical effects on the conductivity (Bisi et al. 2000).
Thus, there has been little consensus on any predominant transport mechanism
in PS. This is evident from Table 1 which shows the reported studies on the
electrical transport characteristics of PS and the different conduction mechanisms
proposed by various workers to explain the observed transport behaviors. In the
electrical measurements of PS samples, an important factor is the direction of the
current flow, that is, whether the measurement is done in sandwich configuration or
in coplanar configuration. Another important consideration is whether the PS
material is freestanding or is still supported by the mother substrate.
Contact Phenomena in Porous Silicon

The characteristics like linear (ohmic), symmetric (quasi-linear), or nonlinear
(rectifying or Schottky types) behavior of IV characteristics in PS have been
reported depending on the type of metal contact (Simons et al. 1995), measuring
(Diligenti et al. 1996), and device configuration (coplanar or sandwich) (Kanungo
et al. 2010), whether the PS is freestanding or attached with base substrate,
microstructure (Dutta et al. 2002), and thickness of PS layer (Ben-Chorin
et al. 1994; Balagurov et al. 2000). Here the term microstructure includes the effect
of all the processing methods and the initial base substrates properties. An ohmic
contact on PS like in any semiconductor material is crucial for the development of a
device. Rectifying behavior can originate due to either unstable contact or workfunction value of the metal chosen, or it can be due to both. For example, according
to the work function of Al, it should provide ohmic contact to PS, but instead it
shows a rectifying behavior. This is due to the existence of large density of surface
states on unmodified PS which create barrier against the current flow. Therefore,
methods or techniques like annealing, oxidation, derivatization by organic groups
and polymer, nitridation, halogenations, and metal (like Cu, Ag, In, etc.)-induced
modification of the porous silicon surface are used to stabilize PS by passivation
of defect states in order to obtain a stable and reliable electrical contact to PS
266
S.K. Ram
Table 1 Summary of electrical transport models described for porous silicon

Year of
study
1993
1993
Reference
Mares et al. (1993)
PS physical
form
PS device form
AuCa/PS/cSi/
Al
Al/PS/Al
Electrical transport model

Tunneling between
thermally vibrating
surface states (Berthelottype conduction)
Band transport
Nanoporous
Al/PS/c-Si/Al
Poole-Frenkel process
Nanoporous
Al/PS/c-Si/Al
Hopping at Fermi level
Mesoporous
film (n+)
Mesoporous
membrane
Al/PS/c-Si/Al
Surface trap dominated
Al/PS coplanar
(CP)
Transport in nearly
extended states and
process similar to
multiple trapping model
Two transport channels:
hopping at transport edge
and thermionic emission
across energy barriers
Quantum confinement
model
Tunneling between the Si
nanocrystals (Si-NCs)
Thermionic emission
across spatially varying
bandgaps
Tunneling of carriers to
localized states near band
edges, at high
temperatures and variable
range hopping near Ef at
low temperature
Coulomb blockade
Koyama
et al. (1993)
Ben-Chorin
et al. (1994)
Ben-Chorin
et al. (1995a)
Lehmann
et al. (1995)
Schwarz
et al. (1995)
1996
Kocka
et al. (1996a, b)
Nanoporous
membrane
Au/PS/Au
1996
Lee et al. (1996)
Al/PS (CP)
1996
Diligenti et al.
(1996)
Ray et al. (1998)
Nanoporous
membrane
Mesoporous
membrane
1994
1995
1995
1995
1998
1998
Mathur
et al. (1998)
1998
Hamilton
et al. (1998)
Balberg (2000)
2000
2001
Mikrajuddin
et al. (2001)
4 probe CP
Al/PS/c-Si/Al
Macroporous
Al/PS/cSi/Al
Two transport channel

via nanocrystal network
and purely amorphous
phase
Activated conduction in
moderate temperature, at
higher temperatures,
conductivity obeys
Vogel-Tammann-Fulcher
law
(continued)
267
Table 1 (continued)
Year of
study
2002
Reference
Axelrod
et al. (2002)
2002
Dutta
et al. (2002)
2004
Forsch
et al. (2004)
Islam
et al. (2007)
2007
2008
Bouaicha
et al. (2008)
2009
Islam
et al. (2009)
PS physical
form
Nanoporous
PS device form
Al/PS/c-Si/Al
Al/PS/c-Si/
Ag-Al
Nanoporous
membrane
Nanoporous
Al/PS (CP) and

Al/PS/Al
Al/PS/c-Si/Al
Al/PS/c-Si/Al
Nanoporous
Al/PS (CP)
Electrical transport model

Thermally activated
hopping within a fractal
network of
nanocrystallites
Generalized effective
medium approximation
(EMA) using porosity
(Po) and uniformity of PS
Poole-Frenkel transport
Carrier generationrecombination in
depletion region formed
on PS side
EMA by considering Si
nanoparticles with size
distribution embedded in
SiO2 and vacuum
Mott hopping and EfrosShklovskii hopping at
low temperature
(Dutta et al. 2002; Zimin and Komarov 1998; Zimin and Bragin 1999). This topic is
the focus of the dedicated chapter Ohmic and Rectifying Contacts to Porous
Silicon elsewhere in this handbook.
Transition from nonlinear (rectifying) to linear (ohmic) behavior of Al contacts
on PS depending on postdeposition treatments has been reported by many workers
(Dutta et al. 2002; Zimin and Bragin 1999). In some cases, the range of linear part
extends only up to few volts, while a broad range of voltages have also been
reported for linear part of IV characteristics. Surface oxidation has been considered a very efficient way of passivating the defects and improving the stability of PS
to a large extent. Although it helps in coplanar configuration to obtain ohmic
contacts, in sandwich design the contacts may still show improved rectifying
behavior because the Fermi level (Ef) gets pinned at the PS/c-Si interface where a
large number of volume traps and interface states exist (Islam et al. 2007). Zimin
et al. (1995) reported a coplanar Al ohmic contact to n-type PS having a contact
resistivity of the order of 103 to 102 cm for low porosity and low resistivity
samples, but they observed a rectifying behavior for high resistive PS, both n- and
p-type. Martin-Palma et al. (1999) reported the same for the Al/PS/c-Si/Al sandwich structure, where rectifying behavior can be seen even after prolonged exposure to the atmosphere. Use of noble metals (Pd, Pt, and Ru) (Kanungo et al. 2009)
or their ions are also reported to modify and stabilize the surface of PS in order to
obtain reproducible metal contacts thereafter.
268
S.K. Ram
Characteristics of Current Versus Voltage (IV) Behavior

in Porous Silicon Diode
There are two types of diode structures in PS that exist in the literature, structure-1:
metal1/PS/c-Si/metal2 and structure-2: metal1/PS/metal2, where the former is the
most widely investigated device structure. The structure-1 leads to three different
junction formations at the interfaces of (1) metal1/PS, (2) PS/c-Si, and (3) c-Si/
metal2. The IV characteristics usually show asymmetric behavior due to current
rectification. Typically the junction, c-Si/metal2 is made to be ohmic with negligible series resistance, so that it plays no role in IV characteristics of the diode. The
effect of metal1 in the junction of metal1/PS on IV behavior is not very clear as
discussed in section Contact Phenomena in Porous Silicon. There has been much
contention in assigning the possible contribution of metal1/PS and PS/c-Si interfaces to the electrical properties of PS diode structures. In some cases (Pulsford
et al. 1994; Giebel and Pavesi 1995), no dependence of the type of metal1 was
found, suggesting that the interface of PS/c-Si instead of metal1/PS may be responsible for rectification (Pulsford et al. 1994). This led to a suggestion that the
transport of carriers within the PS layer thickness and across the PS/c-Si
heterojunction governs the device characteristics (Ben-Chorin et al. 1995b). The
IV characteristics in PS have been contradictorily attributed to both the bulk
(PS) properties and junction properties in the reports (Ben-Chorin et al. 1994;
Zimin 2000). Some authors have attributed the electrical behavior of thin PS
structures to junctions under both reverse and forward bias condition (Zimin
2000; Futagi et al. 1993; Pavesi et al. 1994; Bhattacharya et al. 2000), while others
have contributed the electrical behavior under reverse bias conditions to junctions
and that under forward bias conditions to bulk conduction mechanisms
(Ben-Chorin et al. 1995b). The electrical response of a c-Si/PS heterojunction is
determined by the interplay of band edge offsets and density of defect states in the
PS layer. Therefore, another possibility is that a large density of states associated
with mid-gap defects present in PS pins the Ef and significant band bending and
depletion occur only inside silicon rather than at the metal/PS interface
(Ben-Chorin et al. 1995b; Pulsford et al. 1993).
The thickness of PS layer is also one of the factors that influence the contact
behavior. As thin PS layer show rectifying characteristics while thick PS layer show
an almost symmetric one, Ben-Chorin (Ben-Chorin et al. 1994) proposed that the
rectifying barrier is at the interface between PS and the doped substrate. It was also
suggested by them (Ben-Chorin et al. 1994) that the usual diode structure formed by
a metal contact, a PS layer, and a doped substrate can be visualized as a series
combination of a voltage-dependent resistance and a rectifying barrier. Their study
shows that the temperature- and voltage-dependent conductivity relationship follows Poole-Frenkel (PF)-type conduction, where transport mechanism in high fields
involves field-enhanced thermal excitation from Coulombic traps:
p
Ea
F
F, T 0 e kT e =F0 T
(2)
269
p
kT=q
F0 T pq
= 0 r
In this type of conduction, charge carriers are thermally excited from traps to
some transport band, and barrier energy reduction due to the electric field enhances
conduction. Charges will move along special paths with the lowest barrier energies,
those which offer the lowest resistance (Ben-Chorin et al. 1994). Further, based on
their observations that the conductivity scales correctly with the thickness, they
ruled out the possibility of space charge-limited current (SCLC) type of conduction
(Ben-Chorin et al. 1995a).
In another report, a power law behavior, J / Vn/dm with exponent, n 2 typical
of SCLC was observed (Peng et al. 1996). They argued that the total current of the
device is dominated by carrier transport in the high-resistivity PS layer which can
be modeled as sandwiched between two conducting materials and the band bending
at the metal1/PS interface is so small that the Schottky junction can be neglected.
Superlinear behavior of current with rise in voltage (n < 2) (Koyama and Koshida
1993) was also observed by Kocka et al. (1996a, b; Fejfar et al. 1995); however,
behavior was linear at lower voltages. In addition, Ea obtained from temperature
dependence of transport was also found to be field dependent, where Ea decreases at
high voltages as expected from the PF mechanism. However, the initial rise in Ea at
low voltages (Kocka et al. 1996a) is explained either by assuming a parallel
combination of two transport paths with different Ea (through and over the barrier
between nanocrystals) of which one is voltage dependent (e.g., PF-type) or by
assuming a series combination of Schottky contact and of SCLC controlled by traps
inside the nanocrystals. The contacts dominate at low V and the SCLC at high V.
Within this model the Ea represents the thermal generation of carriers from the
Fermi level to the transport paths.
The influence of temperature on the IV characteristics of PS/c-Si structures was
reported by Ref (Theodoropoulou et al. 2004), which also elucidated the mechanisms dominating under different bias conditions. According to this study, for the
reverse bias condition, the ohmic bulk resistance dominates at first, and junctional
resistance comes into play at a later time. On the other hand, under forward bias
conditions, ohmic bulk conduction dominates, but with time gives way to PF-type
conduction in the bulk. The time at which the change of mechanisms occurs is a
function of temperature, with the change occurring later in lower temperatures.
Based on the analyses of reverse IV characteristics, Islam et al. (2007) proposed
that the characteristics of PS/c-Si heterojunctions are found to behave like the
Schottky junctions where transport is governed by carrier generationrecombination in the depletion region formed on the PS side. Fermi level of c-Si
gets pinned to the defect levels at the interface resulting in ln(I) / V1/2.
In addition, there are several reports which attributed observed IV behavior of
metal1/PS diodes to the formation of a Schottky barrier between PS and the metal1
(Canham 1997). In a reported case (Ray et al. 1998) of low value of ideality factor,
n 1 with low series resistance in the low voltage range, it was proposed that
PS/c-Si junction characteristics are controlled by carrier diffusion in the PS and the
where F is electric field and
270
S.K. Ram
observed rectification of electron current is due to the barrier between c-Si and
PS. However, in most of the cases, high values of ideality factor, n (>5) with either
high (Ben-Chorin et al. 1995b; Futagi et al. 1993; Pulsford et al. 1993) or low values
of series resistance due to PS layer (Pulsford et al. 1993), suggest most of the
applied voltage does not drop on the barrier, but rather on the PS layer, which
impedes a determination of reliable junction parameters in PS/c-Si heterojunctions
using the conventional analysis of forward IV characteristics (Koshida and
Koyama 1992; Pulsford et al. 1993). According to the report (Koshida and Koyama
1992), tunneling of carriers dominates at high voltages.
Temperature-Dependent Conduction Behavior in Porous Silicon

Most of the observations of temperature-dependent electrical conduction in PS
indicate that the transport of electrons is thermally activated, with Ea in the range
of 0.30.7 eV (Koyama and Koshida 1993; Ben-Chorin et al. 1994; Kocka
et al. 1996b; Lee et al. 1996; Fejfar et al. 1995; Lubianiker et al. 1996; Lubianiker
and Balberg 1997). The measured activation energies can be related to activation of
carrier over mobility edges or to typical energy barriers for carrier hopping. In the
former, the activation energy indicates the energy difference between the Fermi
energy and the mobility edge. In the latter, the activation energy is related to a
typical barrier height separating neighboring localized states (Bisi et al. 2000). In
addition, disorder-induced localization of free carrier affects the free carrier motion
in a way similar to amorphous silicon. However, in many cases, it has also been
observed that there is a distinguishable change in the electrical transport behavior
for high and low temperature regions usually at some critical temperature (Islam
et al. 2009; Zimin 2006; Mikrajuddin and Shi 2000). The Ea is found to have
relatively high value in the relatively high temperature region to a low value in the
low temperature region (Ben-Chorin et al. 1995a; Islam et al. 2009; Fejfar
et al. 1995; Lubianiker and Balberg 1997). However, in some cases, the conductivity is almost temperature independent below 200 K (Koyama and Koshida 1993;
Ben-Chorin et al. 1995a). The critical temperature around which the electrical
transport behavior changes is found to depend on the size of Si nanocrystals,
porosity, their size distribution (Zimin 2006), and their microstructures
(Zimin 2006).
According to Ben-Chorin et al. (1994), PS is like a disordered assembly of three
dimensional quantum wells with large bandgaps of the nanocrystallites (NCs).
The transport in PS mainly involves dangling bonds (surface states) near Ef and
hopping of carriers takes place in these surface states in the entire temperature
range. The thermally generated carriers at the mobility edge do not take any part
in the transport, making the bending of bands at the metal1/PS interface irrelevant.
On the other hand, Kocka et al. (1996b) assumed that the transport in PS takes
two paths one through the surface grain barrier and the other over the
surface grain barrier. This mechanism is field dependent in accordance with
PF-type effect.
271
In 2000, Balberg (2000) classified the electrical transport in PS by reanalyzing

experimental data collected from various published papers about the temperature
dependence of DC dark conductivity, according to Meyer-Neldel rule (MNR)
ln 0 BMN Ea =EMN
(3)
where BMN and EMN are MNR parameters. The relationship between conductivity
prefactor 0 and activation energy Ea as per Eq. 1 of various PS samples shows two
well-separated straight lines suggesting two different mechanisms. One of the lines
is similar to amorphous Si, and most of the PS data falling on this line belong to data
of high temperature thermally activated region, suggesting extended state transport.
The other line, which accumulates most of the data from low temperature regions,
represents intercrystallite hopping-tunneling conduction. It must be noted that most
measurements in the group similar to a-Si behavior were taken from nanosize
porous layers, while the second group obeying the MNR in low temperature regions
were low porosity samples. This means two different conduction mechanisms take
place in different parts of the samples. The amount each of them contributes to
the conductivity depends on the sample and the measurement temperature.
Nevertheless, most of the currently available models suggest that the temperature dependence of electrical conductivity obeys the Arrhenius relationship with a
single activation energy for the entire range of temperatures (Ben-Chorin
et al. 1994; Pulsford et al. 1994; Fejfar et al. 1995; Lubianiker and Balberg 1997;
Diligenti et al. 1996). However, according to Mikrajuddin et al. (2001), Arrheniustype activated conduction behavior may be exhibited in moderate temperature
region if both continuous networks of blocked and unblocked sites appear in a PS
layer. At higher temperatures, continuous networks of unblocked sites and blocked
sites occupying discrete positions can be found in PS site, and conductivity obeys
Vogel-Tammann-Fulcher (VTF) law, which can be expressed as
0 T 1 expB=T T 0 ,
(4)
where 0, B, and T0 are constants. Mikrajuddin et al. (2001) derived the VTF
behavior by using mean-field approximation of Ising model and used the model
to fit published experimental data to validate it.
However, at low temperatures carrier conduction is often found to be assisted by
variable range hopping (VRH):
ln / T x =T m
(5)
where m gives the information about type of carrier conduction and depends on
dimensionality (mainly arising from crystallite sizes) and the temperature region.
Tx is a constant for the material and often x is replaced with the name of transport
mechanisms.
So far Mott hopping transport where a T -0.25 (m 0.25) dependence is followed
at low temperatures was considered for most of the varieties of PS: nanoporous
(Islam et al. 2009), mesoporous (Zimin 2006), and macroporous (Mathur et al. 1998;
272
S.K. Ram
Ben-Chorin et al. 1995a). Berthelot-type conduction (m 1) was also reported and
attributed to the fractal structure of PS (Mares et al. 1993; Mehra et al. 1998), and
variable range hopping has been observed in porous-amorphous Si of different
compositions (Yakimov et al. 1995, 1996). Islam et al. (2009) critically analyzed
their temperature-dependent conductivity data over a wide range of temperatures for
the applicability of various transport mechanisms. Their findings suggest extended
state conduction for T > 300 K, Berthelot-type conduction when 180 < T < 280 K,
Mott hopping in the range 140 < T < 180 K, and Efros-Shklovskii hopping for T <
120 K. A clear cross over from Mott to Efros-Shklovskii VRH transport is observed
at low temperatures. It is interesting to note that Berthelot-type conduction in Ref.
Islam et al. (2009) was also observed in the similar range of temperature (190270
K) as in Ref. Mares et al. (1993). Similarly, the temperature range of Mott hopping
transport observed in various types of PS is 140180 K for nanoporous
(Islam et al. 2009), 110200 K for mesoporous (Zimin 2006), and 100150 K for
macroporous (Mathur et al. 1998).
Anisotropy in Electrical Transport of Porous Silicon

The cubic lattice structure of c-Si makes it an isotropic optical medium. However,
nanostructuring of c-Si by porosification of low-symmetry Si surfaces or the
formation of micrometer-sized Si periodic structures converts the resulting
c-Si into a strongly birefringent material (see handbook chapter Optical
Birefringence of Porous Silicon). Anisotropy in electrical properties of PS was
first demonstrated by Forsh et al. in a mesoporous system obtained by (110) c-Si
(Forsh et al. 2004). They observed substantial decrease in the conductivity
measured in parallel to the surface, i.e., (001) crystallographic direction ( ||),
compared to the conductivity in sandwiched configuration, (110) crystallographic
direction ( ). The conductivity in both directions follows exponential dependence
on V1/2 and > > || at any voltage. PF mechanism was used to explain the
dependence of the conductivity on the electric field in the PS. According to Forsh
et al. (Forsh et al. 2004, 2005), an increase in thermal emission of carriers across the
potential barriers at the boundaries of NCs can be due to the electric field-induced
enhancement of thermal ionization of impurity atoms and reduction in fluctuations
of the potential profile (barriers at boundaries of NCs). Previously, the PF
mechanism of conduction was observed in sandwiched configuration PS device
prepared from (100)-oriented p-type c-Si wafers (Ben-Chorin et al. 1994).
The temperature-dependent conduction shows the widening of the gap between
the conductivities in both directions at lower temperatures, which means the Ea in
(110) direction (Ea) is smaller than Ea in (001) direction (Ea)||. Apparently, the
material has a certain distribution of potential barriers by height. As the length of
the percolation path (constituted by Si-NCs) in the perpendicular (110) direction is
shorter than that in the parallel (001) direction owing to the shape anisotropy of
NCs, the average height of potential barriers in the perpendicular direction will also
273
be lower than that in the parallel direction. This will lead to higher values of and
lower values of its (Ea) compared to ||.
Earlier work on both freestanding nanosized PS and mesoporous anodized from
(100) c-Si show almost isotropic behavior (Kocka et al. 1996a). It was argued that
the transport is controlled by the more or less homogeneous (isotropic) tissue part
of PS, in which c-Si islands are embedded. However, in 2006 Borini
et al. demonstrated anisotropic behavior in the conductivity of (100) mesoporous
by measuring temperature-dependent conductivity of their sample using two different electrode configurations (Boarino et al. 2009; Borini et al. 2006). The authors
observed that the electronic transport parallel to the sample surface ( ||) is strongly
inhibited at room temperature but not along the perpendicular direction ( ). This
behavior was well correlated with the typical microstructure of the mesoporous
where, due to the presence of branched columnar morphology, the || pathways are
poorly interconnected, with several bottlenecks in which potential barriers are built
up. Thus, the transport is strongly inhibited in the longitudinal (parallel to the
sample surface direction), while in the transverse direction (perpendicular to the
sample surface) the bottlenecks can be easily bypassed following the alternative
pathways available. It was also shown (Borini et al. 2006) that such electrical
anisotropy can be reversibly removed by heating the samples (increasing temperature from 20 C to 100 C) when || increases almost six orders of magnitude
equaling . The rise of temperature allows the charge carriers to overcome the
nanoconstrictions (Coulomb blockade due to charges trapped in the
nanoconstrictions), opening the longitudinal percolative pathways. The increase
in temperature can remove the Coulomb blockade of a fraction of NCs, until the
percolation threshold is reached and exceeded.
Conductivity Versus Porosity in Porous Silicon

Effective Medium Theory Approach
Among many other microstructural parameters, porosity is one such physical
parameter, which is generally used to describe the degree of porous nature of a
PS layer. Porosity has been well researched with the fabrication methods and
environment. Therefore, if this physical parameter could be correlated with electrical conductivity of the PS using any analytical way, it could serve an important
role in tailoring the microstructure to obtain desired device properties. However,
not much work has been done to explore this correlation. Effective medium
approximation (EMA) as proposed by Bruggeman was used to some extent to
determine a correlation between the effective conductivity of the PS layer and
porosity of the layer:
n
X
i eff
vi
0
i 2 eff
i
(6)
274
S.K. Ram
According to Dutta et al., up to certain low values of porosity, this theory worked
well but failed to explain the effective conductivities of mid to highly porous layer
(Dutta et al. 2002). The major challenge in the pore shape is the possibilities of
different pore branching formations during PS growth (Saha et al. 1998). PS layers
with identical porosity might have different surface-to-volume ratios, leading to
different effective conductivities. They followed generalized EMA (GEMA),
which accounts for the general form of the shape of the inclusions, where they
included the extent of pore branching by uniformity factor (Saha et al. 1998):
n
X
i
1=t
1=t
i eff
vi
0
p
1=t
1=t
i
2 eff
1 p
(7)
where p is the percolation volume fraction and t is a nonlinearity correction factor.

So for spherical inclusions with p 2/3 and t 1, the GEMA reduces to
Bruggemans EMA.
The theoretically calculated values match well with the experimental values up
to the porosity range 70 %. But beyond this range of porosity, the calculated value
underestimates the effective conductivity. Similar problem of mismatch between
calculated and experimental results of effective conductivity was also observed by
Bouaicha et al. in the porosity range exceeding 65 % (Bouaicha et al. 2006):
vox
QD=QW eff
ox eff
v eff
vv
vQD=QW
0
ox 2 eff
v 2 eff
QD=QW 2 eff
(8)
where
E
QD=QW Si e4kT
(9)
They assumed in their theoretical calculation that the nanoporous silicon is

formed by three phases: vacuum, oxide, and c-Si nanocrystallites (quantum dots
(QD) for nanoporous or quantum wire (QW) for mesoporous structure) having the
same mean-size dimension. The contribution of the latter phase in the total electrical conductivity was developed analytically by using the quantum confinement
theory. This assumption worked well when the porosity was within 3065 %, and
beyond that theoretical values were too low compared to the experimental ones.
However, for large porosities (greater than 65 %), where the PS structure exhibit
visible luminescence, they could successfully obtain a perfect agreement between
the theory and the experiment for all porosities when they considered that the base
medium is vacuum in which silicon crystallites are incorporated (Khardani
et al. 2006). This means that for the case of high porosities, the role of porosity is
substituted by the quantum dot volume fraction in the fitting procedure.
They successfully extended this work to obtain a good correlation between
effective conductivity of mesoporous Si material and their corresponding porosity.
275
In 2008, however, they further modified their work by considering the Si-NCs as
being formed by multiple-sized crystalline dots (John and Singh 1994) embedded in
silicon dioxide and vacuum (Bouaicha et al. 2008):
vox
N
X
ox eff
v eff
QDi eff
vv
vQDi
0
ox 2 eff
v 2 eff
QDi 2 eff
i1
(10)
As a result, they obtained a good agreement between theory and experiment for
all porosities. In this case (Eq. 9), all values of E are considered including those
< E0. This avoids the tendency of the medium to be an insulator for higher
porosities unlike what happens when the PS medium is considered to have three
phases with single mean-sized QD.
Percolation Theory Approach

A different approach to correlate porous silicon conductivity with material porosity
was described in Ref. Aroutiounian and Ghulinyan (2003). In this work, the
conductivity was shown to be mainly crystalline for porosities much lower than
the percolation threshold at 57 %, while a fractal behavior was observed at
porosities near percolation threshold. For higher values of porosities, the conductivity was described as a quasi-one-dimensional hopping. The report concluded that
in PS with increasing porosity, at lower temperatures, the dimension of the channels
of electrical current flow decrease from 3 to 1, as described by the Mott law for
amorphous semiconductors. However, the model results described in this work
show some deviation from the experimental results.
In spite of workers having presented models to fit their experimental data for a
range of porosity, none of the works have attempted to fit the data of others with
their models. If these models were tested to fit a wider range of published data, one
could hope to find a more comprehensive model that could find wider application to
make porosity a useful parameter in predicting the electrical behavior of PS.
Attempts on Classification of Electrical Properties of

Porous Silicon
The study of a heterogeneous material as PS could benefit greatly from a classification system that would allow a more systematic understanding and correlation of
its properties. A wide variety of PS has been classified into some broad microstructural groups based on porosity. However, the same agreement has not been reached
in correlating electrical properties of these PS groups to parameters related to
porosity of the material. This is because electrical current which flows through
the Si network depends largely on the size of Si structure and its surroundings and is
not directly linked to pore size.
276
S.K. Ram
In 1997 a comprehensive review of the properties of porous silicon was

published by Canham that included a classification proposed by Ben-Chorin
(Canham 1997). Ben-Chorin classified PS into two broad and distinct classes,
low porosity and nanosized porous Si material, and explained the plausible
electrical transport behavior of these two groups. The low porosity material is
prepared from highly doped c-Si wafers (resistivity < 1 cm), and quantum
confinement does not play any role in transport. The nanosized PS is prepared
from low-doped c-Si wafers and mostly under illumination. Crystallite size in such
material is usually <10 nm and this type of material is luminescent. The consequence of quantum confinement can be seen in the effective bandgap of such
material. The two types described in this classification have been used in describing
the PS materials in Table 1. It can be seen in this table that the electrical transport
properties of nanosized PS and the suggested plausible phenomena vary a lot within
the group itself, although they are significantly distinct from low porosity PS
material.
As discussed before, Balberg et al. showed in 2000 that two different kinds of
conduction mechanisms may occur within the same sample of PS (Balberg 2000;
Lubianiker et al. 1996; Lubianiker and Balberg 1997). They explained this using a
pea-pod model, where the peas are the Si-NCs and the pods are formed by the
disordered matrix. The existence of two rules then suggests that one of two different
mechanisms is dominant in a given sample for a given temperature. Their further
experiments on noise measurements on freestanding PS films, in particular the
observation of a strong dependence of the noise on the voltage, point to a tunneling
contribution superimposed on conduction in the amorphous tissue which coats the
Si-NCs. As far as the tunneling contribution is concerned, evidence was presented
that this occurs via a Coulomb blockade mechanism.
In 2000 Zimin et al. presented a classification of PS into four groups based on
porosity, morphology of pores, and the depletion regions around the pores to
explain the diverse electrical properties of PS material and of multilayer structures
with PS layers (Zimin and Bragin 2004; Zimin 2000). For each group, they also
described not only the most probable properties of metal/PS interface but also the
plausible nature of PS/c-Si junctions. They also pointed out that the electrical
properties of the junction may be different, depending on electrical parameters of
PS itself. According to Zimin, in each of the four groups, there exists a specific
mechanism of drift of charge carriers, which governs not only the electrical
conductivity of the material but also the characteristics of variations in conductivity
with variations in temperature, illumination intensity, and other ambient conditions.
Summary
The study of electrical properties of porous silicon presents a challenge arising from
the diverse mechanisms that may come into play due to the variegated nature of its
microstructure and the influence of ambient conditions. The literature on PS since the
1990s has elucidated to a large extent the transport properties and mechanisms in PS.
277
In particular the attempts to classify PS has brought out correlations between the
electrical transport properties and microstructural parameters such as porosity that
lead to a better understanding of the material properties and also serve to control the
material better to create devices. The reports reviewed in this chapter, while by no
means exhaustive regarding the electrical transport in PS, aim to present an overview
of the knowledge base gathered on the material till now.
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Diamagnetic Behavior of Porous Silicon

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diamagnetism of Silicon and Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
281
283
284
285
Abstract
After a brief introduction to diamagnetism, the magnetic properties of silicon are

briefly outlined. The magnetic behavior of silicon consists of a diamagnetic and
a paramagnetic term, whereas the diamagnetism predominates. Furthermore,
various types of porous silicon like as-etched and oxidized porous silicon are
discussed, and the dependence of the diamagnetism on the surface treatment and
thus on the paramagnetic defects is outlined. Nanostructuring of silicon results in
a modification of the magnetic behavior with reduced diamagnetic contribution,
and a further posttreatment of the samples leads to a smaller diamagnetic
susceptibility.
Introduction
Diamagnetism is present in all matter, and this diamagnetic behavior is caused
by the modification of the motion of the electrons by an applied magnetic
field resulting in a magnetic moment which is antiparallel to the generating field.
K. Rumpf (*) P. Granitzer

Institute of Physics, Karl-Franzens-University Graz, Graz, Austria
e-mail: klemens.rumpf@uni-graz.at
DOI 10.1007/978-3-319-05744-6_29
281
282
Table 1 List of selected
diamagnetic materials with Name
their molar susceptibility
Bismuth
values (wm w V m wM
)
Copper
(Landolt-Bornstein 1986)
Carbon
Gallium
Germanium
Gold
Indium
Silver
Silicon
Silicon dioxide
Sulfur
K. Rumpf and P. Granitzer
Formula
Bi
Cu
C
Ga
Ge
Au
In
Ag
Si
SiO2
S
Molar susceptibility
m (106 cm3 mol1)
280
5.46
3.96
21.6
11.6
27.97
10.2
20.7
3.65
29.6
15.4
The susceptibility of a diamagnetic material is negative ( 1) and normally

varies only slightly with temperature. Ionic and covalent-bonded crystals,
materials with complete filled shells, offer a diamagnetic behavior: the so-called
Lamor or Langevin diamagnetism. Due to an even number of electrons, no net
magnetic moment is present and such materials do not exhibit permanent magnetic
dipoles. In such substances diamagnetism arises in an external field due to
the modification of the motion of orbital electrons in the atoms to shield the
external field.
In systems with free electrons, the so-called Landau diamagnetism is present
which is caused by an orbital motion. In semiconductors and metals, free
electrons can contribute to the diamagnetic behavior because the electrons will
perceive a magnetic force caused by the external field and thus modify their
motion (Cullity and Graham 2008). In the case of semiconductors, the holes
can also deliver a diamagnetic contribution. Corresponding to Lenz law the
occurring local magnetic moment counteracts the applied magnetic field.
In semiconductors the density of the conduction electrons is much lower than
in metals and temperature dependent. Usually in semiconductors the diamagnetism from the lattice predominates.
Diamagnetic materials are not related to a magnetic moment on the atomic scale
without magnetic field, in contrast to para- and ferromagnetic substances. In more
than half of the elements of the periodic table, paramagnetism dominates and thus
the susceptibility offers a positive value.
The susceptibility of diamagnetic materials is in general very small; thus, these
materials are treated as nonmagnetic. The susceptibility of these materials is
dependent neither on the magnetic field nor on the temperature, and thus, the
magnetization is linear with the field and independent of temperature. Table 1
shows the negative susceptibility values of selected materials.
283
Beside electrical investigations of semiconductors, the examination of the magnetic properties has also been of importance to get knowledge of the electronic
structure. Information about the band structure as well as the configuration of
trapping levels could be obtained (Sonder and Stevens 1958).
Diamagnetism of Silicon and Porous Silicon

The literature susceptibility value for bulk silicon is given as 4.2 106
(Blakemore 1985) and for SiO2 16.3 106 (Schenck 1996). Silicon is a weakly
diamagnetic material, where the susceptibility depends on the doping. Measurements
of the magnetic susceptibility of semiconductors show that the lattice term, the
conduction electrons, as well as electrons trapped on donor atoms contribute to
the susceptibility (Sonder and Stevens 1958). The diamagnetic contribution of the
lattice term is due to the core electrons. The contribution of the conduction electrons
decreases with decreasing temperature. At low temperatures electrons are trapped by
donors which results in a superposed Curie paramagnetism, so the magnetic
behavior of doped silicon is composed of the diamagnetism due to core electrons as
well as conduction electrons and the paramagnetic term arising from unionized
donors (Sonder and Stevens 1958). The Curie paramagnetism at low temperatures
arising from trapped electrons on donor atoms shows a deviation from the Curie law
with increasing doping density due to interactions between neighboring donors
(Helms and Poindexter 1994). Measurements of the magnetic susceptibility of
p-type Si (5 1015 carriers) show a small temperature dependence which arises
from the paramagnetic component (Candea et al. 1977).
The paramagnetic behavior will be discussed in the handbook chapter
Paramagnetic and Superparamagnetic Silicon Nanocomposites.
Magnetization measurements of a highly n-doped silicon wafer (1019 cm3) give a
clear diamagnetic signal ( 1.2 106) which can be seen in Fig. 1. Furthermore,
for comparison the magnetization curves of porous silicon in the mesoporous range
prepared from the same substrate are shown. The sample has been prepared by
anodization in a 10 wt% hydrofluoric acid solution with a current density of
40 mA/cm2. The resulting porosity of the porous layer was about 70 %. On the one
hand as-etched porous silicon offering a hydrogen-terminated surface and on the other
hand porous silicon aged in ambient air and thus exhibiting a native oxide layer are
measured. In the case of the porous silicon (mesoporous morphology) samples,
the susceptibility is lowered from 7.5 107 to 2.6 107 which might be due
to the surface modification caused by the etching process and the concomitant
occurrence of dangling bonds (Matsuoka et al. 2012) at the surface and Si/SiO2
interface. These paramagnetic defects are mainly located at regions with high
mechanical stress (Wehrspohn et al. 2000) and lead to a decrease of the occurring
diamagnetic behavior. In comparison hydrogenated amorphous silicon offers a
susceptibility of about 1.0 106 (Baugh et al. 2001).
284
Fig. 1 Comparison of the magnetization curves of bare n+ silicon ( full line), as-etched porous
silicon prepared from the same wafer (dotted line), and aged porous silicon offering a native oxide
layer (dashed line). All three samples show a diamagnetic behavior, whereas the estimated
susceptibility varies between 1.2 106 (Si), 7.5 107 (as-etched), and 2.6 107 (aged).
The measurements have been performed at T 4.2 K. The diamagnetic behavior of porous silicon
decreases if the sample is oxidized (in contrast to hydrogen terminated) which might be caused by
the occurrence of dangling bonds
With increasing porosity these effects become more and more important because
the surface-volume ratio increases. Porous silicon samples with low porosity
(below 30 %) show a similar susceptibility to the bulk silicon substrate.
Conclusion
The magnetic behavior of silicon consists of a diamagnetic and a paramagnetic
term, wherein the diamagnetism predominates. The susceptibility arises from three
contributions, the core electrons, conduction electrons, and trapped electrons. The
paramagnetic term of the susceptibility depends on the temperature and on the
doping density of the substrate. Nanostructuring of silicon results in a modification
of the magnetic behavior with reduced diamagnetic contribution. Further
posttreatment of the porous silicon, e.g., oxidation, leads to a smaller diamagnetic
susceptibility. Porous silicon exhibits predominantly diamagnetic behavior wherein
the paramagnetic term is modified by additional occurring dangling bonds and thus
the magnetic properties also depend on the porosity of the material. In general
silicon as well as porous silicon offers a diamagnetic behavior which is small
compared to materials such as bismuth, gold, or copper (see Table 1). Furthermore,
285
strong diamagnetism is associated with superconductivity in relation with silicon

quantum well nanostructures (Bagraev et al. 2006), which has not been observed in
the case of porous silicon.
References
Bagraev NT, Gehlhoff W, Klyachkin LE, Malyarenko AM, Romanov VV, Rykov SA (2006)
Superconductivity in silicon nanostructures. Physica C 437438:21
Baugh J, Han D, Kleinhammes A, Wu Y (2001) Magnetic susceptibility and microstructure of
hydrogenated amorphous silicon measured by nuclear magnetic resonance on a single thin
film. Appl Phys Lett 78:466
Blakemore JS (1985) Solid state physics, 2nd edn. Cambridge University Press, Cambridge
Candea RM, Gee CM, Hudgens SJ, Kastner M (1977) Temperature dependence of the diamagnetic
and dielectric susceptibility of silicon. Phys Rev B 16:2657
Cullity BD, Graham CD (2008) Introduction to magnetic materials. Wiley, Hoboken
Helms CR, Poindexter EH (1994) The silicon-silicon dioxide system: its microstructure and
imperfections. Rep Prog Phys 57:791
Landolt-Bornstein (1986) Zahlenwerte und Funktionen aus Naturwissenschaft und Technik, Band
16, Diamagnetische Suszeptibilitat, Hrg.: K.-H. Hellwege, A.M. Hellwege, Springer
Matsuoka T, Vlasenko LS, Vlasenko MP, Sekiguchi T, Itoh KM (2012) Identification of a
paramagnetic recombination center in silicon/silicon-dioxide interface. Appl Phys Lett
100:152107
Schenck JF (1996) The role of magnetic susceptibility in magnetic resonance imaging: MRI
magnetic compatibility of the first and second kinds. Med Phys 23:815
Sonder E, Stevens DK (1958) Magnetic properties of n-type silicon. Phys Rev 110:1027
Wehrspohn RB, Deane SC, French ID, Gale I, Hewett J, Powell MJ, Robertson J (2000) Relative
importance of the SiSi bond and SiH bond for the stability of amorphous silicon thin film
transistors. J Appl Phys 87:144
Ferromagnetism and Ferromagnetic

Silicon Nanocomposites
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Intrinsic Ferromagnetism of Mesoporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Deposition of Ferromagnetic Nanostructures into Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Magnetic Properties of the Composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
288
288
289
292
294
294
Abstract
This chapter reviews first the intrinsic magnetic behavior of empty porous
silicon; next the filling of the pores with ferromagnetic metals (Ni, Co, NiCo,
Fe) by electrodeposition; and finally the adjustability of the magnetic properties
of the nanocomposite due to the modification of the porous silicon, as well as
due to a variation of the geometric characteristics of the metal deposits.
The magnetic characteristics of these hybrid materials strongly depend on
the pore structure of the template as well as the geometry and the spatial
distribution of the embedded metal structures. Besides the shape and size of
the nanostructures, a key factor is the magnetic interaction between metal
structures which determines the properties of the system. The ferromagnetic
behavior of the nanocomposites, which is also present at room temperature,
opens the opportunity for new applications.
P. Granitzer (*) K. Rumpf

e-mail: petra.granitzer@uni-graz.at
DOI 10.1007/978-3-319-05744-6_30
287
288
P. Granitzer and K. Rumpf
Introduction
The transformation from bulk silicon into nanostructured silicon provokes new
physical and chemical properties compared to the substrate (Canham 1990, 1995;
Ben-Chorin et al. 1994). Besides such optical (Canham 1990; Koshida and Koyama
1992) and transport (Balberg 2000) properties, also the magnetic behavior is changed
due to the modification of the surface (see next chapter Diamagnetic Behavior of
Porous Silicon). Porosity enables the incorporation of magnetic materials alongside
such nanosized silicon structures resulting in a composite material which merges
the electronic properties of the semiconductor and the magnetic behavior of the
embedded nanostructures. The diamagnetic and paramagnetic properties of bare
porous silicon are in general weak and thus after filling the ferromagnetism of
the metal structures predominates.
Due to the fact that porous silicon can be fabricated with different morphologies
(Foll et al. 2002; Lehmann and Gruning 1997; Lehmann et al. 2000), also with
straight and separated pores, it is an adequate host material for various metal fillings
(Jeske et al. 1995; Herino 1997; Fukami et al. 2011). Porous silicon in the mesoporous
range, for example, from a highly n-doped silicon wafer, offers oriented pores
grown along the (100) direction. The metal filling of the pores leads to a system
with a three-dimensional arrangement of ferromagnetic nanostructures with tunable
magnetic properties.
Such composite materials are of interest because the opportunity to manipulate
the spin of electrons by an electric field would give rise to new applications in
microtechnology. This quite new topic of so-called spintronics is currently under
great investigation (Jansen et al. 2012; Jansen 2012). Silicon as base material is a
precondition to be integrable in todays process technology. A further condition is
the successful operation at room temperature, which is not easily reached yet in
case of diluted magnetic semiconductors (Dietl 2010).
In the following review, first the magnetic behavior of bare porous silicon will be
outlined briefly and second the filling of the pores with ferromagnetic metals (Ni, Co,
NiCo, Fe) by electrodeposition will be discussed followed by the adjustability of the
magnetic behavior of the nanocomposite. The magnetic characteristics of these hybrid
materials strongly depend on the morphology of the template (Rumpf et al. 2012) as
well as the geometry (Granitzer et al. 2012a) and the spatial distribution (Rumpf
et al. 2011) of the embedded metal structures. The ferromagnetic behavior which is
also present at room temperature opens the opportunity for new applications.
Intrinsic Ferromagnetism of Mesoporous Silicon

Bulk crystalline silicon shows negligible ferromagnetism. Considering as-etched,
hydrogen-terminated porous silicon, a weak diamagnetic behavior is generally
observed (see chapter in this handbook Diamagnetic Behavior of Porous
Silicon). In the case of oxidized surfaces, the Si/SiO2 interface offers dangling
bonds, the so-called Pb centers which are the dominant paramagnetic defects in
Ferromagnetism and Ferromagnetic Silicon Nanocomposites
289
Fig. 1 Magnetization curves

of mesoporous silicon of
about 80 % porosity showing
a weak ferromagnetic
behavior (Granitzer
et al. 2008a)
porous silicon (Cantin et al. 1997). However, interestingly, weak ferromagnetic

behavior of porous silicon has been reported by various groups. A magnetic
behavior of luminescent porous silicon has been reported by Laiho et al. (1993).
In this case the observed ferromagnetism has been attributed to the low dimensions
of the material which exhibits dimensions in a similar range than the magnetic
exchange interaction leading to ordering effects. For comparison, the exchange
q
, with A as the exchange constant and MS as saturation
length lex ( lex 2A
M2
0
magnetization) of ferromagnetic metals as Fe, Co, and Ni is between 3 and 10 nm.

Recently a ferromagnetic behavior observed on porous silicon samples which have
been etched in an HF solution and additionally treated with KOH has been attributed
to an interface magnetism (Kopnov et al. 2007) which has also been observed on
other diamagnetic materials as thin gold layers or thiol-capped gold nanoparticles
(Vager and Naaman 2004). Another ferromagnetic behavior has been reported using
Si-ion and Ar-ion implantation into silicon as well as by neutron irradiation
(Dubroca et al. 2006) and is explained by the unpaired spins of the dangling bonds
which interact and lead to a ferromagnetic contribution. Furthermore ferromagnetic
behavior could be observed in mesoporous silicon samples which show a decreasing
saturation magnetization with decreasing porosity, whereas very low porosities
show only a diamagnetic contribution. These ferromagnetic properties have been
observed in a broad temperature range between 4.2 K and room temperature
(Granitzer et al. 2008a). An example can be seen in Fig. 1.
Deposition of Ferromagnetic Nanostructures into Porous Silicon

The deposition of various metals (magnetic, nonmagnetic) into pores has been carried
out by different methods such as electrochemically (Ogata et al. 2006), electroless
(Yae et al. 2009), or by CVD (Aylett et al. 1996). Besides noble metals (Koda
et al. 2012; Fukami et al. 2008), Cu has been deposited within porous silicon
290
Table 1 Various electrolyte compositions used for the deposition of ferromagnetic metals
Metal
Ni
Electrolyte
All chloride NiCl2
Ni
Watts
Co
Sulfate CoSO4
NiCo
Fe
Watts + CoSO4
Sulfate FeSO4
Ni-Fe (Aravamudhan et al. 2007)
NiSO4, NiCl2, FeSO4
Composition
170 g/l NiCl2
40 g/l H3BO3
45 g/l NiCl2
300 g/l NiSO4
45 g/l H3BO3
120 g/l CoSO4
30 g/l H3BO3
2:1
16 g/l FeSO4
10 g/l H2SO4
200 g/l NiSO4
8 g/l FeSO4
5 g/l NiCl2
25 g/l H3BO3
3 g/l saccharin
(Fang et al. 2007; Fukami et al. 2009) also with the aim for applications in microtechnology (Zacharatos and Nassiopoulou 2008). The deposition of elongated Ni
nanostructures has been carried out to investigate the magnetic properties of the system
(Gusev et al. 1994). The deposition of ferromagnetic materials into the pores of porous
silicon such as Ni, Co, Fe, and their alloys leads to a composite material which offers
ferromagnetic properties at room temperature. With increasing aspect ratio, the filling
of the pores becomes more challenging, and thus the loading of high aspect ratio pores
(>100) is not trivial, and so a continuous homogeneous filling of such pores has not
been achieved yet (Dolgyi et al. 2012). In the case of electrodeposition, an aqueous
metal-salt solution is used as electrolyte. In Table 1 a summary of employed
electrolytes can be found. For a review dedicated to this impregnation technique, see
the chapter in this handbook Porous Silicon and Electrochemical Deposition.
During the process, two kinds of metal deposition are occurring. One possible
reaction is electroless metal deposition:
2M2 Si H2 O ! 2M SiO2 4H ,
and furthermore electrodeposition takes place under cathodic conditions:
M2 2e ! M
Gaseous hydrogen is formed, if the current density exceeds a certain value
(Bandarenka et al. 2012) which can influence and hamper the precipitation of the
metal structures.
2H 2e ! H2
291
Fig. 2 Scanning electron micrographs (BSE) showing different arrangements of deposited Ni

nanostructures within the pores of the porous silicon (Granitzer et al. 2008b). The pore diameter in
all templates is around 60 nm, and the length is around 30 m. First row: the spatial distribution of the
deposited metal varies between 2/3 and 1/3 of the depth of the porous layer. Second row: the porous
layers are filled between surface and bottom of the pores, but the shape of the precipitated Ni
structures differs (from left to right: wires, ellipsoids, particles). Third row: zoomed areas of row two
In general, the deposition of metals into porous silicon is a cathodic process and
reduces the metal-salt ions to metal (e.g., Ni2+ + 2e Ni). Imperfections and variations of the pore shape such as dendritic branches can also lead to inhomogeneities of
the metal deposits, and thus a homogeneous filling of the pores is extremely difficult
to obtain. In the case of high aspect ratio pores, it is important to ensure that the
exchange of electrolyte is sufficient along the entire pore length. If it is insufficient,
pores can be blocked and a continuous growth of a metal wire along the whole length
is inhibited. The degree of pore filling depends on the applied current density as well
as on the pulse duration of the current (Granitzer et al. 2009). By choosing the
deposition parameters in an adequate way, the geometry and spatial distribution of
the ferromagnetic deposits are tunable, and thus tailoring of the magnetic properties of
the composite is possible. The metal structures can be deposited in a broad size range
(spheres according to the pore diameter, ellipsoids with a long axis of 100500 nm
and needles up to a few micrometers in length). In Fig. 2 an overview of various Ni
fillings within porous silicon can be seen.
292
Magnetic Properties of the Composite

Characteristics of ferromagnetism are a spontaneous magnetization and the occurrence of a hysteresis (Bozorth 1993). The mechanisms responsible for the formation
of magnetic domains are exchange interaction and anisotropy effects (Bertotti
1998). If the size of the ferromagnetic substance is reduced to below a certain
q
critical radius r d 36 KM1 2 (K1 is anisotropy constant, MS is the saturation
0
magnetization), the domain structure is reduced to one single domain. Such

nanosized structures and especially the arrangement of magnetic nanostructures
on surfaces or in three dimensions give rise to novel properties which depend not
only on the geometry of the structures but also on the interactions between them.
Employing templates with well-separated pores for the incorporation of magnetic
nanostructures improves the coercivity and squareness of a hysteresis compared to
magnetic thin films, and the magnetic easy axis is turned from the in-plane to the outof-plane direction. The deposition of ferromagnetic thin films on porous silicon
results in an in-plane magnetization (Dai et al. 2007). There are three possible
parameters of the samples which can be modified to determine the magnetic behavior,
namely, the kind of metal deposited within the pores, the morphology of the
porous template, and the electrochemical conditions which can be tuned during
the deposition procedure resulting in different geometries of the deposits. All these
features influence the magnetic properties, whereas the morphology of the porous
silicon template mainly influences the dipolar coupling between adjacent pores and
thus the magnetic anisotropy between easy and hard axis magnetization (Granitzer
et al. 2012b). With increasing distance between the pores, the magnetic interaction
between metal structures of adjacent pores decreases. The magnetostatic energy Em of
a couple of two parallel dipoles of length l at a distance r is given by
!
p2
1
1
p ,
Em
20 r
r 2 l2
where p is the pole strength (p 0 d2 m/4) (Samwel et al. 1992). A further
reason for enhanced magnetic anisotropy is the elongated shape of the deposits and
pore walls with a minimum of side branches which strongly influence the stray
fields (Bryan et al. 2012). In the case of nanowire arrays, the magnetic anisotropy is
mainly composed of shape anisotropy and magnetocrystalline anisotropy, whereas
in the case of Ni wires the shape anisotropy is the dominating factor (Vega
et al. 2011). Preliminary investigations showed that the Ni wires embedded in
porous silicon are polycrystalline, and thus the magnetocrystalline anisotropy is
negligible. Different loading of the pores can be achieved by modifying the
deposition parameters (Rumpf et al. 2010) leading to nanostructures of distinct
geometry and in various spatial distributions along the pores (Rumpf et al. 2008).
Figure 3 shows three magnetization curves of porous silicon samples with equal
morphology but different geometry of the Ni deposits, varying between spherical
particles (~60 nm), ellipsoids (~300 nm), and wires (~1 m). The coercivity varies
293
Fig. 3 Hysteresis loops of Ni

particles ( full line), Ni
ellipsoides (dotted line), and
Ni wires (dashed line)
deposited within the pores of
porous silicon, whereas the
morphology has been the
same. The coercivity as well
as the remanence decreases
with increasing elongation of
the metal nanostructures. The
magnetic field has been
applied perpendicular to the
sample surface
Table 2 Variation of the coercivity and squareness with modification of the pore diameter
Pore diameter
PS 60 nm (Vega et al. 2011)
PS 35 nm (Granitzer et al. 2012b)
AAO 80 nm (Vazquez et al. 2004)
AAO 30 nm (Vazquez et al. 2004)
HC,II (Oe)
280
660
360
600
HC, (Oe)
180
190
250
260
(MR/MS)II
0.48
0.89
0.35
0.70
(MR/MS)
1.5
3.47
1.44
2.3
PS porous silicon, AAO anodic aluminum oxide
between 280 Oe (wires) and 500 Oe (spherical particles) and the squareness
(MR/MS) between 0.2 (wires) and 0.52 (particles), MR being the magnetic
remanence and MS the saturation magnetization.
Magnetic remanence, especially the squareness, provides information about
coupling mechanisms between metal nanostructures (Stoner and Wohlfarth 1948).
Ferromagnetic structures with a random distribution of orientations offer a
squareness of 0.5. In comparison structures with the easy axis aligned parallel to
the applied magnetic field exhibit a squareness of 1 whereas with the easy axis
perpendicular to the magnetic field a value of 0 (Coey 2009). A decrease of the
squareness is caused by a diminution of the magnetic remanence. The smaller
values determined from specimens with embedded Ni wires within porous silicon
compared to the ones with Ni particles arise from demagnetizing effects.
If the morphology of the template is modified and the geometry of the deposits is
equivalent (wires), the magnetic characteristics also change as summarized in
Table 2. In all samples the shape anisotropy is the dominating factor because of
the high aspect ratio. The differences in the magnetic behavior are mainly due to
magnetic interactions and the thickness of the Ni wires.
Comparing the magnetization of porous silicon/metal nanocomposites with
oxide heterostructures consisting of CoFe2O4 nanopillars in a BiFeO3 matrix
(Chen et al. 2013), the magnetic moment is about one order of magnitude higher
294
in the case of the porous silicon composite. Other systems with two-dimensional
arrangements of magnetic nanostructures (Enders et al. 2010) need big areas or a
magnetic material with high magnetization. One of the characteristics of the porous
silicon system is the three-dimensional arrangement of the ferromagnetic
nanostructures embedded within high aspect ratio pores which yields to a high
magnetic moment. There is also a report on Ni deposition within porous silicon
which describes the formation of Ni silicide during the electrodeposition process
(Dolgiy et al. 2013) which reduces the magnetic moment of the specimen.
Conclusion
Intrinsic ferromagnetism of nanostructures silicon is very weak, but the
nanocomposites consisting of deposited magnetic nanostructures offer a strong
ferromagnetic behavior. Porous silicon with its tunable morphology is an adequate
template material for metal deposition to gain 3D arrays of deposited
nanostructures. In the case of ferromagnetic metal precipitation, the magnetic
properties of the nanocomposite can be tailored on the one hand by the deposition
procedure and on the other hand by the modification of the template morphology.
The obtained system exhibits a quasi ferromagnetic semiconductor material
which offers its ferromagnetic properties at room temperature. Due to the silicon
substrate, it can be readily integrated in todays microtechnology, and thus the
system is promising for various applications in sensor technology, magneto-optics,
and also the emerging field of spintronics.
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Paramagnetic and Superparamagnetic

Silicon Nanocomposites
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Superparamagnetic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Infiltration of Iron Oxide Nanoparticles Into Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Magnetic Behavior of the Composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
298
298
299
299
302
303
303
Abstract
In this chapter the paramagnetic properties of nanostructured silicon are outlined

and furthermore the magnetic properties of a composite material consisting of
porous silicon with infiltrated superparamagnetic iron oxide nanoparticles are
discussed. The magnetic behavior of the system depends on the nanoparticle size
as well as on the magnetic coupling between them. Both influence the so-called
blocking temperature, the transition between superparamagnetic behavior and
blocked state. A particle size-related assessment shows that the blocking
temperature increases with increasing particle size if the distances between the
particles are equal. The blocking temperature can be decreased by weakening the
magnetic interaction between the particles. Due to the good biocompatibility of
both porous silicon and iron oxide nanoparticles, the composite system is of
interest for biomedical applications in the fields of therapy and diagnosis.
P. Granitzer (*) K. Rumpf

e-mail: petra.granitzer@uni-graz.at
DOI 10.1007/978-3-319-05744-6_31
297
298
Introduction
In the case of paramagnetic materials, each atom possesses a permanent dipole
moment due to a remaining electron spin or orbital magnetic moments. Without
external magnetic field, the magnetic moments offer a random orientation resulting in
no net magnetization. If a magnetic field is applied, the free rotating dipoles align
preferentially in field direction, but there is no interaction between individual dipoles.
Silicon, especially with hydrogen-terminated silicon surfaces, is in general
diamagnetic and free of paramagnetic defects (see handbook chapter Diamagnetic
Behavior of Porous Silicon). Oxidation leads to interface defects (Si/SiO2), so-called
dangling bonds. They are paramagnetic in the neutral charge state which corresponds
to a one-electron spin S 1/2 configuration (Bardeleben and Cantin 1997). These
paramagnetic defects (Pb center) are superimposed on the diamagnetic contribution.
Due to the large surface area in nanostructured porous silicon, much higher
concentrations of defects can occur, contrasting with bulk silicon. The interface
between Si/SiO2 has been investigated by many authors according to the dangling
bond of the silicon atom, the Pb center which is the dominant paramagnetic defect in
porous silicon (Cantin et al. 1997). Their concentration depends on the position of
the Fermi level and it can also be modified by the H-termination. Oxidation of the
surface can increase the Pb center defect concentration. Two further paramagnetic
defects in the oxide layer have been observed, the oxygen vacancy defect E
(Pointdexter et al. 1981) and the EX defect in SiO2 (Pointdexter et al. 1981). EPR
studies give information about these defects from analysis of g-tensors (Cantin
et al. 1995) and hyperfine data (von Bardeleben et al. 2005).
A special kind of paramagnetism is the so-called superparamagnetism which is
dedicated to small magnetic particles which fall below a critical radius of single
domain particles. After the incorporation of such particles into the pores of porous
silicon, the composite system offers specific magnetic properties which will be
discussed in the next section of this review.
Superparamagnetic Nanoparticles
If a ferro-/ferrimagnetic material is fabricated in a nanoscopic size range and goes
below a critical value, the particle becomes superparamagnetic (SPM) which means
that the thermal energy dominates over the anisotropy energy and the whole particle
behaves like a paramagnetic spin (Bertotti 1998). Below this so-called superparamagnetic blocking radius, the particles lose their remanence. The transition takes
place at the so-called blocking temperature TB KV/25kB (K is the anisotropy
constant; V is the particle volume).
SPM nanoparticles are of interest for magnetic applications such as high-density
data storage in fabricating particles with high anisotropy constant and thus overcome the superparamagnetic limit (Frey et al. 2009). Due to magnetic interactions
Paramagnetic and Superparamagnetic Silicon Nanocomposites
299
between them, new properties arise such as soft magnetic alloys (Suzuki 1999) and
hard magnetic materials with an improved energy product (Skomsky and Coey
1993). In biomedicine SPM nanoparticles are also employed for diagnostics and
therapeutics, e.g., magnetic resonance imaging (Yallapu et al. 2011), hyperthermia
(Lee et al. 2011), and cancer therapy (Lee et al. 2011). Especially iron oxide
nanoparticles play an important role due to their low toxicity.
Such magnetic nanoparticles are often prepared by chemical synthesis, and in
general they are coated with a shell of a few nanometers which often is a metal-oxide
(Wei et al. 2010), a silica (Joo et al. 2009), or an organic surfactant (Shukla
et al. 2009) to prohibit agglomeration and to stabilize them. Thus, magnetic exchange
interaction is excluded and only dipolar coupling can take place.
A further approach to stabilize the particles is their incorporation into a
nonmagnetic or weakly magnetic matrix as, for example, polymers (Munoz-Bonilla
et al. 2012), silica (Lee et al. 2008), zeolites (Lukatskaya et al. 2009), or porous
silicon (Granitzer et al. 2010). Furthermore, the use of a matrix adds another
degree of freedom and allows tuning of the properties, depending on the particle
arrangement within the matrix.
Infiltration of Iron Oxide Nanoparticles Into Porous Silicon

Because of its adjustable morphology, porous silicon (Lehmann 2002) is useful as a
host matrix. For example, iron oxide nanoparticles have been deposited onto hydroxyl
functionalized porous silicon samples resulting in a self-organizing dendrite-like
arrangement on the surface which offers a new composite material (Balakrishnan
et al. 2006). The magnetite nanoparticles which are superparamagnetic show
dendrite-like formation caused by a diffusion-limited aggregation model (Witten
and Sander 1981). If Fe3O4 nanoparticles are infiltrated into the pores of mesoporous
silicon, the achieved system leads to a composite material (Fig. 1) showing a
ferromagnetic-like behavior at low temperatures (T < TB) and superparamagnetism
at higher temperatures (T > TB) (Granitzer and Rumpf 2011). This transition
temperature (blocking temperature TB) can be influenced by the particle size but
also by the distance between the particles. In principle the distance between the
particles within the pores can be tuned either by the thickness of the organic coating
or by the filling density. A further degree of freedom is to vary the distance between
particles of adjacent pores by the morphology of the matrix.
Magnetic Behavior of the Composite

The superparamagnetic behavior of the Fe3O4/porous silicon system above a
blocking temperature TB is examined by temperature-dependent magnetization
measurements (Granitzer et al. 2010). For more detail on this technique and
300
Fig. 1 Scanning electron image of magnetite nanoparticles within porous silicon (Granitzer and
Rumpf 2011). The size of the particles is 8 nm and the oleic acid shell is about 2 nm
others, see handbook chapter Magnetic Characterization Methods for Porous

Silicon. In the case of 8 nm particles, zero field-cooled (ZFC)/field-cooled
(FC) investigations performed at an applied field of 500 Oe show a rather
high blocking temperature TB at 170 K which indicates magnetic interactions
between the particles. The strength of the coupling can be modified by varying
the packing density of the particles within the pores. This effect can be achieved
by changing the concentration of the particle solution (Granitzer et al. 2011;
Fig. 2b). By varying the particle size, TB is also strongly influenced which can
be seen in Fig. 2a. Furthermore, a shift of the blocking temperature to lower
temperatures with higher applied fields is observed. This behavior of superparamagnetic particles is known to be proportional to H2/3 at high fields and
proportional to H2 for lower fields (Goya and Morales 2004). The blocking
temperatures determined for different applied magnetic fields are summarized
in Table 1.
Superparamagnetic behavior of porous silicon loaded with a magnetic material
could also be achieved by the deposition of Ni within luminescent stain-etched
porous silicon (Nakamura and Adachi 2012). Furthermore, porous silicon with
adsorbed parabenzoquinone molecules resulted in a nanocomposite which
exhibited paramagnetic properties (Antropov et al. 2012). However, this could be
due to the occurrence of additional dangling bonds due to nanostructuring, rather
than the loading of the porous silicon with organic molecules.
Iron oxide nanoparticles are of particular interest due to their magnetic
behavior (Gubin 2009) but also because of their low toxicity which renders
301
Fig. 2 (a) Shift of the blocking temperature with the particle size in using the same particle
concentration. (b) Change of TB with the concentration of the particle solution. In the latter case the
particle size is 8 nm for all concentrations. In all cases a template with equal morphology has been used
them applicable in biomedicine (Roca et al. 2009). The infiltration of iron

oxide nanoparticles into porous silicon which also is biocompatible (Canham
1995) results in a system of interest for magnetically guided drug delivery
(Gu et al. 2010).
302
Table 1 Shift of the blocking temperature with increasing applied magnetic field to lower
temperatures. The size of the infiltrated particles is 8 nm. The concentration of the magnetite
solution was fixed at 8 mg Fe/ml
Magnetic field [Oe]
5
500
1,000
Blocking temperature [K]

170
75
50
Biomedical Applications
Due to the low toxicity of both materials (porous silicon and iron oxide particles),
the system is of interest for biomedical applications. The handbook chapter
Biocompatibility of Porous Silicon reviews the important in vivo data on the
former material. Drug delivery with porous silicon is under investigation employing
not only particles but also films, chip implants, and composite materials. Nonetheless,
microparticles play a key role because they are compatible to most existing drug
delivery concepts (Anglin et al. 2008). On the one hand nanostructured PS tablets can
be utilized to carry a cocktail of drugs or nutrients which will be delivered in a
predetermined time within the body and on the other hand percutaneous implants of
PS with radioactive content can provide radiation to tumor cells (Anglin et al. 2008).
Serda et al. reports on a multistage delivery system applicable for biological imaging.
The loading of PS microparticles with superparamagnetic (SPM) iron oxide
nanoparticles (NPs) is presented as well as the examination of their cellular uptake
by macrophages. Furthermore the influence of 3-aminopropyltriethoxysilane on the
PS surface and retention of the iron oxide NPs is investigated (Serda et al. 2010).
For biosensing applications there are various approaches such as the fabrication of
arrays of micro test tubes and microbeakers consisting of macroporous silicon with
incorporated iron oxide nanoparticles (Ghoshal et al. 2011). Furthermore, optical
interferometer biosensors based on porous silicon are used for immunoassaying by
combing superparamagnetic particles with an interferometer porous silicon platform
(Ko et al. 2012). The handbook chapters Porous Silicon Immunoaffinity
Microarrays and Porous Silicon Optical Biosensors provide overviews of
these application areas. The combination of porous silicon with Fe3O4 particles and
additional loading with a molecular payload is of interest for controlled transport in
applying an external magnetic field. The loaded molecules (enzymes) can be
transported and subsequently released in an appropriate solution (Thomas
et al. 2006). The in vitro cytotoxicity of porous silicon particles loaded with magnetite
nanoparticles (see the related handbook chapter Cell Culture on Porous Silicon)
has been investigated in using the cell viability of human liver cancer cells and rat
hepatocytes (Kinsella et al. 2013). In vivo studies have been carried out on a
carcinoma rat model to figure out the biodistribution properties of the composite
material (Kinsella et al. 2013). Furthermore, after in vitro cytotoxicity tests, in vivo
assays have been carried out on New Zealand rabbits showing low inflammatory
303
response and no necrosis effect in the tissues of the treated eyes or in the fibrous
tissue formed around the agglomerated explanted flakes (Munoz Noval et al. 2013).
The composite system has been investigated in relation to the magnetic preconditions
for biomedical applications which means no magnetic remanence at room temperature (Rumpf et al. 2013). The magnetic moment is attempted to be high as possible
due to closely packed particle loading. To date, experiments demonstrating transport
of porous silicon loaded with iron oxide nanoparticles of different size (between 5 and
8 nm) in water have been successful. Size-dependent magnetization measurements
and subsequent cytotoxicity evaluation of Fe3O4/porous silicon showed that the
nanocomposite is an encouraging material for drug delivery (Granitzer et al. 2013).
Conclusions
Porous silicon offers in general a diamagnetic behavior, although due to surface
modification and oxidation, paramagnetic defects occur. The magnetic properties of
the material can be extended, for example, by the infiltration of superparamagnetic
nanoparticles. The achieved nanocomposite shows a transition between superparamagnetic behavior and blocked state, depending on the size of the loaded particles and
their particle-particle distance which allows the tuning of the magnetic properties.
Concerning the applicability the system is of interest not only for magnetic but also
for biomedical applications due to the biocompatibility of both materials.
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Photoluminescence of Porous Silicon

Bernard Gelloz
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photoluminescence Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photoluminescence of Individual Nanocrystals from Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . .
Photoluminescence of Porous Silicon Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
307
308
308
309
316
317
Abstract
The photoluminescence of mesoporous silicon and silicon nanocrystals has

received enormous study over the last 25 years. The spectroscopic nature and
efficiency of various emission bands from the near-infrared to the ultraviolet are
briefly reviewed, as are mechanistic studies on individual nanocrystals. Improvements in surface passivation and size control of silicon nanocrystals have led to
impressive photoluminescence quantum efficiencies in the visible range.
Introduction
The demonstration in 1990 that porous silicon could emit efficient tunable visible
photoluminescence (PL) at room temperature and attributed to quantum-size effects
in crystalline silicon (Canham 1990) has induced considerable worldwide research
activities in order to (i) identify the various PL bands and their respective properties
and emission mechanisms, (ii) optimize the PL efficiency, (iii) optimize the
PL stability, and (iv) tailor the PL spectrum (peak wavelength and FWHM).
B. Gelloz (*)
School of Engineering, Nagoya University, Nagoya, Japan
e-mail: gelloz@nuap.nagoya-u.ac.jp
DOI 10.1007/978-3-319-05744-6_32
307
308
B. Gelloz
This chapter reviews briefly the specificities of porous silicon PL measurements,

the PL of individual silicon nanocrystals from porous silicon, and the PL of porous
silicon layers.
Photoluminescence Measurement
The PL of porous silicon is quite broad (see Fig. 1a for spectra examples) and
inhomogeneous in nature and may involve several phenomena taking place in the
silicon nanostructure as well as in the tissue material surrounding it. The chemistry
of the various interfaces (e.g. Si/air, Si/SiOx) in porous silicon may also play a very
significant role in the luminescence. Thus, extreme care is necessary in the PL
measurement procedure and its interpretation (Pelant and Valenta 2012).
When using a single broadband grating, care should be taken to eliminate
contribution of the short wavelength part to the long wavelength part of the
spectrum due to the second order of grating diffraction.
Fine structures in the PL have sometimes been observed. At room temperature,
these structures (peaks modulating the otherwise generally Gaussian-shaped
PL spectrum) were mostly attributed to thin film interference (Kim et al. 2003;
Hooft et al. 1992). For the visible range, such interference effect can mostly be
observed for layer thicknesses ranging from about 0.5 to 3 m. At low temperature
(<200 K), and for clean, hydrogen-terminated porous silicon, fine structures have
been associated with optical phonon-assisted interband transitions (Calcott
et al. 1993; Elhouichet and Oueslati 2002), even for nonresonant excitation
(Xu and Adachi 2010).
Another specificity of porous silicon, particularly in its as-anodized state
(hydrogen-terminated), is its poor stability in air (Wolkin et al. 1999) or other
chemically active environments. Thus, the PL characteristics (e.g., peak wavelength, intensity) may change very rapidly during the measurement itself. When
precision is crucial, such as in measurement of degree of polarization, it is essential
to ensure good stability during the acquisition time of all spectra.
Photoluminescence of Individual Nanocrystals from Porous

Silicon
Single Si nanocrystals in which quantum confinement is expected to take place have
been extracted from porous silicon and studied by a few groups. Table 1 shows a
summary of the findings. The quantum efficiency of a single dot can be rather high
(>20 %). It is limited by the blinking effect, characterized by periods where
an excited nanocrystal does not emit any light for an extended period of time
and which has been seen earlier in various other semiconductor nanodots. A dot
whose surface is not perfectly passivated does not emit light. The surrounding
matrix could affect the PL lifetime as well as the emission spectral tunability at the
high-energy end of the visible range (Kusova et al. 2010).
309
Fig. 1 (a) Room-temperature PL spectra from porous silicon layers with different porosities kept
under Ar atmosphere. (b) Experimental and theoretical PL energies as a function of crystallite size.
The upper line is the free exciton bandgap and the lower line is the lowest transition energy in the
presence of a Si O bond. The solid and open dots are the peak PL energies of PSi samples kept in
Ar and air, respectively (Reprinted figures with permission from Wolkin et al. (1999) as follows:
M. V. Wolkin, J. Jorne, P. M. Fauchet, G. Allan, and C. Delerue, Phys. Rev. Lett., 82, 197200,
1999. Copyright (1999) by the American Physical Society). Image: PL under UV excitation of (c)
a porous silicon layer (initial porosity 68 %) treated by HWA (Gelloz et al. 2005; Gelloz and
Koshida 2005), (d) the same type of porous layer detached from the substrate and then treated by
HWA, and (e) the same type of porous layer heavily thermally oxidized (nanocrystal density
negligible) and then treated by HWA (blue PL) (Gelloz and Koshida 2009b; Gelloz et al. 2009)
Photoluminescence of Porous Silicon Layers

Depending mostly on the degree of quantum confinement and on the chemical state of
its surface, porous silicon could luminesce from the near-infrared (1.5 m) to the
near-UV as a result of distinct emission bands having different origins (Table 2; Cullis
et al. 1997; Bisi et al. 2000). The near-infrared band has not been as extensively
310
B. Gelloz
Table 1 Summary of studies and results related to the photoluminescence of single silicon
nanocrystals
System studied
Si nanopillars oxidized to produce
luminescent silicon cores (Valenta
et al. 2002; Sychugov et al. 2005)
Silicon nanodot with oxide shell
prepared by gas phase pyrolysis
(Martin et al. 2008)
Individual silicon nanocrystals within

porous silicon grains (Valenta
et al. 2008; Martin et al. 2004; Credo
et al. 1999; Mason et al. 1998, 2001;
Gargas et al. 2008)
Organically capped nanosilicon

(Kusova et al. 2010)
Comments
Efficiency: 35 %. FWHM ~ 130 meV (single band).
Emission polarized in arbitrary directions. Blinking
kinetics appear to be different from that of porous
silicon particles (Sychugov et al. 2005)
FWHM ~ 100 meV; satellites at ~150 meV attributed to
coupling to LO or TO SiOSi phonon modes of SiO2.
Strong electronphonon coupling to SiOSi phonons
limiting the tunability of light emission versus size at
high emission energies
Efficiency: 88 % (Credo et al. 1999; Mason et al. 1998);
1020 % for 1 exciton per nanodot; decreases as the
0.7th power of excitation at higher excitation (Valenta
et al. 2008). FWHM ~ 120 meV (Valenta et al. 2008;
Credo et al. 1999; Mason et al. 1998); splitting of
~160 meV (attributed to the stretching vibration of the
SiOSi bridge bond) (Credo et al. 1999; Mason
et al. 1998). Efficiency limited by blinking; in blinking,
OFF state is due to Auger recombinations and
excitonexciton scattering (Valenta et al. 2008).
Blinking obeys a power law statistics (Martin
et al. 2004). Ellipsoid shapes of silicon dots; degree of
polarization strongly anisotropic; depends on
anodization conditions (Gargas et al. 2008)
Efficiency: 20 % (for an ensemble of colloidal
nanodots). FWHM >100 meV; satellite peak at ~150
meV. Decay time: 10 ns at 550 nm
studied as the visible bands. It was observed in both partially oxidized porous silicon
and oxygen-free samples. It has been related to both quantum-size effect and surface
states (Koch et al. 1993). The UV band has been observed only in oxidized porous
silicon. It has been related to oxide luminescence, with the silicon nanocrystals
playing a potential role in the photoexcitation process (Qin et al. 1996).
The F-band, with emission peaks around 415470 nm, FWHM of 0.380.5 eV,
and quantum efficiencies of 0.1 % at best, has been reported in various thermally or
chemically oxidized PSi samples (Koyama and Koshida 1997; Qin et al. 1997;
Cullis et al. 1997; Bisi et al. 2000; Canham 1997). The PL lifetime is in the
nanosecond range. Many reports have attributed this band to oxide-related defects
or contamination (occurring upon storage and prolonged exposure to air) by organic
chromophores (e.g., carbonyl groups) (Loni et al. 1995). Recently, another origin
has been suggested: direct bandgap core luminescence (- transitions) (Prokofiev
et al. 2009). Using layers of oxide-embedded silicon nanocrystals obtained by
sputtering, de Boer et al. (2010) have clearly identified this direct bandgap band
and referred to it as the Hot PL band because it can be observed only under high
excitation. Indeed, getting a reasonable probability of radiative - transitions, a
constant generation of hot carrier at the 15-point (direct gap valley) by Auger
From near-infrared
to yellow
5901,300
surface
including
oxygen atoms
From yellow to blue

425630
From near-infrared
to blue
4001,300
hydrogenterminated
surface
Hot PL band
Sband
Label
IR band
Spectral range/
typical peak
wavelength (nm)
Near IR
1,1001,500
Table 2 Porous silicon luminescence bands
Typical: 110 % (Billat 1996;

Bsiesy et al. 1991; Gelloz and
Koshida 2000; Gelloz
et al. 1998a,b); record: 23 %
(Gelloz et al. 2005)
0.01 %
s range
ps range
Best efficiency
A few ns to
~150 s
Typical
lifetime at RT
10 ns10 s
Yes
Yes
Directly
electrically
excitable
No
(continued)
Generally proposed origin/

comments
States at the silicon surface
(Koch et al. 1993; Fauchet
et al. 1995; Canham 1995)
Quantum confinement in Si
nanocrystals; indirect bandgap
transitions; blueshift upon size
reduction; (Cullis et al. 1997;
Bisi et al. 2000; Wolkin
et al. 1999)
Fast relaxation of excitation to
surface states related to Si O
species sets a limit to the size
effect and a minimum emission
wavelength of ~590 nm.
Quantum confinement in Si
nanocrystals; direct bandgap
transitions; observed only under
high excitation; redshift upon
size reduction (de Boer
et al. 2010)

311
Long-lived band
UV band
Label
F-band
Table 2 (continued)
UV:
~350 (Qin
et al. 1996)
270290 (Gelloz
et al. 2014)
Blue-green
450540
Spectral range/
typical peak
wavelength (nm)
Blue-green
420 ~ 470
18 s up to ~
200 K; ~1 s at
RT
psns
Typical
lifetime at RT
~10 ns
2 % at 300 K; 8.5 % at 4 K
(Gelloz and Koshida 2012)
(including the F-band emission)
Best efficiency
0.1 %
No
Directly
electrically
excitable
No
Oxide-related species; emission

energy strongly dependent on
excitation energy (Gelloz and
Koshida 2012, 2009a; Kovalenko
et al. 1999; Wadayama
et al. 2002; Kux et al. 1995)
Generally proposed origin/

comments
Oxide-related defects (Cullis
et al. 1997; Bisi et al. 2000;
Koyama and Koshida 1997; Qin
et al. 1997)/contamination by
organic groups (Loni et al. 1995)
The Hot PL band may contribute
to the green part (Prokofiev
et al. 2009)
Oxide-related defects (Qin
et al. 1996; Gelloz et al. 2014)
312
B. Gelloz
313
recombination of multiple excitons, is necessary in order to compete with the

otherwise very fast (110 ps) non-radiative relaxation toward the -valley (indirect
gap valley). The Hot PL band characteristics can be found in Table 2. This Hot
PL band has only been clearly identified in a partially oxidized system (de Boer
et al. 2010). It could be a part of the so-called F-band, in particular the green
part, but is unlikely to be the F-band itself, most importantly because (i) it is
red-shifted as the crystalline core decreases, reaching the yellow range of the visible
spectrum, thus not matching any more the blue emission of the F-band, and (ii) a fast
blue band (peak wavelength 420 nm, independent of nanocrystal core size;
lifetime 10 ns) was still observed as an independent oxide-related band (likely to
be part of the F-band) in addition to the Hot PL band (de Boer et al. 2010). This
second point is also consistent with the observation of a fast (nanosecond range)
efficient blue emission peaked at 410 nm (FWHM 50 nm) in heavily oxidized
porous silicon not containing any significant amount of nanocrystals, thus supporting
the attribution of the blue part of the F-band to oxide-related species (Gelloz and
Koshida 2009b, 2012).
This latter fast blue band has been observed together with a long-lived band
(blue-green), which has been studied in details recently (Gelloz and Koshida 2009b,
2012). It is mostly characterized by (i) a long decay time (several seconds) in the
range 4180 K, (ii) a thermally activated quenching from about 180 K (activation
energy 0.2 eV), and (iii) a spectrum strongly dependent on the excitation energy.
The best PL external quantum efficiencies of this blue band was 2 % at room
temperature and 8.5 % at 4 K (Gelloz and Koshida 2012). An emission band
showing some similarities with this long-lived band has been observed previously
by a few other groups (Kovalenko et al. 1999; Wadayama et al. 2002; Kux
et al. 1995). Two of them (Kovalenko et al. 1999; Wadayama et al. 2002) got an
emission band peaked roughly around 540 nm for similar excitation wavelengths
(337 and 325 nm). Kovalenko et al. (1999) got a decay time of 0.5 s (shorter than
that observed by Gelloz et al. (Gelloz and Koshida 2009b, 2012)) at 15 K, in as
prepared (but probably slightly aged) as well as in oxidized porous silicon, and
attributed the emission to quantum confinement in very small silicon nanocrystals.
Wadayama et al. (2002) reported an emission decaying very slowly (>1 s) at room
temperature in porous silicon having been subjected to rapid thermal oxidation
(1,000 C) and quenching in liquid nitrogen. The fast cooling in liquid nitrogen was
the necessary step for the very slow band to be observed, which was not understood.
Kux et al. (1995) also observed this band in oxidized porous silicon (using rapid
thermal oxidation) and suggested it could be related to SiOH groups. Gelloz
et al. (Gelloz and Koshida 2009b, 2012) attributed the origin of this band to
molecular-like species in or at the surface of the oxide tissue in oxidized porous
silicon. Mechanisms based on molecular species are supported by the fact that it
could also be observed in fully oxidized porous silicon, with no silicon nanocrystals
left in the nanostructure, and also in pure porous glass. Moreover, a similar band has
been observed recently in both silica and Al2O3 nanoparticles. The origin of the
band was not completely clear but was hypothesized to be luminescence from
photogenerated OH radicals (Anjiki and Uchino 2012).
314
B. Gelloz
The most studied and technologically interesting band is the so-called S-band
(S for slow; decay times are rather long compared to those of direct bandgap semiconductors). It is electrically excitable and its properties (e.g., emission spectrum,
efficiency, chemical activity) can be in principle engineered. Its main characteristics
are summarized in Table 3. It originates mostly from exciton recombinations in Si
nanocrystals as indicated by polarization memory of PL, PL saturation under high
Table 3 Some characteristics of the S-band at 300 K
Typical values/
characteristics
1,300400 nm
Property
Peak wavelength
External quantum efficiency
FWHM
Bare layer
Porous
silicon
microcavity
Decay
Layers: 110 % (Billat 1996;

Bsiesy et al. 1991; Gelloz
and Koshida 2000; Gelloz
et al. 1998a, b); record: 23 %
(Gelloz et al. 2005)
Powders: 1016 % (Park
et al. 2009; Xia et al. 2012;
Tu et al. 2012) (Values for
red-orange PL)
150180 nm
13 nm (emission: 740 nm)

(Squire et al. 1998)
1040 meV (emission:
1.52.2 eV) (Araki
et al. 1996)
Decay time: ns to ~150 s
from blue to red; increases at
low temperature due to
singlettriplet exciton state
splitting (Cullis et al. 1997;
Bisi et al. 2000)
Multiexponential decay
Comments
Porosity dependent;
generally related to
nanocrystal sizes; can be
strongly influenced by
surface states (Wolkin
et al. 1999)
Key factors: nanocrystal
density (related to porosity),
surface passivation (Gelloz
et al. 2005); exciton
localization (Billat 1996;
Bsiesy et al. 1991; Gelloz
and Koshida 2000; Gelloz
et al. 1998a, b)
Inhomogeneous broadening
(mostly size effect) (Cullis
et al. 1997; Bisi et al. 2000)
Photonic crystal effect
(Pavesi et al. 1996; Araki
et al. 1996; Gong et al. 2010;
Squire et al. 1998)
Depends on quantum
confinement strength (effect
on wavelength) and surface
passivation (limited by
non-radiative
recombinations) (Cullis
Multiexponential shape
attributed to exciton
migration, carrier escape
from Si dots, distribution of
dot shape emitting at the
same energy (Cullis
et al. 1997; Bisi et al. 2000),
or more recently to the
blinking effect (Dunn
et al. 2009)
(continued)
315
Table 3 (continued)
Resonant
excitation
Typical values/
characteristics
0.2; decreases with
increasing detection
wavelength (Cullis
Phonon replica at 56 and
19 meV
Nonresonant
excitation
Multiple-peak structures;
peak separation ~ 64 meV
Property
Degree of polarization
(nonresonant photoexcitation)
Fine
structure at
low
temperature
Excitation density
Stability/surface chemistry
Output scales linearly with

excitation density until
Auger effects become
predominant. (Cullis
et al. 1997; Mihalcescu
Poor/SiH bonds
(as-anodized)
Good/SiH bonds replaced
by more stable SiC bonds
(Buriak 2002)
Improved/SiH bonds
replaced by more stable
SiAg bonds (Sun
et al. 2005)
Good/oxide shell
Comments
Can be anisotropic (effect of
crystallite shape)
Consistent with TO and

TA Si phonons (Cullis et al.
1997; Calcott et al. 1993)
Consistent with TO Si
phonons (Xu and Adachi
2010)
Critical excitation level:
more than one exciton per
silicon nanocrystal. See
Table 1 for more details
SiH bonds are easily

oxidized, even in air
Replacing hydrogen by long
organic chains also enhance
stability by steric hindrance
effect (Buriak 2002;
Boukherroub et al. 2000)
SiSiO2 interfacial defects

should be minimized. Best
techniques: hightemperature oxidation
(Cullis et al. 1997; Takazawa
et al. 1994; Petrovakoch
et al. 1992; Yamada and
Kondo 1992), high-pressure
water vapor annealing
(Gelloz et al. 2005; Gelloz
and Koshida 2005, 2007,
2006), chemical oxidation
(Xia et al. 2012; Tu
et al. 2012)
excitation due to Auger recombinations (Mihalcescu et al. 1995), and resonant

excitation and hole-burning experiments (evidencing phonon-mediated recombinations and singlettriplet exciton state splitting) (Cullis et al. 1997; Bisi et al. 2000).
Very high confinement energy (>0.7 eV) results in the breakdown of k-conservation
rules and direct recombinations become possible (Kovalev et al. 1998).
316
B. Gelloz
Figure 1a shows the progressive shift of the PL band of porous silicon having its
surface terminated by siliconhydrogen bonds (oxygen-free) across the visible
region obtained by changing the anodization conditions (Wolkin et al. 1999).
Generally, its intensity increases and its peak wavelength decreases when the
porosity increases. The efficiency usually decreases in the order n-type, p-type,
n+-type, and p+-type porous silicon due to differences in nanostructures. However,
surface states, in particular those introduced by oxygen via SiO bonds, can greatly
influence the peak wavelength, as shown in Fig. 1b. In zones II and III, localized
states lie inside the bandgap, setting a limit to the emission blueshift expected from
the size reduction and pinning the emission peak wavelength at about 590 nm for
nanocrystals below ~2.5 nm in size (Wolkin et al. 1999).
White PL can be obtained using partially oxidized porous silicon emitting
two-peak PL spectra resulting from the superposition of the blue-green emission of
the F-band (or of both the F-band and the long-lived band) and the yellow-redemitting S-band (Gelloz and Koshida 2005; Gelloz et al. 2009; Dohnalova et al. 2010).
While most data relate to porous silicon layers, recently a lot of effort was devoted
to the fabrication of porous silicon powders, in particular for bio-imaging purposes.
Some powders were obtained by breaking down anodized porous layers followed by
various types of oxidation steps used to tune the emission spectra and improve the
efficiency and stability (Park et al. 2009; Xia et al. 2012; Tu et al. 2012).
Porous silicon layers have also been made using electroless techniques. The
technique is used with thin films of microcrystalline silicon produced by PECVD
and leads to PL intensities (efficiency 110 %) comparable with that obtained from
anodized crystalline silicon (Solomon et al. 2008).
Surface passivation is essential for high emission quantum efficiency to reduce
the competitive defect-related non-radiative recombinations and good stability.
Silicon nanocrystals can be passivated by an oxide shell (Cullis et al. 1997;
Takazawa et al. 1994; Petrovakoch et al. 1992; Yamada and Kondo 1992; Gelloz
et al. 2005; Gelloz and Koshida 2005, 2007, 2006; Xia et al. 2012; Tu et al. 2012)
(one of best technique is high-pressure water vapor annealing (Gelloz et al. 2005;
Gelloz and Koshida 2005, 2007, 2006)) or by replacing SiH bonds of as-anodized
porous silicon by stronger and more stable bonds, such as SiC bonds (Buriak 2002;
Boukherroub et al. 2000). A striking effect of surface termination has recently been
confirmed by Dohnalova et al. (2013), who reported fast (nanosecond range) direct
bandgap-like blue emission using silicon colloids (prepared via a chemical route,
not from porous silicon) with carbon surface termination. The phonon-less transitions were explained by drastic modifications of electron and hole wavefunctions
(these transitions are not direct bandgap - transitions).
Conclusion
Recent developments such as fast phonon-less transitions from carbon-terminated
nanocrystals (Dohnalova et al. 2013), fast direct bandgap transitions (Prokofiev
et al. 2009; de Boer et al. 2010), and very high values of luminescence quantum
317
efficiencies of silicon nanocrystals in layers (in porous silicon, 23 % (Gelloz

et al. 2005; Gelloz and Koshida 2005), and in other assemblies, 18100 % (Ledoux
et al. 2000) and 60 % (Jurbergs et al. 2006)) show that the luminescence of
nanocrystalline silicon is progressively paving its way toward applications.
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Bernard Gelloz
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electroluminescence in Electrolytic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electroluminescence of Solid-State Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
321
322
323
324
329
Abstract
The performance of porous silicon visible light-emitting diodes is reviewed and

compared to those of silicon nanocrystals prepared by other fabrication routes.
Efficiencies up to 1 % have been achieved with porous silicon but almost up to
10 % with silicon nanocrystal-polymer composites. Challenges with simultaneously achieving high efficiency, output power, stability, and modulation speed
are highlighted. Further improvements could be realized from narrowing the
skeleton size distribution and improving the electronic transport and surface
passivation of porous silicon.
Introduction
Single silicon nanocrystals have been claimed to have very high electroluminescence
(EL) yields (up to 20 % (Valenta et al. 2004)). However, a practical LED requires
nanocrystals either dispersed in a matrix (like a polymer, or a wide-gap material) or as
parts of a silicon nanostructure (such as a porous silicon layer). Because the S-band
(see chapter Photoluminescence of Porous Silicon) is electrically excitable,
B. Gelloz (*)
School of Engineering, Nagoya University, Nagoya, Japan
e-mail: gelloz@nuap.nagoya-u.ac.jp
DOI 10.1007/978-3-319-05744-6_34
321
322
B. Gelloz
it was hoped that porous silicon EL could bring a revolution in optoelectronics.

However, after two decades of intensive research, the challenge of getting, for the
same device, high efficiency, high output, and sufficient stability is still open. In the
past few years, the interest in using porous silicon for EL has considerably decreased.
Very recently, encouraging high LED efficiencies (up to 8.6 % (Cheng et al. 2011)
and 1 % (Maier-Flaig et al. 2013)) have been reported using colloidal silicon
nanoparticles exhibiting very high photoluminescence external quantum efficiencies
(4060 %) (Jurbergs et al. 2006; Mastronardi et al. 2012). However, recent new
advances in porous silicon luminescence efficiency (Gelloz et al. 2005b; Gelloz
and Koshida 2005) and stability (Gelloz et al. 2003b, 2005b, 2006) show that
porous silicon remains as well a very promising candidate for EL purposes. This
chapter reviews the many types of devices that have been proposed and emphasizes
the best results.
Electroluminescence in Electrolytic Systems

Well-controlled EL has been observed in porous silicon contacted by a liquid electrolyte during anodic oxidation (Halimaoui et al. 1991; Billat 1996) or using redox
species able to inject carriers inside silicon nanocrystals (Table 1). The apparently
Table 1 EL characteristics of porous silicon contacted by a liquid electrolyte
Experimental
conditions
Anodic
polarization.
Photogeneration of
holes required for
porous silicon from
lightly doped
n-type silicon
Anodic
polarization
Cathodic
polarization.
Photogeneration of
electrons required
for porous silicon
from lightly doped
p-type silicon
(Gelloz and Bsiesy
1998; Peter and
Wielgosz 1996)
Carrier injection
Holes from substrate;
electrons from
oxidation of silicon
(Chazalviel and
Ozanam 1992)
Holes from substrate;

electrons from
oxidation of methyl
viologen (Kooij
et al. 1995) or formic
acid (Green et al. 1995)
Electrons from
substrate; holes from
reduction of S2O82
(Bressers et al. 1992;
Canham et al. 1992;
Peter et al. 1996;
Romestain et al. 1995;
Noguchi et al. 1999)
EL properties
EL triggered by injection of holes into
luminescent nanocrystals; blue shift of EL
during oxidation. EL limited in time because
Si nanocrystals are irreversibly oxidized
(Halimaoui et al. 1991; Bsiesy et al. 1991;
Hory et al. 1995; Cantin et al. 1996; Billat
1996)
EL triggered by injection of holes into
luminescent nanocrystals; not stable due to
simultaneous oxidation of silicon under
anodic polarization
EL triggered by injection of electrons into

luminescent nanocrystals; EL spectrum is
voltage tunable (Romestain et al. 1995).
Reversible; stability affected by ion
consumption, slow oxidation of silicon
surface, and possibly evolution of the location
of charge exchanges (Saren et al. 2002;
Noguchi et al. 1999). Reaction kinetics affects
the EL characteristics (Gelloz and Bsiesy
1998; Gelloz et al. 1996)
323
high EL efficiency was explained by efficient carrier injection at low voltages

(~12 V) within the whole, or a large part, of the porous silicon skeleton (Gelloz
et al. 1996), without significant voltage drop across the porous silicon layer itself
(Gelloz et al. 1999, 2003a; Gelloz and Bsiesy 1998). Related voltage-tunable and
energy-selective photoluminescence quenching (resulting from carrier injection
and non-radiative Auger recombinations) was also reported (Romestain et al. 1995;
Peter et al. 1996).
Electroluminescence of Solid-State Porous Silicon

In solid-state devices, the voltage is applied between the substrate backside and
a top semitransparent electrode (usually gold or indium tin oxide). Due to
the high resistivity of porous silicon, carrier transport and injection in
Si nanocrystals is challenging (see chapter Electrical Transport in Porous
Silicon). As a result, the EL mechanism in porous silicon mainly involves
impact processes (Oguro et al. 1997), even in porosified pn junctions. A porous
silicon structure has been specially designed to favor this excitation mechanism
(Gelloz et al. 2005a).
Porous silicon EL is generally affected by poor efficiency (mainly because of
low carrier injection efficiency, leakage, and high applied voltages), poor stability
(deterioration of surface passivation, or oxidation (Zhang et al. 1996), during
operation and storage), and low output intensity (a few Cd/m2 at best (Gelloz and
Koshida 2004a)). Many strategies have been implemented in order to improve the
EL efficiency and stability (Gelloz and Koshida 2003, 2004b, 2008).
The LED top electrode (usually deposited directly onto porous silicon), also the
optical window for EL output, is also a source of stability concerns. Most devices
use either ultrathin gold (a few nanometer thick in order to have a reasonable
transparency to visible light) or indium tin oxide (ITO) electrodes. ITO shows
better stability than gold (Simons et al. 1997), in particular due to better air
permeability and better mechanical stability (ITO electrodes can be much thicker
than gold ones). Fluorinated tin oxide electrodes exhibited much better stability
(three orders of magnitude in lifetime) than ITO (Macedo et al. 2008). The EL
uniformity and intensity of large area porous silicon LEDs have been reported to
have significantly improved by using a double-layer metallization with a thin
semitransparent metal layer at the bottom and a thick metal grid on top. All EL
characteristics can be enhanced by inserting a buffer layer between porous silicon
and the top electrode. The function of such buffer layer is generally to improve the
mechanical and electrical stability, lower leakage, and improve the physical isolation of porous silicon from the environment (capping effect). Thin amorphous
carbon films (Hong-Jian et al. 2002; Gelloz and Koshida 2004a), polysilicon
(Fauchet et al. 1997), and merely a compact low porosity layer (Gelloz and Koshida
2000) have all been proved very effective. Notice that capping LED with silicon
oxide is a good way to improve stability. The enhancement depends on the oxide
quality (Koshida et al. 2001).
324
B. Gelloz
EL switching speed is limited, in conventional diodes, to the MHz regime by

the luminescence lifetime (Cox et al. 1999). In all types of LED architectures,
tunneling through oxide barriers and capacitive effects (which is the greatest
limitation in electrolytic systems (Gelloz et al. 2003a)) could also limit the
switching speed. However, using a MOSFET configuration, direct modulation
of EL beyond radiative recombination rates (up to, but not limited to, 100 MHz)
has been demonstrated taking advantage of fast non-radiative Auger recombinations (subnanosecond decay rates). EL was obtained using dc gate excitation,
whereas its quenching was obtained from an ac source-to-drain injection
(Carreras et al. 2008).
The first porous silicon devices included as-anodized layers (Table 2). Then,
porosified pn junctions (Table 3), partially oxidized porous silicon (Table 4),
impregnation of porous silicon by another conductive material (Table 5), and
surface modification (Gelloz et al. 2003b) were investigated. The most noticeable
results were obtained using thin pn junctions (about 0.2 % in efficiency) (Loni
et al. 1995; Lalic and Linnros 1996a), thermal (Tsybeskov et al. 1995; Hirschman
et al. 1996) or electrochemical (Gelloz and Koshida 2000; Gelloz et al. 1998a, b)
oxidation (ECO) (from 0.1 % to 1 % in efficiency), and high-pressure water vapor
annealing (HWA) (very good stability) (Gelloz et al. 2006). ECO drastically
reduces the leakage current while optimizing carrier injection into the nanocrystals.
Figure 1 shows a picture of EL obtained for such a device (Gelloz and Koshida
2000). HWA provides a very good surface passivation with stable, good quality,
and relaxed oxide.
The EL spectrum is generally identical to that of the photoluminescence except for
devices where the EL mechanism involves other luminescence bands rather than the
S-band. One-peak voltage-tunable EL between 2 and 5 V was observed using a thin
and efficient device (Gelloz and Koshida 2004a). As for the photoluminescence, the
EL spectrum can be narrowed down to a few nanometers in FWHM using
microcavities (Pavesi et al. 1996; Araki et al. 1996; Chan and Fauchet 1999).
Integration issues have also been investigated (Barillaro et al. 2001). An EL
device was integrated and driven by a bipolar transistor (Hirschman et al. 1996).
Conclusion
The recent data of EL quantum efficiencies (up to 8.6 % (Cheng et al. 2011)) of
devices including silicon nanocrystals from colloidal solutions are very promising
and for now higher than any data obtained from porous silicon (maximum of about
1 % (Gelloz and Koshida 2000)). Also, the size uniformity of silicon nanocrystals
obtained by other methods is generally much better than that obtained in porous
silicon. Stability remains an issue in all types of devices so far, with one exception,
a device including a porous silicon layer treated by HWA, which showed no
degradation in several months, though its efficiency was low (Gelloz et al. 2006).
So far, the best EL devices based on porous silicon, in terms of efficiency, were
those where porous silicon was treated by ECO (optimized PL efficiency and
0.1
n+ (L)
Oxide-free,
from p(D)
L + H2 exposure
for 12 h
n(L)
Au or
ITO
Au
Au
Minutes
>5 h
<210
P(D)
ITO
Stability
EL threshold
V-mA/cm2
450
Structure
p(D)
Contact
Au
Posttreatment
680
430
700
580
Emission peak
(nm)
680
0.05-
Highest efficiency
EQE-EPE (%)
10 3-
References
Koshida and
Koyama (1992)
Namavar
et al. (1992)
Kozlowski
et al. (1992)
Oguro et al. (1997)
Mizuno and Koshida
(1999)
Table 2 EL characteristics of most devices including a single porous silicon layer. D and L mean that anodization was conducted in the dark and under
illumination, respectively. EQE and EPE are external quantum efficiency and external power efficiency, respectively

325
>1010
51.5 10
p+n(L)
p+n+(L)
Au
ITO
ECO
31
Au
2 min exposure in 10 %
HNO3
5-
p and p+n
(L)
p+n(L)
1 min L
Au
EL threshold
V-mA/cm2
<600
1.70.1
2.310 3
Structure
n+p+p(D)
p+n(L)
p+n(L)
p+n(L)
Contact
Au
Au
ITO
Au
Posttreatment
Hours
Seconds
Stability
>6 h
80 h
Hours
Seconds
650
690
670780
650
Emission peak
(nm)
640
700
600
630
1.10.08
0.80.07
0.2-
0.01-
Highest efficiency
EQE-EPE (%)
0.1810 20.180.160.016
References
Chen et al. (1993)
Steiner et al. (1993)
Loni et al. (1995)
Linnros and Lalic
(1995)
Peng and Fauchet
(1995)
Lalic and Linnros
(1996a, b)
Nishimura
et al. (1998)
Gelloz et al. (1998a)
Table 3 EL characteristics of most devices based on porosified pn junction. D and L mean that anodization was conducted in the dark and under illumination,
respectively. EQE and EPE are external quantum efficiency and external power efficiency, respectively
326
B. Gelloz
ITO
ITO
HWA
ECO + HWA
Anneal in N2 or in
10 % O2 in N2
ECO
ECO
ECO
ECO
p+p(D)
Al-poly
Si
ITO
ITO
Al/n+
ITO
n+(L)
n+(L)
p(L)
n+(D)
n+(L)
n +p
n+
Posttreatment
H2O2 oxidation
Structure
n(UV)
Contact
Au
2.27 10
210
210
3.54 10
310 4
1.52
EL threshold
V-mA/cm2
Hours
> 1 week
Days, EQE
is stable
Stable
Stable
1 month
Stability
>7 h
700
820
680
640
640
620770
Emission
peak (nm)
460550
10 3
1.070.37
0.510.05
0.210.02
0.1-
Highest efficiency
EQE-EPE (%)
References
Fauchet et al. (1997), Tsybeskov
et al. (1995, 1996)
Fauchet et al. (1997), Tsybeskov
et al. (1995, 1996)
Gelloz et al. (1998a)
Gelloz et al. (1998b)
Pavesi et al. (1999)
Gelloz and Koshida (2000,
2004a)
Gelloz and Koshida (2006)
Gelloz et al. (2006)
Table 4 EL characteristics of most devices based on partially oxidized porous silicon. D and L mean that anodization was conducted in the dark and under
illumination, respectively. EQE and EPE are external quantum efficiency and external power efficiency, respectively

327
Structure
p(D)
n+(D)
n(L)
n(L:UV)
n(L:UV)
n(L:UV)
n(L:UV)
n(L:UV)
Contact
Au
Au
Au
Au
Au
Au
Au
Au
Al electroplating
Sb electroplating
Ga electroplating
Sn electroplating
Posttreatment
Polypyrrole
electrodeposition
PANI chemical
deposition
Polyaniline chemical
deposition
In electroplating
0.1
0.1
500
3400
EL threshold
V-mA/cm2
2<0.01
Hours
Hours
Hours
Hours
Hours
Stability
480
700750
520
550
455480
790
800
Emission
peak (nm)
590
0.005-
0.0001-
0.0005-
0.01-
Highest efficiency
EQE-EPE (%)
Lang et al. (1997), Steiner

et al. (1994, 1996)
Steiner et al. (1996)
et al. (1996)
et al. (1996)
Lang et al. (1997)
Halliday et al. (1996)
Bsiesy et al. (1995)
References
Koshida et al. (1993, 1994)
Table 5 EL characteristics of most devices based on porous silicon impregnated by another material. D and L mean that anodization was conducted in the
dark and under illumination, respectively. EQE and EPE are external quantum efficiency and external power efficiency, respectively
328
B. Gelloz
329
Fig. 1 Picture of the EL emission of an Al/n+Si/1-m-thick porous silicon/200 nm-thick ITO

device. Orange EL (external quantum efficiency of about 1 %) was emitted through the right
ITO electrode, which was biased at 10 V with respect to the back Al contact. The left ITO
electrode was left unbiased. Each electrode was a quarter of a disk of radius 2.5 mm (Gelloz and
Koshida 2000)
leakage reduction) (Gelloz and Koshida 2000) and those which had an optimization
of both porous silicon luminescence efficiency and carrier injection from the top
electrode (Loni et al. 1995; Lalic and Linnros 1996a; Tsybeskov et al. 1995;
Hirschman et al. 1996).
Owing to recent advances in PL efficiencies (up to 23 % (Gelloz et al. 2005b;
Gelloz and Koshida 2005)) and EL stability (Gelloz et al. 2006), porous silicon is still
promising for EL purposes. The challenge is now to successfully combine high
efficiency and sufficient stability in one device, as well as getting a better control
of the emission color. Techniques of carrier injection (e.g., hole transport layers;
MOSFET structure (Walters et al. 2005)), photonics (e.g., cavity (Pavesi et al. 1996;
Araki et al. 1996; Chan and Fauchet 1999)), and plasmonics (e.g., enhanced absorption cross section; faster EL switching) (Imakita et al. 2006; Takeda et al. 2006) are
promising approaches to be pursued.
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Thermoluminescence of Porous Silicon

Valeriy Skryshevsky
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermoluminescence Measurement for Electronic Trap Detection . . . . . . . . . . . . . . . . . . . . . . . . . . .
Impact of PS Preparation Method on Thermoluminescence Glow Curves . . . . . . . . . . . . . . . . . . .
Possible Use of PS Thermoluminescence for Dosimetry of Ionizing Radiation . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
336
336
337
339
343
343
Abstract
The characteristics of electronics states in porous silicon (PS) from measurements

of thermoluminescence (TL) are presented. The observed shape of the TL peaks at
low temperatures (4250 K) is explained by quasi-continuous spectrum of the
electron traps with activation energy in range of 0.030.4 eV. The high-energy
peaks observed at 100300 C are associated with radiation-induced defects E0
( Si ) and nonbridging oxygen hole centers ( Si O ) that generated in
insulating SiOx layer which covers the PS surface. Currently, the TL of PS is not
exploited as a radiation dosimeter, due to the low activation energies of the traps
and strong fading. Nevertheless, the observations of high temperature peaks of TL
in oxidized PS, its biocompatibility and other properties, suggest a potential use
of this material for in vivo dosimetry. An additional application could be the use of
PS as a template for more established scintillation materials.
V. Skryshevsky (*)
Institute of High Technologies, Taras Shevchenko National University of Kyiv, Kyiv, Ukraine
e-mail: skrysh@univ.kiev.ua; skryshevsky@yandex.ru
DOI 10.1007/978-3-319-05744-6_35
335
336
V. Skryshevsky
Introduction
Thermally stimulated luminescence or thermoluminescence (TL) is emission that
arises during the heating of the pre-irradiated substance. During the excitation by
light, X, rays, or other radiations at low temperatures, the electrons can be
captured onto electron traps. After ending of excitation followed by heating, the
trapped electrons are released from the trap and recombines with a free holes
(or holes trapped at a recombination centers) causing the light emission. The
probability W per unit time that electron will escape from trap is determined by
the Boltzmann equation:
W S expEa =kT ,
(1)
where S is the frequency factor, depending on the frequency of the number of hits of
an electron in the trap which can be considered as a potential well, Ea is the thermal
activation energy required to liberate a trapped charge carrier, k is Boltzmanns
constant, and T is the absolute temperature (Rivera 2011).
TL is a powerful technique extensively used for dosimetry of ionizing radiations
since the irradiation results in generation of electron-hole pairs in material, followed by
their capture in traps, and contains information about the absorbed dose. The efficiency
of material as dosimeter is characterized by luminescence yield Y, i.e., the number of
photons emitted after exposure to irradiation (in photon/MeV). TL dosimeters are used
in a variety of medical applications including radiation therapy, diagnostic radiology,
and radiotherapy. Among TL dosimetry, the most widespread is radiation monitoring
of personal working around sources of ionizing radiations allowing detection of small
doses (Moscovitch and Horowitz 2007; Kortov 2007).
Another TL application is the analysis of the electronics states in materials, which
are defined by both material and technology of its production. For example, for PS
different contact methods to define the electronics states in metal/PS structures have
been already applied: thermally stimulated depolarization currents (TSDC) and
thermally stimulated current (TSC) (Ciurea et al. 1998;Anastasiadis and Triantis
2000; Brodovoy et al. 2002), optical charging spectroscopy (OCS) (Ciurea
et al. 2000), and deep-level transient spectroscopy (DLTS) (Pincik et al. 1999;
Tretyak et al. 2003). The mentioned methods determine the parameters of traps
related with both PS material and metal/PS interface and often differ from results
obtained from TL experiments. Two advantages of the TL method are that it is
contactless and it can reveal the energy distribution of both bulk and/or surface states.
The obvious drawback of TL is that it can only be applied to luminescent materials.
Thermoluminescence Measurement for Electronic Trap Detection

In the usual TL experiments, the samples are irradiated at low temperature (when
kT << Ea) then kept in the dark at the excitation temperature Tex in order to quench
the isothermal luminescence. A uniform heating with small constant velocity
337
continues up to a temperature at which all the charges have been thermally excited
out of traps and luminescence completely disappears. The intensity of TL emission
does not remain constant at constant temperature but decreases with time and
eventually ceases altogether (Rivera 2011; Chen and McKeever 1997).
To calculate the activation energy of the thermal release of charge carriers from
electron traps, the method of the fractional heating TL technique is applied (Tale
1981). This method allows separating the contributions of two effects to TL
intensity: (i) the reduction of the concentration of the traps filled by the charge
carriers and (ii) the increase of probability of the trap release at the sample heating.
The method is based on cycling with a large number of small temperature oscillations superimposed on a uniform heating ramp during measurement. Only a part of
traps with close energies are released during these temperature oscillations. The
activation energy is determined during each temperature cycle as
ET dln = T =d 1=kT ,
(2)
where I(T) is the intensity of the TL. The frequency factor at the TSL peak, S, is
given by

S Ea = kT m 2 exp Ea =kT ,
(3)
where Ta is the temperature of the TL peak and is constant heating rate,

respectively.
Impact of PS Preparation Method on Thermoluminescence

Glow Curves
In the case of excitation by white light, the TL glow curve of luminescent PS
exhibits the wide weak-structured band in the temperature range from 4.2 to
250 K. The temperature position, intensity, and shape of TL peaks depend on PS
formation regimes. The weakly expressed maxima are situated at near 50, 120, and
160 K for PS formed on n-Si of moderate resistivity (Fig. 1) (Skryshevskii and
Skryshevskii 2001). The activation energy of the thermal release of traps linearly
increases with temperature growth from 0.03 to 0.38 eV. The observed shape of
the TL signal is typical for disordered and amorphous systems and explained by
quasi-continuous spectrum of the electron traps.
The presence of quasi-continuous spectrum of the electron traps in PS is illustrated
in Fig. 2. The deeper traps are filled when Tex increases gradually resulting to the drop
of total TL intensity, the TL band is narrowed, and observed maximum is monotonically shifted to higher temperatures. The profile of energy distribution of traps with
PS layer depth can be analyzed by varying the excited light wavelength. Due to strong
adsorption, the short wavelength excitation displays electron traps situated in top of
PS layers. For PS layers with negative porosity gradient (when the porosity and
energy band gap gradually decreases with PS depth), the deeper electron traps are
338
V. Skryshevsky
Fig. 1 The normalized TL

glow curves for PS formed on
n-Si at 20 mA/cm2 for 15 min
(1) and at discrete
subsequence steps of the
currents (40, 32, 24, 16, and
8 mA/cm2 for 3 min of each
current value) (2) and for the
powder scrapped from PS
formed on p-Si (20 mA/cm2
for 15 min) (3). Tex 4.2 K,
the excitation by white light
of mercury lamp for 60 s
(Skryshevskii and
Skryshevskii 2001)
Fig. 2 The TSL glow curves

of PS powder versus . The
excitation by the white light
of mercury lamp for
60 s. Tex 4.2 (1), 30 (2),
77 (3), 130 (4), 175 (5), 200 K
(6) (Skryshevskii and
Skryshevskii 2001)
detected in near-surface region (curves 2 and 3, Fig. 3). Conversely, the TL glow
curve only slowly depends on for homogeneous PS powder (Skryshevskii and
Skryshevskii 2001).
In order to identify the nature of photoluminescence (PL) centers, the TL
emission spectra are measured. Figure 4 demonstrates the component of TL
corresponding to different spectral range of PL of highly oxidized PS: the main
680 nm PL band corresponds to the wide high temperature component of TL; the
blue 440 nm PL corresponds to the narrow doublet at 25 K in TL (Blonskyy
et al. 2001, 2003).
Kovalev and coworkers (1998) reported on luminescence hole-burning experiments that provide evidence that luminescence of PS arises from radiative recombination between states insides the nanocrystals. Weak anti-Stokes TL at energies
above the burning energy was observed indicating that part of the carriers were
re-excited via Auger process to crystallites with higher band gaps.
339
Fig. 3 The normalized TSL

glow curves for PS formed on
n-Si at different excitation
wavelengths: white light of
mercury lamp (1), 365 nm (2),
546 nm (3). Tex 77 K for
60 s (Skryshevskii and
Skryshevskii 2001)
Fig. 4 The spectral

dependence of TL for highly
oxidized PS: (1) total signal
< 800 nm, (2) > 640 nm,
(3) > 690 nm, (4) > 730
nm, (5) < 580 nm
(Blonskyy et al. 2003)
Possible Use of PS Thermoluminescence for Dosimetry

of Ionizing Radiation
The generally accepted requirements imposed on materials for TL dosimeters are
the following:
High TL signal per units absorbed dose (i.e., high luminescence yield Y )
Wide interval in which the luminescence intensity is linear with absorbed dose
Low dependence of the TL response on the energy of the incident radiation
Low fading (i.e., ability to store dosimetric information for a long time)
Simple TL glow curve (i.e., one isolated peak is observed)
340
V. Skryshevsky
The TL dosimetric materials should also be chemically inert, mechanically

strong, and radiation resistant (Moscovitch and Horowitz 2007; Chen and McKeever
1997). Today, commercial TL dosimeters have been designed using alkali-earth
haloids LiF:Mg, Ti (TLD-100, TLD-600, TLD-700), CaF2:Dy (TLD-200), CaF2:
Mn (TLD-400), oxides Al2O3:C (TLD-500), BeO, SiO2, sulfates MgSO4, CaSO4, AS
sulfides (A Mg, Sr, Ca, Ba), and others materials (Rivera 2011; Moscovitch and
Horowitz 2007; Kortov 2007; Chen and McKeever 1997). The typical radiation range
of such dosimeters is 0.01 Gy100 Gy. The majority of the commercial TL
dosimeters have small fading (less than 5 % annually). Spectra of commercial
luminescent dosimeters exhibit emission at 380480 nm, TL peak is maximum at
180260 C, making it easy to read (Kortov 2007).
From the simple band model of luminescence, it follows that fading is small if the
electron traps, which produce luminescence excitation centers, have a sufficiently large
energy depth. The temperature of glow peak maximum (180260 C) corresponds to
the relatively deep centers (Ea 0.81.2 eV). So, the requirement of small fading
leads to TL dosimetric materials being wide band gap dielectrics (Kortov 2007).
The main motivation to use the PS thermoluminescence for dosimetry of ionizing
radiations lies in the following: (i) high PL quantum yield of PS (tens of percent) (see
handbook chapter Photoluminescence of Porous Silicon), (ii) TL spectra of
nano-PS as well as commercial dosimeters exhibits emission in the visible region,
and (iii) PS is a biocompatible material (see handbook chapter Biocompatibility
of Porous Silicon) that allows to create a vivo dosimetry systems of high spatial
resolution. However, low-energy depth of the traps in the PS (less than 0.4 eV) results
in low temperature of TL peaks (less than 250 K, Figs. 1, 2, 3, and 4) and high fading
comparing with commercial dosimeters that restricts the PS application.
Despite this, further study is warranted, taking into account that various forms of
silica (Trukhin et al. 2007; McKeever 1984) and quartz crystals (McKeever 1984; de
Carvalho et al. 2010; Wintle 1997; Koul 2008) reveal above room temperature
TL peaks up to 400500 C. For non-sensitized natural quartz, the increase in TL
intensity near 100 C and 325 C is observed with particle size decreasing, and it is
explained by the increase in the specific surface area (Fig. 5) (de Carvalho et al. 2010).
Also, there is at present interest in the TL response and dosimetric utility of
commercially available doped optical fibers. Optical fibers based on Ge-doped
(GeD2) silica are characterized by storage stability and reliability and provide
higher luminescence yield in comparison to the undoped fiber or to those containing
impurities like Al, F, P and some commercial TLD. As can be seen from Fig. 6, the
TL of the GeD2 fiber has higher yield compared to two commercially available TL
dosimeters TLD500 and TLD700, commonly used as in vivo radiation dosimeters
for patients undergoing radiotherapy (Benabdesselam et al. 2013). The dosimetric
peak of GeD2 is located at 530 K, throughout the temperature range; one can
observe only one blue-violet emission (at around 3.1 eV). This well-known
emission has been ascribed to the luminescence of the twofold Ge center (Ge:).
TL response of GeD2 is linear with absorbed dose up to 900 Gy with 5 % fading
341
Fig. 5 Glow curve of quartz particles different sizes sensitized with 50 Gy of -radiation and heat
treatments at 400 C. The particle size: 300 425 m ( filled square), 75 150 m (open circle),
38 75 m ( filled triangle), and less than 38 m (open rhomb) (de Carvalho et al. 2010)
Fig. 6 TL superposition of the GeD2 optical fiber, TLD500 and TLD700 under the same
conditions of irradiation and readout (Benabdesselam et al. 2013)
342
V. Skryshevsky
8
PMT Current (109 A)
7
6
5
219C 271C
103C
155C
3
2
1
50
100
150
200
250
300
350
400
Temperature (C)
Fig. 7 TL glow curve of PS irradiated by X-rays at room temperature and heated to 400 C. The
solid line is experimental data, and the dashed lines are fits of the standard TL expression to the
data (Cooke et al. 1997)
during 8 h (Benabdesselam et al. 2013). Clinical applications based on TL properties of Ge-doped optical fibers are also described (Abdul Rahman et al. 2012).
The most sensitive TL material was found to be 4.0 mol% aluminum-doped
silica, providing 3.5 times the luminescence yield of TLD100 and 5.4 times that of
germanium-doped silica with TL peaks at 160 C, 225 C, and 310 C. The photon
dose response of aluminum-doped silica was observed to be linear over the range of
investigated dose, 0.510.0 Gy (Yusoff et al. 2005). For 6-, 9-, and 12-MeV
electron energies, the minimum detectable doses were in the range 35, 3050,
and 8001,400 Gy for TLD-100 chip, Ge-doped, and Al-doped fibers, respectively
(Hashim et al. 2009).
Since PS is easily oxidized, it should be checked as an attractive dosimeter
material. It was found that TL glow curve of PS irradiated by X-rays at Troom and
heated in 50400 C interval exhibits wide curve with peaks at 103 C, 155 C,
220 C, and 270 C (Fig. 7). Each of the peaks emits similar emission of red-orange
PL spectra (Cooke et al. 1997). It is assumed that these high-energy peaks are
associated with radiation-induced defects E0 ( Si ) and nonbridging oxygen hole
centers (NBOHCs) ( Si O ) that generated in insulating SiOx layer which
covers the PS surface.
Another potential application is using PS as a template for various scintillation
materials. For example, the dosimeter based on TL of InxTl1xI nanostructures
synthesized in PS voids and exposed to hard -radiation (60Co) was studied (Franiv
et al. 2004). It was shown that the integrated emission intensity depends on the size
of nanocrystals and luminescence yield of TL linearly increases with the increasing
dose absorbed in the crystal (Fig. 8).
343
Fig. 8 Glow curve of

InxTl1xI in mordenite (1)
and PS (25) matrices and
exposed to hard -rays for
different time (Hours): 0.5
(2), 2.0 (3), 6.0 (4), 12.0 (5).
Irradiation source: 60Co, 1.25
Mev, 8 mR/h (Franiv
et al. 2004)
Conclusion
Along with alternative methods, TL is a useful tool to study the energy levels of
electron traps in PS, since it is contactless and sensitive to the formation mode of
the luminescent material. Currently, TL in PS has not been developed for radiation
dosimeter applications, due to the low depth of the traps and strong fading.
Nevertheless, with the progress in the creation of a competitive commercial TL
dosimeters based on doped silica, observations of high temperature peaks of TL in
oxidized PS, the biocompatibility, and other properties of PS, it makes sense to
further study this material for dosimetry of ionizing radiations in vivo. Also of
interest is the use of PS as a template for other scintillation materials.
References
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Nisbet A, Bradley DA (2012) An investigation of the thermoluminescence of Ge-doped SiO2
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Anastasiadis C, Triantis D (2000) Thermally stimulated detrapping in porous silicon. Mater Sci
Eng B 6970:149151
Benabdesselam M, Mady F, Girard S (2013) Assessment of Ge-doped optical fibre as a TL-mode
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Blonskyy IV, Brodyn MS, Vakhnin AY, Kadan VM, Kadashchuk AK (2001) Thermoluminescent
study of porous silicon. Phys Lett A 279:391394
Blonskyy IV, Kadan VM, Kadashchuk AK, Vakhnin AY, Zhugayevych AY, Crervak IV (2003) New
mechanism of charge carriers localization in silicon nanowires. Phys Low Dimens Struct 7/8:25
Brodovoy OV, Skryshevsky VA, Brodovoy VA (2002) Recombination properties of electronic
states in porous silicon. Solid State Electron 46(1):8387
Chen R, McKeever SWS (1997) Theory of thermoluminescence and related phenomena. World
Scientific, Singapore
Ciurea ML, Baltog I, Lazar M, Iancu V, Lazanu S, Pentia E (1998) Electrical behaviour of fresh
and stored porous silicon films. Thin Solid Films 325(12):271277
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V. Skryshevsky
Ciurea ML, Draghici M, Lazanu S, Iancu V, Nassiopoulou A, Ioannou V, Tsakiri V (2000)

Trapping levels in nanocrystalline porous silicon. Appl Phys Lett 76:30673069
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stimulated luminescence from x-irradiated porous silicon. Appl Phys Lett 70:3594
de Carvalho lB Jr, Guzzo PL, Sullasi HL, Khoury HJ (2010) Effect of particle size in the TL
response of natural quartz sensitized by high dose of gamma radiation and heat-treatments.
Mater Res 13(2):265271
Franiv AV, Bovgyra OV, Savchyn OV (2004) Thermostimulated luminescence spectra of
InxTl1xI nanostructures synthesized in porous silicon. Funct Mater 11(4):742745
Hashim S, Al-Ahbabi S, Bradley DA, Webb M, Jeynes C, Ramli AT, Wagiran H (2009) The
thermoluminescence response of doped SiO2 optical fibres subjected to photon and electron
irradiations. Appl Radiat Isot 67:423427
Kortov V (2007) Materials for thermoluminescent dosimetry: current status and future trends.
Radiat Meas 42:576581
Koul DK (2008) 110 C thermoluminescence glow peak of quartz-a brief review. Pramana J Phys
71(6):12091229
Kovalev D, Heckler H, Averboukh B, Ben-Chorin M, Schwartzkopff M, Koch F (1998) Hole
burning spectroscopy of porous silicon. Phys Rev B 57(7):37413744
McKeever SWS (1984) Thermoluminescence in quartz and silica. Radiat Prot Dosim 8(1/2):8198
Moscovitch M, Horowitz YS (2007) Thermoluminescent materials for medical applications: LiF:
Mg, Ti and LiF:Mg, Cu, P. Radiat Meas 41:S71S77
Pincik E, Bartos P, Jergel M, Falcony C, Bartos J, Kucera M, Kkos J (1999) The metastability of
porous silicon/crystalline silicon structure. Thin Solid Films 343344:277280
Rivera T (2011) Synthesis and thermoluminescent characterization of ceramics materials. In:
Sikalidis C (ed) Advances in ceramics synthesis and characterization, processing and specific
applications. InTech, Rijeka, Croatia pp 127164
Skryshevskii YA, Skryshevskii VA (2001) Thermally stimulated luminescence in porous silicon.
J Appl Phys 89(5):27112714
Tale IA (1981) Trap spectroscopy by the fractional glow technique. Phys Status Solidi A66:6575
Tretyak OV, Skryshevsky VA, Vikulov VA, Boyko YV, Zinchuk VM (2003) Surface electronic
states in metal-porous silicon-silicon structures. Thin Solid Films 445(1):144150
Trukhin AN, Troks J, Griscom DL (2007) Thermostimulated luminescence and electron spin
resonance in X-ray- and photon-irradiated oxygen-deficient silica. J Non-Cryst Solids
353:15601566
Wintle AG (1997) Luminescence dating: laboratory procedures and protocols. Radiat Meas
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Yusoff AL, Hugtenburg RP, Bradley DA (2005) Review of development of a silica-based
thermoluminescence dosimeter. Radiat Phys Chem 74:459481
Optical Gain in Porous Silicon

Katerina Herynkov and Ivan Pelant
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Stimulated Emission in Silicon Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photoluminescence of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Optical Gain in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
345
346
347
349
350
352
Abstract
Realization of a silicon-based laser, integrated with optical and electronic

components on a single chip, remains one of the main challenges in optoelectronic
technology. Achievement of optical amplification in silicon nanocrystals is a
complex problem depending on many factors; however, it is theoretically possible.
The chapter discusses the potential of luminescent porous silicon for lasing and
lists observations of positive optical gain in various types of silicon nanocrystals.
Several different approaches lead to observation of small positive optical gain in
porous silicon-based samples; however, a real injection silicon-based laser has not
yet been demonstrated.
Introduction
Realization of an efficient silicon-based light source or laser, integrated with
optical and electronic components on a single chip, remains one of the main
challenges in silicon-based optoelectronic technology. Positive net optical gain
K. Herynkov (*) I. Pelant
Institute of Physics, Academy of Sciences of the Czech Republic, Prague 6, Czech Republic
e-mail: katerina.herynkova@fzu.cz; pelant@fzu.cz
DOI 10.1007/978-3-319-05744-6_36
345
346
K. Herynkov and I. Pelant
(i.e., amplification of light incident on the material) due to the presence of

stimulated emission and population inversion is, together with a positive feedback,
a necessary prerequisite for lasing. Featuring efficient room-temperature luminescence, porous silicon and other systems containing silicon nanocrystals belong
among possible candidates.
The history of searching for optical gain in (bulk) silicon reaches back to the era
of the first theoretical prediction of lasing in semiconductors (Bernard and
Duraffourg 1961) and successful construction of the first worldwide semiconductor
laser in the beginning of the 1960s (Hall et al. 1962; Nathan et al. 1962).
Since then, there has been an intensive discussion whether it is possible to observe
light amplification also in indirect band gap materials such as silicon or germanium
(Adams and Landsberg 1968). Even though the indirect band gap materials show
very weak luminescence due to the involvement of the third particle phonon in
the radiative recombination process, there is no nonexistence theorem stating
that lasing is impossible in indirect semiconductors (Landsberg 1967).
Nevertheless, W.P. Dumke in his theoretical work in 1962 (Dumke 1962) ruled
out both silicon and germanium as he concluded that a small positive optical
gain for band-to-band transitions achievable in these indirect semiconductors
is always overcompensated by stronger positive free carrier absorption (FCA)
where a photon absorbed by a material excites a free carrier from a filled state
to an unoccupied state in the same band. It is true that to date no experiment
has found stimulated emission in bulk silicon, even though some recent theoretical
works pointed out that Dumke probably did not formulate his calculations
fully correctly. These works also particularized the conditions for at least theoretical achievement of optical amplification in bulk silicon (Trupke et al. 2003;
Chen et al. 2006).1
Stimulated Emission in Silicon Nanocrystals

Discovery of strong visible luminescence of porous silicon (a system of
interconnected silicon nanoparticles) by L. Canham (1990) gave a new motivation
for the search of optical gain in silicon. In silicon nanocrystals, the conditions for
achieving optical amplification might be generally more favorable compared to the
bulk material. The main reasons are as follows: (i) Strong spatial localization of the
carriers increases the overlap of their wavefunctions and consequently the rate of
radiative recombination. Moreover, the complementary overlap of the electron and the
hole wavefunctions in k-space due to Heisenbergs uncertainty relations should result
In bulk germanium, first attempts to obtain real germanium lasing structure failed too
(Chynoweth AG et al (1963) Bell telephone laboratories technical memorandum no 63-1151-12,
63-1131-8); however, 40 years later J. Michel et al. successfully demonstrated positive optical gain
taking advantage of heavy Ge n-doping along with tensile-strain-induced modification of the
germanium electronic band structure (Liu J et al (2009) Opt Lett 34:1738).
347
in gradual appearance of the quasi-direct electron-hole recombination without phonon

assistance. (ii) The quantum confinement effect in quantum dots opens their bandgap
and raises consequently the energy of the emitted photon h coming from the radiative
recombination of an electron and a hole across the band gap. As the cross section of
FCA is, according to the Drude model, proportional to 1/2, the undesirable FCA
effect is strongly suppressed in nanocrystals compared to bulk silicon. Smaller
nanocrystals with higher band gap have in general better conditions for stimulated
emission. (iii) The stronger wavefunctions overlapping, however, has also a negative
impact because of enhancing non-radiative Auger recombination which can deplete
possible population inversion. Nevertheless, the three- or four-particle (when an extra
phonon is involved) Auger process may be strongly inhibited using moderate excitation fluencies when less than two electron-hole pairs per quantum dot are excited
(Mghaieth et al. 1999).
More complexity to the problem of the optical gain in nanocrystals is added
by the size distribution of the silicon nanocrystals in real samples and a
substantial role of the surface due to increased surface/volume ratio (Wolkin
et al. 1999). Isolated theoretical analyses were not able to give a satisfactory
answer to the problem of light amplification in silicon so far (Dal Negro
et al. 2003; Degoli et al. 2009); therefore, the experimental approach is usually
chosen to decide whether optical gain is present in the particular sample or not.
The first successful observation of positive optical gain in silicon nanocrystals
dispersed in a silicon dioxide matrix was reported in 2000 by the Trento group
(Pavesi et al. 2000), and similar results were achieved also by several other
groups shortly afterwards (see Table 1 for the list of the relevant publications).
In order to illustrate a variety of possible alternative approaches, Table 1
lists studies of optical gain in silicon nanocrystals (Si-ncs) prepared by other
techniques than via porous silicon.
Experimental Methods
The direct evidence of stimulated emission and optical gain can be provided either by
pump and probe optical transmission measurements where a weak probe beam is
amplified by the sample in which the population inversion was generated by an
intense pump beam (Pelant and Valenta 2012) or by the so-called variable stripe
length (VSL) technique (Shaklee and Leheny 1971; Shaklee et al. 1973). In the VSL
technique, the photoluminescence propagating in a narrow laser-excited stripe
(playing the role of the probe beam) is amplified by stimulated emission; this is the
so-called amplified spontaneous emission, ASE. Positive optical gain is then
evidenced by i) exponential growth of the luminescence intensity with the stripe
length, ii) an accompanying spectral narrowing for longer stripes, and iii) superlinear
increase of the emission intensity with increasing pump power. The VSL method,
however, is prone to experimental gain-like artefacts (Dal Negro et al. 2004b; Valenta
et al. 2003), e.g., waveguide leaky (substrate) modes may be easily misinterpreted as
the optical gain (Luterov et al. 2006; Valenta et al. 2002). Therefore, extreme care
348
Table 1 Optical gain studies in various kinds of silicon nanostructures (apart from porous
silicon). All data refer to room temperature
Material
Si-ion-implanted
quartz or thermal
SiO2
Si-ncs prepared by
PECVD
Gain
coefficient
100 cm 1
Detection
wavelength
800 nm
52 cm
760 nm
Si-ncs/SiO2
multilayers in SiO2
50 cm
730 nm
Si/SiO2 lattice by
reactive deposition on
fused quartz
Superlattices with
monodispersed Si-ncs
Si-ion-implanted
SiO2 films
Si-ion-implanted
SiO2 films
Si-ion-implanted
SiO2 layers
Nitride-passivated
Si-ncs grown by
PECVD
Si-ncs embedded in
silicon nitride grown
by PECVD
Si-rich silica
waveguides with Er3+
ions
Si-ncs-based laser
cavity
Si-ncs by reactive
deposition on fused
quartz
6 cm
720 nm
26 cm
750 nm
12 cm
760 nm
No value
given
No gain
450 nm
No gain
52 cm
1.12
dB/cm
438
cm/MW
Publication
Pavesi
et al. (2000)
Dal Negro
et al. (2003,
2004a)
Ruan
et al. (2003);
Fauchet
et al. (2005)
Khriachtchev
et al. (2001)
Cazzanelli
et al. (2004a)
Luterova
et al. (2005)
Luterov
et al. (2002)
Elliman
et al. (2003)
Chen
et al. (2007)
700 nm
Monroy
et al. (2011)
1.53 m
Navarro-Urrios
et al. (2006)
1.54 m
Koshel
et al. (2011)
Sirleto
et al. (2012)
Comment
Only fast ns
component having
gain
Only fast ns
component having
gain
Small size dispersion
of Si-ncs
Comparison of
oxygen/nitride
passivation of Si-ncs
cw Raman gain
has to be given to the experiment, and it was suggested to complete the VSL
measurement by the so-called shifted-excitation-spot (SES) measurement (Valenta
et al. 2002) in order to exclude possible experimental artefacts. However, it should be
mentioned that some concerns persist in the research community all the time about
correctness of interpretation of the whole family of experimental results indicating the
presence of optical gain in silicon nanostructures.
349

Porous silicon emits bright room-temperature luminescence in the visible region
(Fig. 1). The emission spectrum depends on the preparation conditions and in
general contains two emission bands: The main, slow (S) or red-emission band,
is peaked at 600850 nm and decays slowly on 10100 s scale. The microscopic
origin of the S-band is usually explained as a radiative recombination in the
nanocrystal core supplemented with some oxygen-related surface recombination
channel (Wolkin et al. 1999). The second, fast (F) or blue-emission band, is
located between 420 and 500 nm and has a very fast decay in nanosecond
time scale. No consensus exists so far about its origin: It has been interpreted
as due either to some structural defects in the silicon nanocrystal oxide shell
(Tsybeskov et al. 1994), to an intrinsic emission in the core of small silicon
nanocrystals (Valenta et al. 2008), or to direct-band-gap electron-hole recombination at the -point of the energy band structure of silicon nanocrystals (Prokofiev
et al. 2009).
For more data on the efficiency and spectral characteristics of the visible photoluminescence, the reader can consult the dedicated chapter Photoluminescence of
Porous Silicon in this handbook.
Fig. 1 (a) Example of

room-temperature
photoluminescence spectra of
porous silicon samples. (b)
and (c): temporal evolution of
the F and S bands,
respectively (Dohnalov
et al. 2009) (Reprinted with
permission from IOP
Publishing)
350

In as-prepared standard porous silicon layers on silicon wafers, positive optical gain
has not been achieved. This is likely due to two facts: (i) huge light scattering loss in
the spongy structure and (ii) strong absorption of pump light in the opaque underlying wafer, local heating, and rapid burning (eruption) of the thin and fragile
porous layer. Nevertheless, positive optical gain was reported in specially prepared
samples made of porous silicon. The first successful approach, used by Luterov
et al. (2004) and Dohnalov et al. (2008, 2009), used silicon nanocrystals embedded
into a transparent SiO2 matrix (which has lower absorption in the UV region than
bulk Si) in order to avoid excess heating owing to intense pump laser pulses. Here,
Fig. 2 (a) The S-band: VSL for low (0.4 MW/cm2, black symbols; 10 times magnified) and high
(1.5 MW/cm2, red symbols) excitation laser intensity. Exponential increase of the high excitation
curve yields a net gain coefficient of 41 cm 1. (b) The F-band: Two-dimensional map of the
normalized amplified spontaneous emission (ASE) spectra as a function of the stripe length shows
remarkable narrowing. (c) The F-band: Dependence of the ASE on the excitation density in a
log-log scale for three different stripe lengths, 0.1 mm (red), 1 mm (black), and 4.8 mm (blue),
reveals a superlinear increase. (d) Microscopic mechanism selective absorption scheme
(F, excited state (F-band); S, metastable state (S-band); G, ground state shared by F and S states)
(After Dohnalov et al. (2008, 2009). Reprinted with permission from IOP Publishing)
351
Table 2 Reports on optical gain in porous silicon. If not explicitly stated otherwise, all studies
were done at room temperature
Material
Reconstituted films from
colloidal solution of
ultrasmall silicon
nanoparticles
Dried films from colloidal
solution of ultrasmall
silicon nanoparticles
Heavily oxidized porous
silicon
Gain
coefficient
103105
cm 1
Detection
wavelength
F-band,
390 nm
Publication
Nayfeh
et al. (2001)a
Comment
7 104
cm 1
S-band,
610 nm
Nayfeh
et al. (2002)a
Observation of
laser oscillations
F-band,
450460
nm
S-band,
650 nm
S-band,
620 nm
F-band,
430 nm
Cazzanelli
et al. (2004b)
Polarizationresolved gain
Luterov
et al. (2004)
Dohnalov
et al. (2010)
Dohnalov
et al. (2009,
2010)
Zdek
et al. (2011)
Femtosecond
excitation
Time-resolved
measurements
74 cm
Porous silicon grains in

sol-gel SiO2 matrix
Oxidized porous silicon in
sol-gel SiO2 matrix
Oxidized porous silicon in
sol-gel SiO2 matrix
25 cm
Porous silicon with

different surface cappings
100 cm
Dye-impregnated
oxidized porous silicon
waveguides
Nanopatterned Si
9 cm 1
(40 dB/cm)
Carbon-enriched
nanopatterned Si
Porous silicon planar
waveguides co-doped by
Er and Yb ions
5 cm
22 cm
S-band,
590 nm
700 nm
Oton
et al. (2006)
1.278 m
Cloutier
et al. (2005)
No value
given
1.278 m
Rotem
et al. (2007)
6.4 dB/cm
IR, 1.53
m
Najar
et al. (2007,
2009)
260 cm
Femtosecond
excitation,
ultrafast (<1 ps)
transient gain
Pulsed regime,
dye having gain
Low
temperatures:
10 K
Low
temperatures:
25 K
Optically
activated erbium
ions
Reported values of the optical gain are exceptionally high and were not confirmed in subsequent
studies
as small as possible nanocrystals (with the S-band considerably blue shifted) were
extracted from the porous layer in order to minimize losses due to free carrier
absorption (Fig. 2; Dohnalov et al. 2008, 2009). Another way consists in investigating optical gain of colloidal dispersions of a silicon-nanocrystal powder, prepared by pulverizing porous silicon (Zdek et al. 2011). Here, applying an extension
of the commonly used VSL method, short-lived stimulated emission effects (<1 ps)
with transient optical gain of 100 cm 1 were observed. Alternative approaches such
as impregnating porous silicon structure with laser dye or doping with rare-earth
352
ions yielded a successful demonstration of positive optical gain too; however,

porous silicon was not the bearer of the optical gain but served here as a host
material and/or provided an efficient energy transfer to the active rare-earth ions
(Kik and Polman 2002). Table 2 summarizes the observations of the optical gain in
porous silicon.
However, many obstacles are still to be overcome on the route towards a
first successful silicon-based laser. In the first place, a wide nanocrystal size
distribution, overall inhomogeneity of the samples, and low optical quality caused
by a tendency of silicon nanocrystals to form larger aggregates result to the fact
that only a fraction of the samples exhibit gain and, if so, the values of optical gain
(i.e., negative optical absorption) coefficients are rather low, about 2030 cm 1 in
most cases. Furthermore, the first attempt to incorporate porous silicon as an active
material into a distributed-feedback laser cavity (Dohnalov et al. 2006, 2008) did
not prove lasing, although a shift of the emission wavelength coherent with the
resonator tuning was clearly resolved. Some clues on how to get over the
abovementioned obstacles have been sketched in Pelant 2011.
Acknowledgments Financial support was provided by GAAVCR (grants No. KJB100100903
and No. IAA101120804), GAUK (grant No. 73910), and GACR (grant No. P204/12/P235).
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Phys Rev B 84:085321
Chemical Reactivity and Surface Chemistry

of Porous Silicon
Michael J. Sailor
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reduction Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Covalent Bonding to Porous Si Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Oxides by Thermal Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Oxides by Water Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Oxides by Chemical Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Oxides by Electrochemical Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Aqueous Stability of Porous Silicon Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modification of Oxidized Porous Si Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Grafting to Porous Silicon via SiC Bonds: Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Grafting to Porous Silicon via SiC Bonds: Electrochemical Grafting . . . . . . . . . . . . . . . . . . . . . . .
Confirmation of SiC Bond-Forming Reactions: The HF-Resistance Test . . . . . . . . . . . . . . . . . . .
Grafting to Porous Silicon via SiC Bonds: Carbonization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Attachment of Biomolecules to Functionalized Porous Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Comparison of SiC vs. SiO Chemistries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
The chemical reactions of porous Si, involving formation of Si-O, Si-C, Si-N, or
Si-metal surface bonds, is reviewed. The reactivity of as-formed porous Si is
dominated by the chemistries of silicon-hydrogen (Si-H) and silicon-silicon
(Si-Si) bonds, which are strong reducing agents. Depending on the oxidant,
various surface species can be generated in oxidation-reduction reactions of
M.J. Sailor (*)

Department of Chemistry and Biochemistry, University of California, San Diego,
La Jolla, CA, USA
e-mail: msailor@ucsd.edu
DOI 10.1007/978-3-319-05744-6_37
355
356
M.J. Sailor
porous Si: in particular metal nanoparticles, silicon oxides, or silicon-carbon

species. The oxidation chemistry of porous Si, involving air, water, chemical
oxidants, or electrochemical oxidation is discussed. The aqueous stability of
these various silicon oxides is quite dependent on the means by which a
particular oxide is formed. Si-C bond forming reactions including
hydrosilylation, hydrocarbonization, carbonization, and reductive electrochemical grafting, and the chemical method used to confirm Si-C bond formation
are presented. Because much interest in the chemistry of porous Si is focused
on the generation of functional nanostructures to graft molecules such as drugs,
proteins, targeting agents, or biological receptor molecules to porous Si surfaces,
the review emphasizes the covalent chemistry of Si-O and Si-C surface
species for the attachment of functional species (particularly biomolecules)
to porous Si.
Introduction
The chemistry of porous Si is driven by four main features: (1) the strong reducing
power of surface SiH and SiSi bonds; (2) the nanostructure, in particular its high
surface area and fragile nature; (3) the relative stability of SiO, SiN, and SiC
surface bonds; and (4) the photochemical activity of the material, derived from the
semiconducting nature of silicon and quantum confinement effects in its
nanostructures. The main reactions of porous Si involve formation of SiO, SiC,
SiN, or Simetal surface bonds. Much interest in the chemistry of porous Si is
focused on the generation of functional nanostructures; the reactions of SiO or SiC
bonds are most important here, because these chemistries can be used to graft
functional molecules such as drugs, proteins, targeting agents, or biological receptor
molecules to porous Si surfaces. The ability of the porous material to template or host
other species, such as carbon (Kelly et al. 2011), metals (Steiner et al. 1995a, b; Jeske
et al. 1995; Coulthard and Sham 1997; Tsuboi et al. 1998; Ogata et al. 2000, 2006;
Harraz et al. 2001, 2002a; Hamadache et al. 2002; Sasano et al. 2003a, b; Harraz
et al. 2003a, b; Hamm et al. 2004; Presting et al. 2004; Sasano et al. 2005; Kawamura
et al. 2005; Panarin et al. 2007; Fukami et al. 2008, 2009; Fuertes et al. 2009;
Liu et al. 2011), and magnetic nanoparticles (Kinsella et al. 2011; Serda et al. 2010;
Gu et al. 2010; Ferrati et al. 2010; Thomas et al. 2006) is another area of interest
where the chemistry is critical to the properties and performance of the material.
Particularly for applications in sensors (chapters Porous Silicon Gas Sensing,
Porous Silicon Optical Biosensors, Porous Silicon Immunoaffinity
Microarrays), solar cells (chapter Porous Silicon and Solar Cells), lithium ion
batteries (chapter Porous Silicon and Li-Ion Batteries), and therapeutics (chapters
Porous Silicon in Brachytherapy, Drug Delivery with Porous Silicon, and
Porous Silicon in Photodynamic and Photothermal Therapy), the chemistry of
the porous Si surface plays important roles: it provides functionality; it determines
compatibility with the electronic, optical, or living system; and it controls longevity or
Chemical Reactivity and Surface Chemistry of Porous Silicon
357
degradability of the material. The chemistry of porous Si has been reviewed previously (Mescheder 2004; Buriak 2002; Sailor and Lee 1997). The 2002 review by
Buriak (2002) provides a thorough background and places the chemistry of porous Si
in context with flat (nonporous) silicon and germanium.
Reduction Chemistry
The reactivity of as-formed porous Si is dominated by the chemistries of siliconhydrogen (SiH) and siliconsilicon (SiSi) bonds. Both of these species are
competent reducing agents (Eqs. 1 and 2), and both are able to reduce water to
hydrogen (Eqs. 3 and 4). The surface of porous Si contains a mixture of Si-H, SiH2,
and SiH3 species (Gupta et al. 1991), which are represented notionally in the
reactions of Eqs. 2 and 4 by the molecular species silane, SiH4.
Si 2 H2 O ! SiO2 4 e 4 H
(1)
SiH4 2 H2 O ! SiO2 8 e 8 H
(2)
Si 2 H2 O ! SiO2 2 H2
(3)
SiH4 2 H2 O ! SiO2 4 H2
(4)
Oxidation of SiSi bonds by water can also generate new surface SiH species in
addition to oxides of silicon.
Redox reactions involving Si or SiH and small molecules are another important
aspect of the chemistry of porous Si. The strong reducing power of Si and SiH
sometimes leads to undesirable side reactions with drugs or bioassays. For example,
the MTT cellular viability assay (a common means to count live mammalian cells)
yields false positives in the presence of porous Si, due to reduction of the MTT
indicator (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) by
porous Si (Laaksonen et al. 2007). This reaction is not surprising, as the assay
chemistry involves reduction of MTT by cellular oxidoreductase enzymes. Indeed,
any assay that functions under (or is interrupted by) mild reducing conditions
should be carefully evaluated when porous Si is present. In addition, small molecule
drugs such as daunorubicin that contain reducible moieties (in this case, a quinone
substructure) are degraded by porous Si (Wu et al. 2011a).
Molecules containing coinage metals are particularly susceptible to reduction by
porous Si. With thermodynamic potentials of 0.9 and 1.04 V versus NHE,
respectively, Si and SiH4 are effective reducing agents for many metals, and the
reaction is more effective with the more noble metals. For example, the anticancer
agent cisplatin (cis-Pt(NH3)2Cl2) is spontaneously reduced to metallic platinum
by porous Si (Park et al. 2011). This ability of porous Si to reduce metals has
been harnessed to spontaneously reduce many metal salts to their elemental
358
M.J. Sailor
forms (Tsuboi et al. 1998; Ogata et al. 2006; chapter Porous Silicon and
Electrochemical Deposition). Commonly referred to as electroless deposition,
immersion plating, or spontaneous deposition, the reaction chemistry involves
one or both of the half-reactions of Eqs. 1 and 2 and a metal ion reduction step
idealized by Eq. 5. Immersion plating provides a route into porous Si/metal
composites of nickel (Harraz et al. 2002a, 2003a, b), palladium (Parbukov
et al. 2001; Lin et al. 2001), platinum (Kawamura et al. 2005; Parbukov
et al. 2001), gold (Fukami et al. 2008; Peng and Zhu 2004), silver (Harraz
et al. 2002a; Panarin et al. 2007; Peng and Zhu 2004; Sakka et al. 2000; Lin
et al. 2004; Yang and Meng 2010), and copper (Ogata et al. 2000; Harraz
et al. 2001, 2002a, b; Sasano et al. 2003b; Hamm et al. 2004; Fukami et al. 2009;
Peng and Zhu 2004). Metal deposition can be augmented or suppressed by light due
to the photovoltaic property of Si-liquid junctions (Sasano et al. 2003a, 2004;
Kawamura et al. 2005). The ability of porous Si to undergo spontaneous electroless
deposition of metals is also important in the metal-assisted chemical etch, or
MACE, process used to prepare porous Si (Li and Bohn 2000) and Si nanowires
(Peng et al. 2005; Mikhael et al. 2011) (see chapters Porous Silicon Formation
by Metal Nanoparticle-Assisted Etching, MACE Silicon Nanostructures). In
the MACE process, a metallic nanoparticle (usually Ag or Au) catalyzes the
decomposition of a chemical oxidant such as peroxide to supply oxidizing equivalents that then drive the etching reaction. The reducing ability of porous Si serves
to maintain the metallic etching catalyst in its active form (Mikhael et al. 2011).
Mn n e ! M
(5)
Much of the chemistry of porous Si has been developed to either minimize or

harness the reduction reactions represented by Eqs. 1 and 2 for example, one of
the key limitations of optical biosensors based on porous Si is the oxidation and
subsequent dissolution of the mesoporous matrix in aqueous buffers, which leads to
undesired zero point drift and reduces the ultimate sensitivity of the devices (Dancil
et al. 1999). In some cases this oxidation reaction can be used to amplify a sensing
event for example, negatively charged oligonucleotides can accelerate the corrosion of porous Si in aqueous media (Voelcker et al. 2008). By contrast, the use of
porous Si as an in vivo drug delivery or imaging material relies on the ability of the
material to degrade into harmless, water-soluble constituents (Anglin et al. 2008;
Chiappini et al. 2010; Salonen et al. 2008).
Covalent Bonding to Porous Si Surfaces

The most important covalent chemistry of porous Si involves SiSi, SiH, SiO,
SiC, and SiF bonds. The strengths of these bonds, obtained from thermodynamic
measurements of molecular analogues, are compared in Table 1. While bond
359
Table 1 Enthalpies of some SiX bonds

Compound
Me3SiSiMe3
Me3SiCH3
Me3SiH
Me3SiOMe3
Me3SiF
Bond
SiSi
SiC
SiH
SiO
SiF
Enthalpy kcal/mol
79
94
95
123
158
Taken from Robin Walsh, Gelest, Inc. Catalog: http://www.gelest.com/
strength plays a role in determining the stability of each of these species on the
porous Si surface, the electronegativity of the elements is much more important.
Highly electronegative elements such as O and F form polar SiX bonds,
which make the silicon atom susceptible to nucleophilic attack. As discussed in
chapter Porous Silicon Formation by Stain Etching, in the context of etching
chemistry, a surface Si atom containing an SiF or SiO bond is preferentially
attacked by F ions (or other nucleophiles), disrupting the SiSi bonds anchoring
it to the surface and resulting in its removal. In contrast, SiH and SiC bonds tend
to passivate the silicon surface in aqueous solutions due to the lower relative
electronegativity of H and C. This is why, even though SiF bonds are the strongest
bonds in silicon chemistry, the surface of a porous Si sample prepared in an
electrolyte containing HF is almost completely terminated with SiH species
(Zhang 2004).
For biosensor or drug delivery applications, the SiO and SiC chemistries
constitute an important means to attach probe molecules, tissue-targeting moieties,
or drugs. As discussed above, SiC bonds are much less polar than SiO bonds, and
reactions that form surface SiC bonds show greater resistance to attack by
nucleophiles such as water or hydroxide leading to slower rates of degradation
in biological fluids.
Porous Silicon Oxides by Thermal Oxidation

With its high surface area and reactive SiH and SiSi moieties, porous Si is
particularly susceptible to air, water, or chemical oxidation. Thermal oxidation
is employed by the microelectronic industry to produce high-quality oxides on
silicon, and this approach also works with porous Si. However, the extent of
oxidation of a porous Si sample can be significantly greater than with flat silicon
due to the small features in the porous nanostructure. For example, 1 nm of oxide
on the surface of a flat Si wafer is considered a minor degree of oxidation, whereas
1 nm of oxide on a microporous Si sample that consists of 2 nm features is
essentially completely oxidized. Thus it is important to know not only time
and temperature but also feature size in the micro-, meso-, or macroporous structure
360
M.J. Sailor
to understand the oxidation process in porous Si (see chapter Oxidation of

Macroporous Silicon).
Thermal oxidation (in air or O2) generates different types of surface
species, depending on the temperature at which the reaction is performed and
the ambient humidity (Ogata et al. 1995). The reactions shown in Eqs. 6, 7, and 8
are representative of the type of material produced in different temperature
regimes during air or O2(g) oxidation (Sailor 2012). The SiSi bond is
weaker than the SiH bond (Table 1), and mild conditions tend to result in
attack at SiSi bonds preferentially. Room-temperature oxidation in ambient
conditions produces a fairly thin oxide within a few hours (Eq. 6), which
grows over the course of several months, assisted by traces of stronger
oxidants such as ozone and nitrogen oxides in the atmosphere. Significant
quantities of SiH species can persist on porous Si surfaces stored in
air for weeks or longer. However, higher temperatures or photolytic conditions
will remove these surface SiH groups. Depending on the duration of the
reaction, atmospheric oxidation at temperatures between 60 C and 100 C
(Eq. 7) will begin to remove SiH species and generate surface SiO and
SiOH species (Ogata et al. 1995).
At a temperature of 900 C, the porous Si skeleton will completely convert to
silicon oxide (Eq. 8), although the length of time needed to accomplish this
transformation depends on the type of sample: microporous silicon will typically
convert within an hour, mesoporous silicon requires 3 h (Pacholski et al. 2005),
and the conversion of macroporous silicon may not be complete even after
12 h. As mentioned above, this is directly related to the thickness of the silicon
features and the rate of oxygen diffusion through the oxide layer.
H
Si
Si
+ O2
Si
Si
Si
25 C
Si
Si
Si
H
O
Si
Si
Si
Si
OH
Si
H
+ O2
Si
Si
Si
H
Si
Si
Si
60-100 C
Si
Si
Si
Si
H
Si
Si
+ O2
Si
200-900 C
O
O
Si
O
Si
O
8
O
361
Thermal oxidation tends to remove the smaller silicon features first, which is
sometimes not desirable. For example, the quantum-confined, luminescent domains
in porous Si are on the order of only a nanometer in thickness (Cullis et al. 1997),
and they can rapidly convert to nonluminescent SiO2 under oxidative conditions.
Rapid thermal oxidation (RTO) (Petrova-Koch et al. 1992) or high-pressure water
vapor annealing (Ghulinyan et al. 2008; Salhi et al. 2007) can better preserve these
fine-grained, crystalline silicon domains in porous Si. Both methods provide a
stable oxide and can generate material with strong fluorescence (Gelloz
et al. 2009; Gelloz and Koshida 2009).
Porous Silicon Oxides by Water Oxidation

Water is a competent oxidant for porous Si even at room temperature
(Gupta et al. 1991). In liquid water, the oxidation of Si (Eq. 9) is often in
competition with the dissolution of the product of the reaction, SiO2 (Eq. 10).
Dissolution is faster at larger pH values: while stable in acidic solutions, above pH
7 hydrogen-terminated porous Si slowly dissolves, and at pH 10 complete
dissolution of a microporous layer will occur within a few seconds. These water
dissolution rates can be understood in the context of the two reactions represented
by Eqs. 9 and 10.
OH
H
Si
Si
Si
Si
Si
Si
OH H
Si
Si
Si
Si
Si
O
Si
Si
Si
+ H2
Si
Si
Si
Si
+ H+
H
Si
Si
Si
Si
Si
Si
9
SiO2 2 OH aq ! SiO2 OH2 2 aq
(10)
The oxidation reaction (Eq. 9) occurs by an associative mechanism at the

surface silicon atom (Lehmann 2002); attack by a nucleophile generates a
5-coordinate intermediate which then induces SiSi bond cleavage. In basic
solutions the nucleophile is usually hydroxide (OH, Eq. 9), but other nucleophiles
such as amines are also effective (Sweryda-Krawiek et al. 1996). The susceptibility
362
M.J. Sailor
to nucleophilic attack increases if the surface silicon atom has electron-withdrawing

substituents like oxygen, and so oxidation of silicon by hydroxide is selfaccelerating. The rate of aqueous dissolution can also be substantially enhanced if
cationic surfactants are present in the solution (Canaria et al. 2002).
If it were not solubilized, the surface oxide layer formed in Eq. 9 would protect
the underlying elemental silicon from further oxidation. This is indeed the case at
low pH values (pH < 7), where the dissolution of silica is quite slow. However, in
basic solutions hydroxide ions attack and dissolve the surface oxide via Eq. 10,
revealing a fresh Si surface.
Porous Silicon Oxides by Chemical Oxidation

Chemical oxidants other than oxygen and water can also be used to prepare
oxide surfaces on porous Si. Ozone oxidation (Eq. 11) forms a hydrophilic,
hydrated oxide that readily dissolves in aqueous media (Dancil et al. 1999). Milder
chemical oxidants, such as dimethyl sulfoxide (DMSO, Eq. 12) (Song and Sailor
1998a), benzoquinone (Harper and Sailor 1997), ketones and aldehydes
(Boukherroub et al. 2000a), or pyridine (Mattei et al. 2000), can also be used.
These mild chemical oxidants tend to produce thin oxide layers, and often the
by-product of the organic reagent is grafted to the porous Si surface during the
process, as shown in Eq. 13. Thus aldehyde, ketone, and quinone reagents provide a
means to oxidatively functionalize porous Si surfaces (Harper and Sailor 1997).
An advantage of the aldehyde, ketone, and quinone reagents is that, unlike water
oxidation, they do not generate hydrogen gas as a reaction by-product. When
oxidized in a liquid environment, hydrogen bubble formation can generate strain,
cracking, and disintegration of porous Si films.
OH
Si
H
+ O3
Si
Si
Si
Si
Si
Si
S
H3 C
O
+
Si
Si
Si
H
Si
11
O
O
Si
Si
Si
25 C
Si
CH3
DMSO
Si
Si
Si
Si
+ (CH3)2S
Si
12
363
OH
13
Si
Si
Si
Si
Si
Si
+
Si
Si
Si
Si
Si
Si
Si
Si
Stronger oxidants such as nitrate or peroxide are effective in generating surface

oxide, although electron transfer kinetics of the oxidant plays a significant role in the
uniformity of the oxide. For example, nitric acid, commonly used in chemical stain
etching (Kolasinski 2005), reacts heterogeneously and can generate patchy oxide
surfaces. Other chemical oxidants such as Fe(III) or V(III) show more favorable
kinetics. Although studied extensively as stain-etching reagents (see chapter Porous
Silicon Formation by Stain Etching), the oxides prepared from these oxidants (in the
absence of fluoride ion) have not been characterized in detail (Kolasinski 2005).
Porous Silicon Oxides by Electrochemical Oxidation

Porous Si can be efficiently oxidized by electrochemical anodization in a mineral acid
such as aqueous H2SO4, Eq. 14 (Letant et al. 2000). This procedure generates a
hydrophilic oxide, enabling the incorporation and adsorption of hydrophilic drugs or
biomolecules within the pores. When carried out in the presence of Ca2+ ion, a calcified
form of porous Si results (Canham et al. 1996) that can also include phosphate or other
ions (Coffer et al. 2003). This formulation has been shown to be bioactive and is of
particular interest for in vivo applications. Oxide growth is enhanced by passing a DC
electric current through the sample, although oxidative calcification can also occur in
the absence of an external current (Canham 1995; Canham et al. 1997).
OH
Si
H
anodize
Si
Si
Si
Si
1 M H2SO4
O
O
Si
Si
Si
14
364
M.J. Sailor
Aqueous Stability of Porous Silicon Oxides

Oxide chemistries are perhaps the most ubiquitous chemistry for porous Si. As can
be seen from the previous sections, there are many routes into silicon oxides in the
porous Si system. Although it is convenient to classify them all as porous SiO2,
the structure and chemical nature of these oxides can be quite different. Perhaps the
most obvious chemical manifestation of these differences is seen in the dissolution
behavior of the materials in aqueous media. For example, for a fixed value of pH,
the rate of dissolution of a thermally oxidized porous Si sample strongly depends on
its thermal history. Material oxidized at 700 C or above tends to be much more
kinetically stable than the low-temperature oxides of porous Si (Sailor 2012). The
reason for the strong dependence of the dissolution kinetics on thermal history
derives from the nature of the oxide; samples oxidized or annealed at higher
temperatures tend to have less strain than the low-temperature oxides (Gelloz
et al. 2006). In addition, oxides generated at temperatures >300 C are dehydrated,
with a predominance of SiOSi bonding and few SiOH species (Zangooie
et al. 1998). Although the dissolution reaction may be thermodynamically favored
for all oxide types, the kinetics of dissolution are more important.
In addition to the dependence on pH and thermal history of the sample, porosity
and feature size play roles in determining the rate of dissolution of porous Si and its
oxides in aqueous media. The rate of dissolution of porous Si at physiologic pH
generally increases with increasing sample porosity (Anderson et al. 2003), and the
rate of dissolution tends to decrease with increasing feature size in the order
microporous >> mesoporous > macroporous (Sailor 2012).
As mentioned above, silicon oxides will dissolve in strong base following
Eq. 10. The product shown in Eq. 10 is the species [SiO2(OH)2]2, the doubly
deprotonated form of silicic acid, Si(OH)4. While it is the dominant species that
exists in highly basic (pH > 12) water (pKa of [SiO(OH)3] 12), in neutral or
acidic solution, silicic acid exists in its fully protonated form, Si(OH)4 (pKa of
Si(OH)4 10) (Greenwood and Earnshaw 1984). Thus at neutral, physiologic pH
the dissolution of SiO2 proceeds as given in Eq. 15.
SiO2 2 H2 O ! SiOH4aq
(15)
When the solution concentration of Si(OH)4 is sufficiently large, the reaction of

Eq. 15 runs in reverse, and silicic acid condenses back into a solid (Eq. 16). In the
course of this condensation reaction, various polysilicic acids with the general
formula [SiOx(OH)42x]n, where 2 < < 0, are present in solution (Greenwood
and Earnshaw 1984). In neutral or acidic solutions, these oligomers can condense to
the point of precipitation.
SiOH4aq ! SiO2 2 H2 O
(16)
The reaction of Eq. 16 is the chemistry that occurs during the solgel process,
used to prepare colloids, films, or monoliths of porous silica from solution
365
precursors (Brinker and Scherer 1990). This reaction explains why elemental
silicon does not corrode appreciably at pH values <7; the oxide is insoluble at
low pH and so provides a protective, passivating layer. The same is not true in
highly basic solutions; here the solubility of silicon oxide drives silicon dissolution
by Eqs. 9 and 10.
Modification of Oxidized Porous Si Surfaces

Due to its similar chemical nature, oxidized porous Si (porous SiO2) can be
modified using many of the same chemistries used to modify silica or glass
surfaces. This includes a wide range of conventional silanol-based chemistries
(Janshoff et al. 1998; Tinsley-Bown et al. 2000; Schwartz et al. 2005). One of the
most popular coupling reactions is the reagent 3-aminopropyltriethoxysilane
(APTES), Eq. 17. Because it places a reactive NH2 group on the surface,
APTES is very commonly used to link molecules such as proteins and DNA to
silica (Anderson et al. 2008), oxidized silicon (Nijdam et al. 2007), and oxidized
porous Si (Tinsley-Bown et al. 2000) surfaces.
NH2
H2C
NH2
CH2
H2C
H
O
Si
H2C
O
O
Si
25 C
+
Si
Si
17
CH2
H 2C
O
O
Si
Si
EtO
EtO
OEt
+ 3 EtOH
Si
Si
APTES
One of the key limitations of the APTES organosilane reagent is that it can
couple to itself, forming SiOSi links between two or more organosilanes. If too
many organosilane reagents couple to each other rather than to the surface of the
porous Si material, a cross-linked, SiOSi bonded network polymer will result.
These structures can clog the pores of a mesoporous Si sample, leading to low
coverage and blocking of access for additional reagents, drugs, or other intended
payloads. To increase penetration and coverage, the trialkoxysilane can be
introduced from dilute solution or from the gas phase. Alternatively, monoalkoxydimethylsilanes, ROSi(Me)2R0 , can be used (Sailor 2012; Tinsley-Bown
et al. 2000; Husseini et al. 2003). Monoalkoxysilane reagents possess only a single
SiO linkage, and so they cannot form network polymers. For example, the silanol
366
M.J. Sailor
3-aminopropyldimethylethoxysilane (APDMES) of Eq. 18 possesses only a

single SiO linking group, eliminating the possibility of undesirable cross-linking
reactions between other silanols, and provides better penetration into mesoporous
substrates (Stefano et al. 2013).
NH2
H2C
NH2
CH2
H2C
H2C
CH2
H2 C
OH
25 C
+
O
O
O
Si
Si
Si
O
+ EtOH
Si
Si
H3C
H3C
APDMES
18
Si
H3C
H3C
Si
OEt
O
O
Si
Si
Si
Grafting to Porous Silicon via SiC Bonds: Hydrosilylation

In aqueous environments, SiC bonded species show greater kinetic stability
than SiO bonded species. The excellent stability of the SiC chemistry
on silicon surfaces was first demonstrated by Chidsey in the early 1990s
(Linford and Chidsey 1993). Despite the lower bond strength of SiC vs. SiO
(Table 1), SiC bonds are kinetically more stable. This is due to the lower
electronegativity of C relative to O, which lowers the susceptibility of silicon
to associative attack by nucleophiles. The most ubiquitous reaction used to
form a SiC bond to hydrogen-terminated porous Si is hydrosilylation (Eq. 19),
a reaction first demonstrated by Buriak (1999, 2002; Buriak and Allen 1998)
and developed by Boukherroub, Chazalviel, Lockwood, and many others
(Canham et al. 2000; Boukherroub et al. 2000b, 2001, 2002, 2003; Mattei
and Valentini 2003; Sieval et al. 1998, 2000). Hydrosilylation involves
addition of SiH across a CC double or triple bond. The CC multiple bond
of the alkene or alkyne is usually at the terminal end of the hydrocarbon chain.
On porous Si, the reaction is promoted by heat (Boukherroub et al. 2002),
light (Stewart and Buriak 1998, 2001), mechanical scribing (Niederhauser
et al. 2002) or by Lewis acid catalysts (Buriak 2002; Buriak and Allen 1998).
For a dedicated review, see chapter Silicon-Carbon Bond Formation on
Porous Silicon.
367
R
H
R
+
Si
Si
Si
Si
19
Si
Si
Si
Si
Thermal hydrosilylation provides a means to place a wide variety of organic

functional groups on a porous Si surface, including carboxylic acid or ester groups
that then allow further chemical modification (Buriak 2002). A requirement of the
reaction is that the surface contain SiH species to react with the alkene or alkyne;
thus it is important to use freshly etched porous Si and to exclude oxygen and water
from the reaction.
It is important to note that the thermal hydrosilylation reaction does not completely
remove all SiH species from the surface. The procedure typically converts just a
few percent of SiH species on porous Si (Boukherroub et al. 2003). Maximum
conversion efficiency of this reaction has been reported to be <30 % due to steric
requirements of the functional group (Buriak and Allen 1998). Larger, functional
organic molecules cannot fit into the smaller micropores in a porous Si sample, and
most molecules are too large to fit on adjacent Si atoms on the surface. In addition,
side reactions with traces of water or oxygen can remove SiH species faster than they
can react with the alkene. With the thermal hydrosilylation reaction, the extent of
surface coverage is often a race between the rate of hydrosilylation and the rate of
oxidation of the porous Si sample by impurities.
One means to improve coverage and avoid spurious side reactions during the
hydrosilylation reaction is to heat the porous Si sample very rapidly using microwaves.
First demonstrated by Boukherroub, Ozanam, and Chazalviel, the reaction involves
microwave irradiation of a porous Si sample while it is immersed in neat alkene
(Boukherroub et al. 2003). The reaction is much more rapid than the conventional
thermal reaction, and so it tends to minimize sample oxidation from traces of water or
oxygen. Reaction efficiencies as high as 38 % have been reported (Boukherroub
et al. 2003). Due to the rapid conversion of microwave energy to heat in a conductive
silicon wafer, and the high flammability of most alkenes, this reaction can be quite
hazardous if the proper precautions are not observed. A microwave reactor designed
for chemical reactions should be used, and the microwave power and temperature of
the silicon chip should be carefully monitored (Boukherroub et al. 2003).
Grafting to Porous Silicon via SiC Bonds: Electrochemical

Grafting
Covalently attached layers have been formed by coupling Grignard, alkyl- or
aryllithium reagents (Linford and Chidsey 1993; Linford et al. 1995; Terry
et al. 1997, 1999; Song and Sailor 1998b, 1999; Bansal and Lewis 1998;
368
M.J. Sailor
Bansal et al. 1996), or organohalides (Gurtner et al. 1999; Thompson et al. 2010;
Orosco et al. 2006; Lees et al. 2003) to porous Si surfaces. These reactions
generally involve reduction of the species of interest to generate a reactive
carbon-based radical or carbanion, which then replaces a hydride on the SiH
surface. The reaction usually requires electrochemical assistance (Eq. 20). In the
case of methyl-Grignards, nearly complete coverage of methyl species can be
achieved (Dubois et al. 1997). These reactions are performed in nonaqueous
solvents, and they are air- and water sensitive. The Grignard and electrochemical
approaches allow attachment of a methyl group to the porous Si surface, which is
not possible to accomplish by hydrosilylation.
20
As with the hydrosilylation reaction, steric requirements limit the surface coverage of electrochemical grafting reactions. Thus infrared spectra show a significant
quantity of surface SiH groups remaining after these reactions. The electrochemical method allows one to reduce the amount of residual SiH species by
endcapping the surface with small methyl groups following modification with a
functional species, Eq. 21 (Thompson et al. 2010; Lees et al. 2003). The endcapping
reaction can also be performed on a hydrosilylated porous Si surface. Methyl
endcapping of porous Si surfaces can improve their stability in aqueous media
significantly (Lees et al. 2003).
H
H
Si
Si
Si
Si
+e, RI
Si
Si
Si
Si
Si
Si
H
Si
+e, CH3I
Si
Si
Si
Si
Si
Si
CH3
Si
Si
Si
Si
21
The above modification reactions impart good stability to porous Si surfaces for
two reasons: (1) the low polarity of the SiC bond makes it kinetically inert toward
attack by nucleophiles such as water or amines, and (2) the attached organic species
(typically a hydrocarbon chain 8 or more CH2 units long) is sufficiently hydrophobic that water is excluded from the immediate vicinity of the attachment point
(Gorostiza et al. 2006). For example, porous Si modified by hydrosilylation of
dodecene (a 12-carbon aliphatic hydrocarbon) is stable to hydroxide solutions of
pH > 10, whereas unmodified (H-terminated) porous Si dissolves rapidly under
369
such conditions (Buriak and Allen 1998). If the grafted species possesses a shorter
chain or a hydrophilic group such as an ester, the modified porous Si surface is
significantly less stable in water (Lees et al. 2003). In addition, porous Si modified
by SiC grafting is still susceptible to air oxidation due to the small size and lack of
polarity of molecular oxygen (Ruminski et al. 2010).
Confirmation of SiC Bond-Forming Reactions: The

HF-Resistance Test
Fourier transform infrared (FTIR) spectroscopy is typically used to confirm
the outcome of an organic grafting reaction on porous Si. An example is
shown in Fig. 1. The FTIR spectrum displays strong bands associated with
the CH stretching vibrations of the grafted organic species. However, FTIR
evidence can be misleading. Silicon oxide surfaces also react with alkenes under
thermal hydrosilylation conditions to graft the organic via an SiOR bonding
motif (Mischki et al. 2006). Also, an oxide layer can trap the organic starting
Fig. 1 Confirmation of SiC grafting reaction by HF treatment. Fourier transform infrared

(FTIR) spectrum of a porous Si sample modified with a dodecyl functionality by thermal
hydrosilylation of 1-dodecene (Eq. 19) and then treated with an aqueous HF/ethanol solution.
The hydrosilylation reaction replaces some of the SiH bonds at the surface with SiC bonds,
which are not attacked by HF. If the SiC grafting reaction is successful, vibrational bands
associated with the organic group (primarily the CH stretching and CH2 wag, or scissors,
modes from the grafted species) should be observed even after the sample has been thoroughly
rinsed with the HF solution
370
M.J. Sailor
material within the porous matrix. The differences in the FTIR spectrum
between SiC bonded, SiO bonded, and physically trapped surface species
can be difficult to resolve. To test if a species is bonded via SiC bonds, the
sample can be treated with an ethanolic aqueous HF solution. Since SiO
bonds are attacked by HF but SiC species are not, the FTIR spectrum of
a sample containing organic species grafted via SiC bonds will retain the CH
stretching signatures after treatment with HF(aq). Species grafted to the SiO
surface, or trapped within a silicon oxide matrix, will be removed by HF
treatment and thus not be seen in the FTIR spectrum after the sample has been
treated with HF(aq).
Grafting to Porous Silicon via SiC Bonds: Carbonization

Biosensor and drug delivery applications which require longer-term (hours to
months) stability in aqueous media have driven efforts to improve on the SiC
bond-forming reactions described above. The hydrosilylation and electrochemical grafting reactions suffer from the fact that reactive SiSi and SiH species are
still present in the modified porous Si material, and they are still susceptible
to aqueous dissolution (Wu et al. 2011a). Similarly, the SiO bonds that
result from the preparations of oxidized porous Si are hydrolytically unstable.
By contrast, silicon carbide (and to a lesser extent, silicon nitride) is a very stable
material that could potentially withstand years of exposure to aqueous
solutions without degradation. It was this idea that led Salonen and coworkers
to develop a carbonization reaction analogous to those that produce silicon
carbides (Salonen et al. 2002). The reaction involves decomposition and
partial pyrolysis of acetylene gas on a porous Si sample held at elevated temperatures, Eq. 22 (Salonen et al. 2000, 2002; Bjorkqvist et al. 2003). The resulting
material, termed thermally hydrocarbonized porous Si, or THCPSi, generally
remains porous, although the porosity value diminishes somewhat with the
treatment. The surface is chemically composed of a mixture of CH, aromatic
CC, and COH species. The temperature of the pyrolysis reaction plays a
key role in determining the degree of hydrophobicity or hydrophilicity
of THCPSi (Salonen et al. 2000; Bjorkqvist et al. 2004a). When the reaction
is carried out at temperatures >500 C, significant carbonization occurs (Salonen
et al. 2004), leading to black films with a sooty appearance (Ruminski
et al. 2010). This more extensive pyrolysis removes the residual hydrogen
from the hydrocarbon layer, and the high carbon content material is referred
to as thermally carbonized porous Si, or TCPSi. The acetylene precursor
used in these reactions can be replaced with an organic polymer (polyfurfuryl
alcohol) to generate similar materials (Kelly et al. 2011). Although less
well defined than material prepared by the hydrosilylation route, the pyrolyzed
porous Si formulations are chemically stable (Salonen et al. 2004; Bimbo
et al. 2010; Jalkanen et al. 2009; Limnell et al. 2007; Tsang et al. 2012),
leading to strong interest in these formulations for bioimplant, drug delivery
371
(Salonen et al. 2005a, b, 2008; Lehto et al. 2005; Limnell et al. 2006; Heikkila
et al. 2007; Kaukonen et al. 2007), and biosensor (Ruminski et al. 2010; Jalkanen
et al. 2009; Tsang et al. 2012; Salonen et al. 2006; Bjorkqvist et al. 2004b, 2005)
applications.
H
Si
Si
Si
Si
Si
H
+H
Si
485 C
Si
C
H
Si
C
22
Modification strategies that generate functional nanostructures from

pyrolyzed, carbon-containing porous Si have been demonstrated (Jalkanen
et al. 2009; Salonen et al. 2006; Bjorkqvist et al. 2004b, 2005; Sciacca
et al. 2010). The radical coupling method of Iijima (Iijima and Kamiya 2008),
developed to functionalize carbon fibers and diamond-like carbon, has
been found to work on hydrocarbonized porous Si as well (Sciacca et al. 2010).
For hydrocarbonized porous Si, the reaction involves a radical initiator
(benzoyl peroxide) and a dicarboxylic acid linker (Eq. 23). The chemistry
allows permeation of aqueous solutions and attachment of specific biological
capture probes.
23
Porous Silicon Nitrides

After silicon oxide, silicon nitride is probably the most important modification of
silicon in the semiconductor industry. A common etch stop and dielectric layer
used in integrated circuit manufacture, the fracture toughness and durability of
silicon nitride (Si3N4) has also spurred its use in high performance parts such as
bearings and gas turbine blades. The larger index of refraction of Si3N4 relative to
SiO2 (2.0 vs. 1.5, respectively) makes silicon nitride an attractive alternative to
372
M.J. Sailor
silicon oxide for optical devices made from porous Si. The industrial processes
used to prepare silicon nitride involve direct reaction of Si with N2 at
high temperature (for the bulk material) and CVD or plasma-enhanced CVD
deposition from N2, NH3, and silane precursors (for thin films). Similarly, porous
Si can be nitrided by heating in NH3 or N2 ambients (Bjorkqvist et al. 2003;
Morazzani et al. 1996) or by plasma-assisted CVD. A typical thermal preparation
involves heating in pure N2 at 1,100 C for 12 min (Bjorkqvist et al. 2003).
Such high temperatures tend to decrease surface area, pore diameter, and pore
volume in the resulting material (Bjorkqvist et al. 2003). A low temperature
(600 C) process has been developed using a rapid thermal processor in a pure
N2 ambient (James et al. 2010). Although the lower temperature preserves the
pore structure, it introduces a significant quantity of silicon oxide (Lai
et al. 2011). The stability of porous Si samples modified with silicon nitride
is improved compared with as-formed porous Si, though it is comparable to
samples prepared with a thermally grown silicon oxide (Bjorkqvist et al. 2003;
James et al. 2009, 2010; Lai et al. 2011).
Attachment of Biomolecules to Functionalized Porous Si

Biologically active molecules have been covalently attached to porous Si
surfaces for a variety of medically relevant applications: antibodies have been
attached to porous Si to impart molecular selectivity for biosensing (Serda
et al. 2010; Tinsley-Bown et al. 2000; Gu et al. 2012; Lowe et al. 2010; Andrew
et al. 2010; Wu et al. 2009; Rossi et al. 2007; Meskini et al. 2007; Bonanno and
DeLouise 2007; Park et al. 2006; Starodub et al. 1996); therapeutics have been
attached to porous Si for slow release drug delivery (Wu et al. 2008, 2011a, b;
Chhablani et al. 2013; Sailor and Park 2012); and sugars and polyethers have been
attached to porous Si as antifouling coatings in bioimplants (Schwartz et al. 2005;
Kilian et al. 2007a, b; Godin et al. 2010). The strategy generally involves a linker
molecule that connects the biologically active species to the porous Si
surface. Many suitable surface attachment chemistries for such linkers have
been described in this chapter. To attach a biological species to an immobilized
linker, an activating step is usually employed to allow formation of a covalent
bond between the species and the linker. The book Bioconjugate Techniques
by Hermanson (1996) is a leading reference on the chemical reactions that
can be employed to form these bonds. The most common approach for porous
Si involves the use of carbodiimide coupling reagents such as 1-ethyl-3[3-dimethylaminopropyl]carbodiimide hydrochloride, or EDC. EDC is employed
to couple a primary amine (NH2) group to a carboxyl group, forming an amide
bond. Thus the chemistry is amenable to a porous Si surface that has been
modified with carboxyl (CO2H) or amine (NH2) species as long as the target
molecule has a corresponding amine or carboxyl group. One example is given in
Eq. 24 (Wu et al. 2008).
373
24
Comparison of SiC vs. SiO Chemistries

For situations where the functionalized material must eventually dissolve, such as
in vivo drug delivery, chemistries involving SiO bonds represent an attractive
alternative to SiC chemistries. The time needed for highly porous SiO2 to dissolve
in aqueous media can be on the order of hours to days appropriate for many shortterm drug delivery applications. In contrast, the SiC chemistries of porous Si
generally display significantly longer degradation times, which can be as long as
several months or even years (Canham et al. 1999, 2000; Cheng et al. 2008). This is
particularly true of the pyrolysis-derived (carbonized and hydrocarbonized) materials (Eq. 22) (Salonen et al. 2008). The well-defined degradation mechanism for
porous SiO2 generates silicic acid (Si(OH)4) as the end product (Eq. 15), which is a
naturally occurring species that is present in body tissues at a mean concentration of
~5 ppm (Van Dyck et al. 2000). In contrast, samples prepared by pyrolysis of
organic materials may contain polycyclic aromatics or other potentially toxic
species that could be difficult to identify or characterize. For both the thermal
oxide and carbon pyrolysis reactions, the degree of stability in aqueous media can
be tuned by longer thermolysis times or higher temperatures.
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Biocompatibility of Porous Silicon

Suet P. Low and Nicolas H. Voelcker
Contents
Biocompatibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biodegradability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cytotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fate of Porous Silicon Particles in the Body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
In Vivo Behavior of Porous Silicon Implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Toward In Vitro and In Vivo Biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon for Tissue Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Localized Drug Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Vaccine Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
The biocompatibility of porous silicon is critical to its potential biomedical uses,

both in vivo within the human body for therapy and diagnostics, and in vitro for
biosensing and biofiltration. Published data from cell culture and in vivo
studies are reviewed, and a number of emerging applications for bioactive or
biodegradable silicon are discussed.
Biocompatibility
The term biocompatibility is defined as the ability of a material to perform with an
appropriate host response in a specific situation (Williams 2008). A biocompatible
material can be inert, where it would not induce a host immune response and have
S.P. Low (*) N.H. Voelcker
Mawson Institute, University of South Australia, Adelaide, SA, Australia
e-mail: peng.low@flinders.edu.au; nico.voelcker@unisa.edu.au
DOI 10.1007/978-3-319-05744-6_38
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S.P. Low and N.H. Voelcker
little or no toxic properties. A biocompatible material can also be bioactive, initiating

a controlled physiological response. For porous silicon, bioactive properties were
initially suggested based on the observation that hydroxyapatite (HA) crystals grow
on microporous silicon films. HA has implications for bone tissue implants and bone
tissue engineering (Canham 1995). An extension of this work showed that an applied
cathodic current was able to further promote calcification on the surface (Canham
et al. 1996). More recently, Moxon et al. showed another example of bioactive porous
silicon where the material promoted neuron viability when inserted into rat brains as a
potential neuronal biosensor, whereas planar silicon showed significantly fewer viable
neurons surrounding the implant site (Moxon et al. 2007).
Biodegradability
A comprehensive review on pSi biodegradability is covered in chapter
Biodegradability of Porous Silicon. We discuss this here as the degradation
rate, and products can influence its biocompatibility in biomedical applications.
Porous silicon is instable in aqueous solutions and degrades into orthosilicic acid
(Si(OH)4) (Allongue et al. 1993) as a result of oxidative hydrolysis (Scheme 1).
Silicic acid is a nontoxic small molecule and the common form of bioavailable
silicon in the human body (Carlisle 1972, 1982). Silicic acid does not accumulate
within the human body and has been shown to be absorbed readily by the
gastrointestinal tract of humans and is rapidly excreted via the urinary pathway
(Reffit et al. 1999). Although silicic acid at concentrations of 2 mM has been
reported to be cytotoxic to fibroblasts and macrophages (Tanaka et al. 1994), high
concentrations of silicic acid up to 100 mM have been tested in vitro on cells with
no apparent affect on their viability (Mayne et al. 2000). The rate of dissolution can be
controlled by the porosity of porous silicon (Anderson et al. 2003) and by its surface
chemistry (Canham et al. 1999, 2000). Silicon with medium porosity (62 % porosity)
Scheme 1 Proposed mechanism for porous silicon degradation in aqueous solutions, adapted
from Allongue et al. (1993). (a) A Si-H-terminated surface immersed in H2O. (b) The Si-H bond
undergoes hydrolytic attack and is converted to Si-OH and produces a hydrogen molecule. (c) The
Si-OH at the surface polarizes and weakens the Si-Si backbonds, which are then attacked by H2O,
producing HSi(OH)3. (d) In solution, the HSi(OH)3 molecule is quickly converted to Si(OH)4
releasing a second hydrogen molecule
383
shows slow degradation, whereas higher porosity silicon (>80 % porosity) showed
exponential release of silicic acid over time (Anderson et al. 2003). Surface modification has been applied to the porous silicon surface to impart protection against
hydrolytic attack and has the dual role of being able to change the surface chemistry
(Low et al. 2006). By applying different surface modifications, porous silicon
degradation rates can be tuned anywhere from minutes to months (Godin et al.
2010). This makes porous silicon as an ideal transient material for localized drug
delivery or cell delivery purposes. The degradation rate of porous silicon increases with
increasing pH (Anderson et al. 2003), and the local tissue pH therefore has to be taken
into consideration when designing porous silicon for a certain biomaterial application.
Different methods for surface modification and subsequent effect on cells
are covered in chapters Functional Coatings of Porous Silicon and SiliconCarbon Bond Formation on Porous Silicon. In brief, the functional groups presented
on the surface of porous silicon allow for the attachment of biological factors and
proteins in culture medium, which in turn influence cell attachment. Several in vitro
culture studies have shown that surface modification of the porous silicon surface can
modulate cell attachment and growth (Low et al. 2006; Yang et al. 2010). Neuroblastoma (Low et al. 2006; Yang et al. 2010; Gentile et al. 2012; Khung et al. 2006),
human embryonic kidney cells (Sweetman et al. 2011), B50 cells (Mayne et al. 2000;
Bayliss et al. 1997, 1999), and primary mesenchymal cells (Clements et al. 2011;
Noval et al. 2012) are a few cell types that have been successfully cultured on porous
silicon surfaces.
Cytotoxicity
As discussed above, the degradation products of porous silicon have been
shown to be relatively harmless and have opened the use of this material in
biological environments. The interaction of porous silicon and cells is covered
in chapter Cell Culture on Porous Silicon, but silicic acid is not the
only degradation product that may induce cytotoxicity. It has been recently
demonstrated that porous silicon is capable of producing reactive oxygen
species (ROS) (Belyakov et al. 2007; Kovalev et al. 2004). ROS have important
physiological roles such as signalling molecules to regulate cell proliferation,
apoptosis, and differentiation (Finkel and Holbrook 2000). ROS generation by
porous silicon is directly related to the surface chemistry (Kovalev et al. 2002,
2004), and therefore, porous silicon particles are more susceptible to generating
ROS. Recent investigations have demonstrated that untreated particles generate
ROS at concentrations that lead to cell death, whereas simple surface stabilization
with oxidation was able to mitigate this effect (Low et al. 2010; Santos
et al. 2010).
The size of porous silicon particles is also an important factor. Particles smaller
than 3 m have been demonstrated to be cytotoxic to monocytes (Ainslie
et al. 2008); loss in Caco-2 cell metabolic activity was seen with particles between
1.2 and 25 m in size (Santos et al. 2010). In contrast, particles below 500 nm were
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demonstrated to be nontoxic to lymphoma cells (De Angelis et al. 2010), and

particles smaller than 1 m did not cause any cytotoxic effects with macrophage
and endothelial cells (Godin et al. 2012).
Fate of Porous Silicon Particles in the Body

The retention of porous silicon in the body has recently been shown to be transient.
Intravenous injection of porous silicon nanoparticles into mice leads to its accumulation within the liver and the spleen, demonstrating rapid removal from the
circulatory system (Bimbo et al. 2010; Park et al. 2009). Another study intravenously injected oxidized and aminosilane-functionalized porous silicon microparticles into mice. The study revealed that surface chemistry and charge affected
microparticle distribution within the body (Tanaka et al. 2010a). In this study,
porous silicon microparticles after intravenous administration were also found to
accumulate within the liver and spleen. The enzyme lactate dehydrogenase (LDH)
is often used as an indicator of tissue damage, and this study found LDH levels were
only increased after multiple administrations of the particles and cytokine levels
remained stable. There was no difference in LDH levels between particles with
different surface chemistries. Other studies have shown that intravenously administered particles that accumulated within the liver and spleen degraded over a period
of 4 weeks, and cells within these organs retained their normal morphology (Park
et al. 2009).
Tanaka et al. showed in a mouse model that injected porous silicon particles
loaded with siRNA accumulated primarily within the liver and spleen (Tanaka
et al. 2010b). Clearance or degradation of the particles within these organs occurred
within 3 weeks for the spleen but significantly longer in the liver, indicating that
degradation kinetics of the porous silicon particles was organ dependent. No tissue
injury or inflammatory cytokines were detected for the organs investigated, and the
morphology of the cells within these organs remained unchanged. This study again
demonstrated that porous silicon did not cause any adverse tissue effects when
injected into the body.
For drug delivery applications, ingestion of porous silicon is of particular
interest. Porous silicon is reasonably stable at low pH (Anglin et al. 2008), showing
degradation kinetics that are suitable for drug delivery to the intestine. An investigation into the distribution of ingested porous silicon microparticles showed that
they passed through the gastrointestinal tract without signs of uptake of particles
within the lining of the gastrointestinal tract (Bimbo et al. 2010). Another study
utilized 18F-radiolabeled thermally hydrocarbonized porous silicon particles to
investigate the accumulation and retention of ingested particles in a rat model.
Once again, the particles were stable in stomach acid, remained in the GI tract, and
did not cross the intestinal cell layer (Sarparanta et al. 2011). Another article by the
same authors attached the protein hydrophobin class II to the thermally carbonized
particles. This conveyed mucoadhesive properties to the particles, allowing them to
attach to gastric cells. The particles were stable in gastric fluid, and in vivo
385
experiments showed that the particles were retained within the stomach cavity for a
period of time. However, upon entering the intestinal tract, the particles lost their
adhesive properties and were quickly expelled (Sarparanta et al. 2012). Particle size
can also be used to control the distribution throughout the body and can be a form of
targeted drug delivery. Porous silicon particles larger than 519 nm in diameter are
unable to cross the placenta into a fetus and can help prevent fetal exposure to
administered drugs (Refuerzo et al. 2011).
In Vivo Behavior of Porous Silicon Implants

A range of in vitro cell culture studies have been carried on porous silicon to
demonstrate the suitability of this material as a support for mammalian cells.
Implants, on the other hand, can experience a variety of tissue and host immune
responses, such as generalized cytotoxic effects, microvascularization, and
hypersensitivity to the implant. To date, there have been limited numbers of studies
on the effects of porous silicon in vivo. In 2000, Rosengren et al. implanted
unmodified porous silicon into the abdominal wall of rats with flat silicon and
titanium as controls. An inflammatory response was observed with a resultant
fibrous capsule forming around the implant with minimal cell death at the
cell-porous silicon interface, and it was noted that the tissue response was similar
for porous silicon, flat silicon, and titanium (Rosengren et al. 2000). Fibrous
encapsulation of an implant is a common tissue response to a foreign body
(Ratner and Bryant 2004). The factor determining the outcome of the implantation
is the thickness of the capsule and the degree of inflammation around the capsule,
often measured by the frequency of inflammatory cells such as macrophages and
foreign body giant cells. Excessive capsule thickness or inflammation can cause
pain or discomfort around an implant and can ultimately result in implant rejection.
For active pSi implants, such as devices for drug delivery, this encapsulation may
also influence the rate of drug release.
With the aim of developing a drug delivery vehicle, hydrosilylated and thermally
oxidized porous silicon microparticles were injected into the vitreous of rabbit eyes
(Cheng et al. 2008). It was noted that the particles settled into the inferior vitreous
cavity over a few days. Degradation of the hydrosilylated particles took considerable
time (>4 months) in comparison to untreated particles which degraded within a
period of 34 weeks. No adverse effects were observed in ocular tissues including
the retina and the lens. Furthermore, normal ocular pressure was maintained.
Implants of porous silicon membranes under the rat conjunctiva demonstrated
similar results (Fig. 1). A small inflammatory response was initially observed, but
histological examination of the implant site showed that a thin fibrous capsule formed
around the porous silicon membrane with only a small fraction of inflammatory cells
surrounding the implant site (Low et al. 2009). The capsule around was significantly
thinner than the fibrous capsule surrounding the surgical sutures used to hold the
membranes in place. Tissue erosion and vascularization were absent, indicating that
porous silicon was highly biocompatible within tissues of the eye.
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Fig. 1 Thermally oxidized and amino-silanized porous silicon membranes containing cultured
limbal cells were implanted under the conjunctiva of rats. (a) Images of the implant site after 0, 3,
6, and 9 weeks showing gradual dissolution of the membrane. (b) Histological analysis of the
implant site with the porous silicon (PS). Small amount of inflammatory cells (IC) are found and
the formation of a fibrous capsule around the porous silicon membrane (F) (Low et al. 2009)
Outside of the eye, the bioactive properties of pSi implants were investigated in
contact to nerve tissue. Porous silicon films on bulk silicon supports were implanted
into the sciatic nerve of a rat. Nerve tissue could hence grow on the porous region or
the flat region. The authors observed that the formed fibrous capsule formation was
significantly thinner on the porous silicon region in comparison to the flat silicon
region. They postulated that the porous nature allowed for the implant to anchor
strongly to the tissue and thus prevent sheer forces that may influence the formation
of fibrous capsules. They also determined that a greater percentage of axons formed
on the porous silicon, further highlighting the bioactivity of porous silicon in terms
of promoting neural cell formation (Johansson et al. 2009).
Toward In Vitro and In Vivo Biosensors

Porous silicon is rousing interest in the biosensor community because of several
unique intrinsic material properties. First and foremost are the optical properties
which include photoluminescence, thin-film reflectance, and photonic effects (Jane
et al. 2009). Second, the material has a high surface area (allowing higher binding
density as compared to flat surfaces), the ability to introduce size exclusion layers
(filtering out undesired molecules), and a well-developed surface chemistry with a
range of options for bioreceptor immobilization. The photoluminescence properties
of porous silicon have been exploited since the initial discovery of this effect
(Canham 1990). Quenching of the photoluminescence signal has been utilized to
detect proteins and enzyme activity (Letant et al. 2004), selectively capture
streptavidin biomolecules (Letant et al. 2003), selectively detect myoglobin from
a serum solution (Starodub et al. 1999), and capture DNA (Chan et al. 2000).
387
However, the simplest form of a porous silicon biosensor utilizes thin-film interference effects, resulting in a characteristic Fabry-Perot fringe pattern. Changes in
the position of the fringe pattern indicate the binding or loss of molecules within the
porous layer (Brecht and Gauglitz 1995). This technique has been utilized to detect
down to femtomolar concentrations of proteins and DNA binding to the porous
silicon surface (Lin et al. 1997; Steinem et al. 2004; Szili et al. 2011). Porous silicon
structures with alternating layers of low and high porosity show 1D photonic effects
with sharp stop bands. Depending on the interface between the layers, these
structures are termed Bragg mirrors or rugate filters (Pavesi and Dubos 1997).
The binding to or release of molecules from the porous layer leads to shifts in the
spectral peak (Guillermain et al. 2007).
The photonic properties of porous silicon have been used by the Sailor group for
the in situ monitoring of cell viability. This concept has been coined the smart Petri
dish. A light source is aimed at an incident angle which is reflected away from the
detector. Cells attached to the porous silicon surface scatter some of the light back to
the detector, leading to a small spectral peak. Change in cell morphology as a result of
cell death leads to an increase in light scattering and therefore an increased detector
signal. This allows the label free and in situ monitoring of cell viability without the
need for adding dyes into the cell culture medium (Schwartz et al. 2006).
The described optical effects could also be used for implanted biosensors which
combine the aspects of biocompatibility and biodegradability with the optical effects
which are retained upon implantation. Monitoring of a sensor implanted underneath
the skin can be accomplished by merely irradiating the sensor with a light source and
collecting the reflected spectra. A drawback is the fouling of the sensor when
placed into a complex biological environment which will interfere with the sensor
readout. The Gooding group utilized hydrosilylation and subsequent conjugation of
oligoethylene oxide (OEG) moieties to produce a non-fouling layer, which effectively
prevented the adhesion of proteins while still maintaining reflectivity, even
when placed into human blood plasma (Kilian et al. 2007). This feat bodes well for
the possibility of in situ monitoring in biological fluids and in vivo.
Porous Silicon for Tissue Engineering

The biocompatible, bioactive, and biodegradable properties of porous silicon render this material a suitable scaffold for tissue reengineering. For example, with
relevance to neural engineering, it has been demonstrated that porous silicon is able
to support the growth of neuronal cells that still maintain their action potential
capabilities (Ben-Tabou de Leon et al. 2004). Another study has found that porous
silicon with an average pore diameter of 300 nm is able to guide axonal growth
(Johansson et al. 2005, 2008) suggesting a potential application for porous silicon in
nerve regeneration.
The early studies identifying bioactive porous silicon in the ability to form HA
crystals have generated interest in its use as a bone matrix alternative. Porous
silicon-substituted HA structures implanted into the femur displayed better bone
388
integration around the implant compared to a nonporous HA implant (Porter

et al. 2006). This was attributed to the porous silicon degradation, revealing voids
for bone ingrowth and allowing dynamic remodeling.
The biodegradable nature of porous silicon makes it an ideal carrier for cell
therapy applications. Here, stem cells on a suitable carrier are implanted into a host,
for example, in order to regenerate tissue function. After delivery of the cells into
the host, it is desirable that the carrier be degradable in vivo. As a potential
treatment for ocular surface disease, human limbal stem cells isolated from the
cornea have been expanded on porous silicon membranes as carriers and used to
demonstrate cell outgrowth from membranes in an animal model. The stem cell
migrated from the porous silicon membrane into the surrounding tissue, and
histological analysis of the porous silicon membranes after 8 weeks showed low
inflammatory response and absence of vascularization of the implant and significant
implant degradation (Low et al. 2009).
Localized Drug Delivery

Porous silicon has also been shown to be an effective platform in sustained drug
delivery exploiting the large drug loading capacity that stems from the large internal
surface. A study looked at five different orally received drugs and their compatibility
with a porous silicon delivery vehicle. The drugs were loaded into thermally carbonized and thermally oxidized porous silicon particles. Water-soluble drugs usually
display fast drug release profiles, while poorly soluble drugs show slow release
kinetics (Salonen et al. 2005). Porous silicon particles were able to moderate the
drug release kinetics, on the one hand reducing the release rate of water-soluble
drugs while on the other hand enhancing release kinetics for poorly soluble drugs
(Wang et al. 2009). Coupled with its stability at low pH (Anglin et al. 2008), porous
silicon makes an ideal carrier for oral drug delivery into the small intestine. A tenfold
increase in permeation of insulin across intestinal cell layers was achieved when
delivered with porous silicon particles over traditional soluble permeation solutions
(Foraker et al. 2003), suggesting that apart from moderating drug release, porous
silicon can enhance drug absorption by the body. Another significant advantage
of using porous silicon particles is to be loaded with a high payload of drug so that
a single dose of the drug delivery system suffices for continuous therapeutic
effects, avoiding repeated drug administrations. Here, amino-functionalized porous
silicon particles have been used to deliver siRNA to successfully silence a gene
for an oncoprotein in vivo where the silencing effect was maintained for several
weeks, whereas traditional applications required multiple administrations (Tanaka
et al. 2010b).
The porous silicon particles have also been used for sustained peptide delivery
in rats. In this case, surface modification was used to modulate peptide release
from the particles. Thermally carbonized, thermally oxidized, and undecylenic
acid-conjugated thermally carbonized particles were loaded with a peptide. They
found that as peptide release was partially related to the degradation kinetics of pSi,
389
the thermally oxidized particles, which degraded the fastest, had the greatest release
over a 2-week period both in vitro and in vivo, whereas the more stable thermally
carbonized particles released less peptide (Kovalainen et al. 2012). This was also
demonstrated with a ghrelin antagonist; sustained release was achieved with this
peptide over 17 h when loaded into pSi particles, and without the particles, the
peptide lost its activity within 4 h (Kilpelainen et al. 2009). These studies demonstrate the advantages of using pSi as a carrier vehicle for protein delivery. Bioactivity of proteins can be preserved, and the lifetime of a loaded protein can be
extended, leading to a sustained drug delivery profile.
Vaccine Development
A further application for biocompatible porous silicon relates to vaccination using
antigen-loaded particles. Porous silicon particles were conjugated to antigens that
specifically target the toll-like receptors on dendritic cells (DC). This stimulated
phagocytosis by dendritic cells, maturing the cells to become antigen-presenting cells
(Fig. 2) (Meraz et al. 2012). The activated DCs increased proinflammatory cytokines
IL-1, TNF-, and IL-6, and when the activated DCs were injected into mice, they
migrated into the lymphatic system where they activated T cells by upregulation of cell
surface receptors and presenting the antigen along with major histocompatibility
(MHC), all of which play a role in mediating an active immune response. This study
demonstrated effective stimulation of the immune system with antigen-loaded porous
silicon which is highly relevant to the development of vaccines for various diseases.
Fig. 2 Pseudocolored SEM images of dendritic cells at low (top) and high (below) magnification.
(a) Cells only; (b) dendritic cells phagocytosing porous silicon particles and (c) porous silicon
particles loaded with liposaccharide antigen being taken up by the dendritic cells (Meraz et al. 2012)
390
Summary
Since the discovery that porous silicon can stimulate the formation of HA crystals
in simulated body fluid, the use of porous silicon in biomaterial applications has
soared. Apart from bioactivity, properties such as in vitro and in vivo biocompatibility, biodegradability, high surface area, tunability of pore size and porosity, and
finally ease of surface modification have contributed to this increasing interest.
These properties open exciting avenues for neural, ocular, and bone tissue engineering and also for drug and vaccine delivery. Combining the biocompatibility
with the materials optical properties of porous silicon enables diagnostic applications such as smart tissue cultureware and implantable biosensors.
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Biodegradability of Porous Silicon

Qurrat Shabir
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mechanism of Biodegradation and Degradation Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Kinetics of Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
395
396
398
400
400
Abstract
In the biomaterials field there is an increasing interest in medically biodegradable

materials. The medical biodegradability of mesoporous silicon is now established
both in vitro and in vivo. The review highlights the techniques used to date to
characterize this phenomenon, the degradation kinetics, and the various factors
that can influence the kinetics of dissolution into orthosilicic acid.
Introduction
There is growing interest and acceptance in replacing permanent prostheses by
temporary ones in the human body. These would in effect help the body to heal
itself and require biomaterials to have biodegradability within physiological
environments (Ratner et al. 2004). Currently four different terms are found in the
literature to signify that a material or device will eventually disappear after having
been introduced into a living organism: biodegradation, bioerosion, bioabsorption,
Q. Shabir (*)
pSiMedica Ltd, Malvern, Worcester, UK
e-mail: qshabir@psivida.com
DOI 10.1007/978-3-319-05744-6_39
395
396
Q. Shabir
POLYMERS
PLGA/PLA
Grafts, sutures,
implants, depots
CERAMICS
Hydroxyapatite/Tri
calcium phosphate
Orthopaedic devices
&tissue engineering
scaffolds
METALS
SEMICONDUCTORS
Mg / Fe alloys
Mesoporous Silicon
Coronary Stents
Paediatric implants
Brachytherapy
Tuneable drug delivery
Fig. 1 Biodegradable materials of different classes and their medical uses
and bioresorption (Ratner et al. 2004). Unfortunately no agreed distinctions exist;

we will use the biodegradability term here. Figure 1 shows examples of biodegradable
materials and their uses.
The in vitro discovery in 1995 that high porosity mesoporous silicon (pSi) can
be rapidly biodegradable, unlike solid crystalline silicon (Canham 1995), and subsequent in vivo demonstrations of biodegradability and biocompatibility (Bowditch
et al. 1999; Park et al. 2009; Sarparanta et al. 2012, 2014) have been very significant
in this regard. The huge surface area (e.g., 100500 cm2/cm3) of pSi coupled with
its nanostructured skeleton promotes solubility in water and biological media.
An increasing level of research is being conducted on the use of both porous
silicon and silica materials in drug and nutrient delivery (see handbook chapters
Drug Delivery with Porous Silicon and Porous Silicon and Functional
Foods). A biodegradable porous matrix offers the dual advantages of sustained
release at target sites in the body and gradual biological elimination after administration (Ahuja and Pathak 2009). The performance of porous silicon in this regard should
be compared with that of biodegradable polymers that can microencapsulate drugs
(Park et al. 2005) and mesoporous biodegradable silicas that can also entrap them
(Finnie et al. 2009).
This review discusses the hydrolysis mechanism underlying mesoporous
silicon biodegradability; the factors affecting typical kinetics of that biodegradability,
together with techniques used to date to tune those kinetics and timescales achieved.
Mechanism of Biodegradation and Degradation Products

In vitro degradation studies of porous silicon have shown release of orthosilicic
acid from both anodized films and microparticles using molybdate blue assays
or ICP analysis (Anderson et al. 2000; Anglin et al. 2008; Chiappini et al. 2010).
Mesoporous silicon membranes/microparticles in simulated body fluids
change color, becoming transparent as biodegradation proceeds to completion
(Fig. 2). These results are more evident as the released silicic acid forms a
blue-colored complex with molybdenum blue and the color intensity increases
397
Fig. 2 In vitro biodegradation of an 83 % porosity mesoporous silicon membrane
Fig. 3 Molybdenum blue assay for orthosilicic acid released from mesoporous silicon membranes
at different time points
with time (Fig. 3). Both in vitro (Canham 1995) and in vivo studies (Bowditch
et al. 1999; see Fig. 4) have used electron microscopy to reveal mesoporous film
corrosion and disappearance. The first in vivo study (Bowditch et al. 1999) of
implanted discs used a combination of electron microscopy and monitoring of disc
weights (2014).
Porous silicon in aqueous conditions undergoes hydrolysis to form orthosilicic
acid and the reaction is catalyzed by OH-; hence the rate of dissolution increases
398
Q. Shabir
Fig. 4 In vivo biodegradation of a 30 % porosity mesoporous silicon layer in the subcutaneous

site of the guinea pig. Plan view HREM images of porosified silicon disc surfaces (a) prior to
implantation, (b) after 4 weeks in vivo, and (c) after 12 weeks in vivo
with increasing pH. Dissolution of unoxidized silicon can be described with a

simplified two-step process:
Si 2H2 O ! SiO2 2H2
SiO2 2H2 O ! Si OH4
The oxidative first step involves electronic carrier (hole) injection and is dependent on both electronic bandgap and doping of the semiconductor. Complete
hydrolysis of the oxide phase then generates orthosilicic acid, which is the natural
bioavailable form of silicon, freely diffusible in human tissues, and readily excreted
via the kidneys (Jugdaohsingh et al. 2002; Refitt et al. 1999). The biocompatibility
of porous silicon is reviewed in detail elsewhere in this handbook (Biocompatibility of porous silicon) so is not discussed here.
Kinetics of Degradation
The kinetics of biodegradation is affected by physical parameters like degree of
crystallinity, porosity, surface area, and pore size distribution. A striking example is
the difference in solubility between amorphous and polycrystalline silicon (Shabir
et al. 2011).
The kinetics is also tunable by pore wall surface chemistry which affects
wettability by body fluid and resistance to initial hydrolysis. Mesoporous silicon
399
Table 1 Biodegradation kinetics with differing pSi structures, surface chemistries, and biological
environments
Surface
chemistry
Native oxide
(autoclaved)
pSi structure and

physical parameters
Low porosity layer on
n + Si discs (30 %
porosity and 30 m
thickness)
Biological
fluid/body site
Blood plasma
(subcutaneous
site)
Degradation
kinetics
>3 months
half-life
Native oxide
Multilayer
microparticles (~67 %
porosity)
Multilayer
porosity)
Multilayer
porosity)
Microparticles (40 nm
APD)
Microparticles (40 nm
APD)
Nanoparticles (126 nm
diameter, 7.5 nm APD)
Nanoparticles
(80120 nm diameter,
~5 nm APD)
Microparticles (2050
m, 446 m2/g, 1.5 ml/g,
10.7 nm APD)
Microparticles (2050
m, 367 m2/g, 0.84
ml/g, 7.6 nm APD)
Films and
microparticles
Vitreous
humor (eye)
1 week halflife
Reference
Bowditch
et al. (1999)
Canham
(2014)
Cheng
et al. (2008)
Vitreous
humor (eye)
5 weeks
half-life
Cheng
et al. (2008)
Vitreous
humor (eye)
16 weeks
half-life
Cheng
et al. (2008)
Phosphate
buffered saline
Phosphate
buffered saline
Phosphate
buffered saline
Phosphate
buffered saline
100 % after
2 days
100 % after
34 days
100 % after
4h
3 h half-life
Godin
et al. (2010)
Godin
et al. (2010)
Park
et al. (2009)
Hon
et al. (2012)
Phosphate
buffered saline
80 % after
96 h
Tzur-Balter
et al. (2013)
Phosphate
buffered saline
~5 % after
300 h
Tzur-Balter
et al. (2013)
Phosphate
buffered saline
Microparticles
Simulated
body fluids
Difficult to
quantify but
slow kinetics
Difficult to
quantify but
slow kinetics
McInnes
et al. (2009,
2012)
Henstock
et al. (2014)
Thermal
oxidation
Hydrosilylation
Silicon native
oxide
PEGylation
Silicon native
oxide
Rapid thermal
oxidation (800C)
Silicon native
oxide
Hydrosilylation
(dodecyl groups)
Composites with
PLLA
Composites with
polycaprolactone
is often manufactured by electrochemical etching techniques (see handbook chapter

Routes of Formation for Porous Silicon) resulting in hydrogen-terminated
surfaces (Si-Hx). For drug delivery applications, a less reactive surface is crucial,
and the hydrogen termination of the freshly etched pSi is normally replaced
(Li et al. 2009). By converting the reactive groups into a more stable oxidized,
hydrosilylated, or (hydro) carbonized form, the pSi surface can be modified in terms
of hydrophilicity and resistance to hydrolysis (Canham et al. 1999). Such changes
in pore wall chemistry have been shown to significantly change biodegradation
kinetics, as summarized in Table 1.
400
Q. Shabir
The hydrolysis of silica-based surfaces is also strongly pH dependent (Iler 1979).

Comparison of hydrolysis rates at pH 2 and 9 shows an increase in excess of
three orders of magnitude in the alkali fluid. Significant differences are
therefore expected and observed between physiological environments of varying
pH. Examples of relevance to medical uses are the low pH condition inside lysozymes
(Gu et al. 2012) and the low pH microenvironment in polymer-pSi composites due to
polymer biodegradation products (Henstock et al. 2014; McInnes et al. 2009, 2012).
Another is the widely varying stabilities observed in foodstuffs and beverages for oral
consumption (Canham 2007). The implications of the latter case are discussed in the
handbook chapter Porous Silicon and Functional Foods.
Conclusions
There has been growing interest in development of nanostructured porous
silicon-based medical therapy over the past few years. Porous silicon dissolves
in body fluids into orthosilicic acid, a benign bone nutrient bioavailable from the
diet. To make pSi more compatible with loaded drugs and nutrients, various
strategies are used to make the nanostructured surfaces less reactive, resulting
in slower biodegradation in body fluids. As expected, nanoparticles completely
biodegrade much faster than microparticles and films of similar morphology.
Composites of biodegradable polymers and porous silicon are likely to exhibit
much slower biodegradation rates of the semiconductor component. There is
much potential to tailor the silicon surfaces in terms of chemistry, pore size,
pore structure, and porosity making it a versatile carrier system for controlled
release applications.
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Bowditch AP, Waters K, Gale H, Rice P, Scott EAM, Canham LT, Reeves CL, Loni A, Cox TI
(1999) In-vivo assessment of tissue compatibility and calcification of bulk and porous silicon.
Mat Res Soc Symp Proc 536:149154
Mater 7:10331037
Canham LT (2007) Nanoscale semiconducting silicon as a nutritional food additive. Nanotechnology 18:185704
Canham LT (2014) Porous silicon for medical use: from conception to clinical use, Chap 1. In:
Santos HA (ed) Biomedical uses of porous silicon. Woodhead publishing, UK. pp 320
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blood plasma. Adv Mater 11(18):15051507
drug-delivery vehicle. Br J Ophthalmol 92(5):705711
Chiappini C, Liu X, Fakhoury JR, Ferrari M (2010) Biodegradable porous silicon barcode
nanowires with defined geometry. Adv Funct Mater 20(14):22312239
Finnie KS, Waller DJ, Perret FL, Krause-Heuer AM, Lin HQ, Hanna JV, Barbe CJ (2009)
Biodegradability of solgel silica microparticles for drug delivery. J Sol Gel Sci Technol
49:1218
Godin B, Gu J, Serda RE, Bhavane R, Tasciotti E, Chiapinni C, Lu X, Tanaka T, Decuzzi P, Ferrari
M (2010) Tailoring the degradation kinetics of mesoporous silicon through PEGylation.
J Biomed Mater Res 94(4):12361243
Gu L, Ruff LE, Qin Z, Corr M, Hedrick SM, Sailor MJ (2012) Multivalent porous silicon
nanoparticles enhance the immune activation potency of agonistic CD40 antibody. Adv
Mater. doi:10.1002/adma.201200776
Henstock JR, Ruktanonchai UR, Canham LT, Anderson SI (2014) Porous silicon confers bioactivity to polycaprolactone composites in vitro. J Mater Sci 25(4):10871097
Hon NK, Shaposhnik Z, Diebold ED, Tamanoi F, Jalali B (2012) Tailoring the biodegradability of
porous silicon nanoparticles. J Biomed Mater Res 100(12):34163421
Iler RK (1979) Chemistry of silica: solubility, polymerization, colloid and surface properties and
biochemistry. Wiley, New York
Jugdaohsingh R, Anderson SH, Tucker KL, Elliott H, Kiel DP, Thompson RP, Powell JJ (2002)
Dietary silicon intake and absorption. Am J Clin Nutr 75(5):887893
Li HL, Zhu Y, Xu D, Wan Y, Xia L, Zhao X (2009) Vapour-phase silanization of oxidised porous
silicon for stabilizing composition and photoluminescence. J Appl Phys 105:114307
McInnes SJP, Thissen H, Choudbury NR, Voelcker NH (2009) New biodegradable materials
produced by ring opening polymerisation of poly(L-lactide) on porous silicon substrates. J Coll
Interf Sci 332:336344
McInnes SJ, Irani Y, Williams KA, Voelcker NH (2012) Controlled drug delivery from composites of nanostructured porous silicon and poly(L-lactide). Nanomedicine 7(7):9951016
Park JH, Ye M, Park K (2005) Biodegradable polymers for microencapsulation of drugs. Molecules 10:146161
Park J-H, Gu L, von Maltzahn G, Ruoslahti E, Bhatia SN, Sailor MJ (2009) Biodegradable
Ratner BD, Hoffman AS, Schoen FJ, Lemons JE (eds) (2004). Biomaterials science: an introduction to materials in medicine, 2nd edn. Elsevier, US. p 851
Refitt DM, Jugdaosingh R, Thompson RPH, Powell JJ (1999) Silicic acid: its gastrointestinal
uptake and urinary excretion in man and effects on aluminium excretion. J Inorg Biochem
76:141147
Sarparanta M, Bimbo LM, Rytkonen J, Makila E, Laaksonen TJ, Laaksonen P, Nyman M,
Salonen J, Linder MB, Hirvonen J, Santos HA, Airaksinen AJ (2012) Intravenous delivery
of hydrophobin-functionalized porous silicon nanoparticles: stability, plasma protein adsorption and biodistribution. Mol Pharm 9:654663
Shabir Q, Pokale A, Loni A, Johnson DR, Canham LT, Fenollosa R, Tymczenko M, Rodrguez I,
Meseguer F, Cros A (2011) Medically biodegradable hydrogenated amorphous silicon microspheres. Silicon 2011:173176
Tzur-Balter A, Rubinskia A, Segal E (2013) Designing porous silicon-based microparticles
as carriers for controlled delivery of mitoxantrone dihydrochloride. J Mater Res
28(2):231239
Part III
Characterization
Characterization Challenges with Porous

Silicon
Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Skeleton Dimensionality and Nanostructure Packing Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pore Size Distribution and Morphology: Euclidean or Fractal? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mechanical Strength at High Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The Metastable Silicon Hydride Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The Effects of Very Low Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
405
406
407
408
409
409
410
410
Abstract
Mesoporous silicon is a complex nanostructure whose optoelectronic properties

and morphology have received intense study over the last 25 years. Its properties
often depend on both its skeleton size distribution and the chemical nature of its
high internal surface area. This review collates some of the lessons learned with
regard characterization, highlighting potential issues that need to be considered
and artifacts that can arise. These have in the past both complicated data
interpretation and even caused problems in reproducing published data.
Introduction
High porosity mesoporous silicon is a complex nanostructure whose optoelectronic
properties and morphology have received intense continuous study over the last
25 years, following the publication of its dramatic luminescence properties in 1990.
There are a series of reviews that historically chart progress in understanding and
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_40
405
406
L. Canham
Densely packed
interconnected
nanostructures
Difficult
microscopy
Inaccurate size
metrology
Hierarchical
porosity
Morphological
complexity
Complex
theoretical
modelling
Low mechanical
strength
Degradation
upon liquid
removal
Properties
change during
processing
Unstable surface
chemistry
Aging during
storage
Properties
change with time
Low thermal
transport
High temperature
rises
Properties
change during
study
Fig. 1 Problem areas for characterization of mesoporous and microporous silicon
exploitation of its luminescent, optical, and electrical properties (Fauchet et al. 1995;
Hamilton 1995; Cullis et al. 1997; Bisi et al. 2000; Boarino et al. 2009; Torres-Costa
and Martin-Palma 2010; Chao 2011; Golovan and Timoshenko 2013; Pacholski 2013).
This review highlights the five problem areas shown in Fig. 1 with regard to
characterization that have often hindered progress in optoelectronic applications.
They also have relevance to the many other application areas under more recent
development (see handbook chapter Porous Silicon Application Survey). The
objective is to alert the reader to some general issues, prior to other handbook
reviews that analyze in detail the insight gained from specific techniques, like gas
adsorption, microscopy, calorimetry, infrared spectroscopy, and so on. In this
regard it is also complementary to the handbook review Effects of Irradiation
on Porous Silicon which focuses on changes that can occur as a result of photon
beam or particle beam irradiation.
Skeleton Dimensionality and Nanostructure Packing Density

The length scale at which dramatic quantum size effects occur in silicon lies in the
range 13 nm (see Fig. 1 in handbook review Electronic Band Structure in
Porous Silicon). Silicon quantum dots or wires of this size push the spatial
resolution of many microscopy techniques, and when very small size variations
cause large changes in properties, accurate metrology becomes increasingly important and difficult. This is not helped if those nanostructures are very close together,
Characterization Challenges with Porous Silicon
407
interconnected to varying degrees, and arranged in complex three-dimensional

networks. The first challenge therefore relates to those properties that are tunable
by size metrology of the silicon skeleton: how do we accurately extract the silicon
nanocrystallite size distribution throughout its volume? The handbook review
Microscopy of Porous Silicon discusses such issues and progress to date.
Pore Size Distribution and Morphology: Euclidean or Fractal?

The size of mesopores (250 nm) and particularly micropores (02 nm) also makes
their accurate metrology via microscopy difficult. The handbook review Gas
Adsorption Analysis of Porous Silicon discusses how mesopore size can be
evaluated over the entire sample volume accessible, but it is not an accurate
technique for micropores.
However porous silicon is normally not exclusively riddled with only one class of
pore. There is now significant evidence that many electrochemical etching regimes,
for example, produce more than one class of porosity in a given structure; macropore
walls can themselves be mesoporous; structures can contain both mesopores and
micropores. In extreme cases, so-called hierarchical porosity is present with pore
diameters covering a huge range of length scales. This type of wide-ranging length
scale of porosity, together with a fractal geometrical arrangement of pores
(see Fig. 2), is a topic only briefly mentioned elsewhere in this handbook (see, e.g.,
the chapter Mesoporous Silicon), and so it will be highlighted here.
Extremely regular arrays of large macropores with smooth sidewalls and Euclidean geometry are a regular feature of the porous silicon literature (see Fig. 3a), as
are highly directional mesopore arrays with minimal pore branching under specific
anodization conditions (Canham 1990; Ouyang et al. 2005). Very different fractallike etching patterns were first revealed from electrochemically etched macropores,
also under certain conditions (Harsanyi and Habermeier 1987). Seminal investigations of the anodization formation mechanisms by Smith and co-workers (Chuang
et al. 1989; Smith and Collins 1992; Tondare et al. 2008) then provided strong
microscopic evidence for the broader occurrence of fractal pore morphology.
Fig. 2 Fractal-like pore arrangement in a porous silicon membrane (Lysenko et al. 2004)
408
L. Canham
Fig. 3 LHS: Euclidean macropore array in p-type silicon (Kim et al. 2009); RHS: Fractal-like
oxide replica of the pore volume in n-type silicon (Tondare et al. 2008)
At least with their specific etching conditions (n-substrates with both mesopores
and macropores), macropore walls were clearly also mesoporous at decreasing
length scales (see Fig. 3b).
An increasing number of properties of primarily mesoporous silicon are
now being modeled using a fractal geometry for the porous silicon surface.
Examples include the exterior surface roughness of layers (Happo et al. 1998)
and their hydrophobicity (Cao et al. 2008; Gentile et al. 2011), optical absorption
(Derlet et al. 1995), electrical transport (Ben-Chorin et al. 1995; Axelrod
et al. 2002), gas transport (Lysenko et al. 2004), hydride content (Nychyporuk
et al. 2005), vapor adsorption within pores (Moretti et al. 2007), and low
temperature thermal conductivity (Valalaki and Nassiopoulou 2014). In contrast,
much of the theoretical modeling of the band structure of mesoporous silicon
has been based on idealized nanoscale silicon building blocks (quantum wires
and dots) or Euclidean geometry-based subtractive models which introduce
periodic porosity via supercells (see handbook chapter Electronic Band Struc
ture in Porous Silicon).
Mechanical Strength at High Porosity

Crystalline silicon is a strong but brittle material. The introduction of porosity
often lowers hardness, stiffness, and fracture strength (see handbook chapter
Mechanical Properties of Porous Silicon), and if the structure becomes too
weak, it cannot often survive common material processing techniques
without alteration. Examples include air drying (see handbook chapter Drying
Techniques Applied to Porous Silicon), reduction of particle size via communition
(see handbook chapter Milling of Porous Silicon Microparticles), and
oxidation of layers. The properties of electrochemically etched layers can depend
not only on etch parameters but how the material was dried. The properties of
microparticles can be sensitive to how they were milled.
409
In addition, for materials with very low strength, characterization techniques

normally deemed quite gentle can become destructive. One example is the widespread
use of gas adsorption to measure pore size which produces irreversible changes in
ultrahigh porosity silica aerogels (Scherer et al. 1995) and is likely to run into
similar issues with characterization of silicon aerocrystals (Canham et al. 1994).
The Metastable Silicon Hydride Surface

Processing silicon in hydrofluoric acid solutions has been an invaluable route to
generating all classes of porous silicon, but the resulting silicon hydride bonds are
metastable in ambient air and gradually replaced by native oxide growth. The
effects on the chemical composition of highly porous stain-etched silicon were
recorded by infrared spectroscopy in the 1960s (Beckmann 1965), and effects of air
storage on many properties (photoluminescence, refractive index, electrical resistivity) emphasized much later for microporous silicon (Canham et al. 1991). If
structures are not chemically passivated immediately after etching then the
properties will evolve with storage time until ambient oxidation is complete. This
can take many months (Canham 1997).
In addition, many characterization techniques utilize energetic beams that can
accelerate this process if carried out in ambient air or even vacuum (see handbook
chapter Effects of Irradiation on Porous Silicon). In some cases, such as ion
beam analysis in vacuo of chemical composition, capping of layers is required to
provide reliable data (Giaddui et al. 1998).
The Effects of Very Low Thermal Conductivity

The incredibly low thermal conductivity of high porosity silicon is reviewed in
two chapters of this handbook: Thermal Properties of Porous Silicon and
Thermal Isolation with Porous Silicon. It can be utilized in specific applications
but also introduce challenges with many characterization techniques and processes.
Particular care must be taken with characterization techniques that utilize high energy
excitation in localized volumes. Examples include micro Raman spectroscopy,
cathodoluminescence spectroscopy, and photoluminescence microscopy. The effects
of exothermic reactions are also often amplified by poor energy dissipation, such as in
thermal passivation of mesoporous silicon powders (Loni and Canham 2013).
Massive temperature rises in the silicon skeleton can occur, so much so that
some degree of sintering or even localized melting occurs during analysis. This
becomes more pronounced for porous silicon membranes and powders which are
removed from the bulk silicon heat sink and more pronounced when data is
collected in vacuum, removing gaseous heat transport. Figure 4 provides an example where Raman analysis at gas pressures was used to demonstrate silicon nanoparticle temperatures up to 800 C under focussed photoexcitation.
410
L. Canham
Fig. 4 Temperature of
silicon nanoparticles under
micro Raman analysis, as a
function of gas pressure
(Costa et al. 1998)
15
600
(cm-1)
10
400
5
Temperature (C)
800
200
c-Si
100
101
102
103
104
Pressure (Pa)
A particularly striking example of this is the visible light emission from some porous
silicon and silicon nanoparticle structures originally ascribed to photoluminescence
but later revealed to be blackbody thermal radiation by careful experimentation (Costa
et al. 1998; Roura and Costa 2002). Some very spectrally broad cathodoluminescence spectra published are also likely to be primarily thermal radiation.
Much of the nonlinear optical properties reported for porous silicon over the
period 19922002 may also need reinterpretation accounting for thermal effects, as
discussed by Roura and co-workers (Roura and Costa 2002). This topic does not
have a dedicated review in this handbook, but is an important issue, mentioned at
the end of a recent review on the topic (Golovan and Timoshenko 2013).
Concluding Comments
High porosity mesoporous silicon is a fascinating nanostructure with low dimensionality that has a number of novel properties. It also can possess chemical
instability, mechanical weakness, and low thermal transport. These latter properties
can necessitate very careful characterization in order to avoid data misinterpretation
and unwanted changes to the nanostructured material.
References
Axelrod E, Givant A, Shappir J, Feldman Y, Saar A (2002) Dielectric relaxation and transport in
porous silicon. Phys Rev B 65:165429
infrared spectroscopy. Surf Sci 3(4):314332
411
Ben-Chorin M, Moller F, Koch F, Schirmacher W, Eberhard M (1995) Hopping transport on a

fractal: ac conductivity of porous silicon. Phys Rev B 51(4):21992213
optoelectronics. Surf Sci Reports 38(13):1126
Boarino L, Borini S, Amato G (2009) Electrical properties of mesoporous silicon: from a surface
effect to coulomb blockade and more. J Electrochem Soc 156(12):K223K226
dissolution of waters. Appl Phys. Lett 57(10):10461048
Canham LT (1997) Properties of porous silicon, EMIS datareview series no 18. IEE Press, London
Canham LT, Houlton MR, Leong WY, Keen JM (1991) Atmospheric impregnation of porous
Canham LT, Cullis AG, Pickering C, Dosser OD, Cox TI, Lynch TP (1994) Luminescent anodized
silicon aerocrystal networks prepared by supercritical drying. Nature 368:133135
Cao L, Price TP, Weiss M, Gao D (2008) Super water- and oil-repellent surfaces on intrinsically
hydrophilic and oleophillic porous silicon films. Langmuir 24(5):16401643
Chao Y (2011) Optical properties of nanostructured silicon. Compr NanoSci Technol 1:543570
Chuang SF, Collins SD, Smith RL (1989) Porous silicon microstructure as studied by transmission
electron microscopy. Appl Phys Lett 55:15401543
Costa J, Roura P, Morante JR, Bertran E (1998) Blackbody emission under laser excitation of
silicon nanopowder produced by plasma-enhanced chemical-vapour deposition. J Appl Phys
83(12):78797885
Derlet PM, Choy TC, Stoneham AM (1995) An investigation of the porous silicon optical
absorption power law near the band edge. J Phys Condens Matter 7:25072523
Fauchet PM, Tsybeskov L, Peng C, Duttagupta SP, von Behren J, Kostoulas Y, Vandyshev JMV,
Hirschman KD (1995) Light-emitting porous silicon: materials science, properties and device
applications. IEEE J Sel Topics Quant Electron 1(4):11261139
Gentile F, Battista E et al (2011) Fractal structure can explain the increased hydrophobicity of
nanoporous silicon films. Microelectron Eng 88:25372540
Giaddui T, Earwaker LG, Forcey KS, Loni A, Canham LT (1998) Improved capping layers for
suppression of ambient ageing in porous silicon. J Phys D Appl Phys 31:11311136
Golovan LA, Timoshenko VY (2013) Nonlinear optical properties of porous silicon
nanostructures. J Nanoelectron Optoelectron 8:223239
Hamilton B (1995) Porous silicon. Semicond Sci Technol 10:11871207
Happo N, Fujiwara M, Iwamatsu M, Horii K (1998) Atomic force microscopy study of self-affine
fractal roughness of porous silicon surfaces. Jpn J Appl Phys 37:39513953
Harsanyi J, Habermeier HU (1987) Fractal micropatterns generated by anodic etching.
Microelectron Eng 6(14):575580
Kim JH, Kim KP, Lyu HK, Woo SH, Seo HS, Lee JH (2009) Three dimensional macropore arrays
in p-type silicon fabricated by electrochemical etching. J Korean Phys Soc 55(1):59
Loni A, Canham LT (2013) Exothermic phenomena and hazardous gas release during thermal
oxidation of mesoporous silicon powders. J Appl Phys 113:173505
Lysenko V, Vitiello J, Remaki B, Barbier D (2004) Gas permeability of porous silicon
nanostructures. Phys Rev E 70:017301
Moretti L, De Stefano L, Rendina I (2007) Quantitative analysis of capillary condensation in
fractal-like porous silicon nanostructures. J Appl Phys 101:024309
Nychyporuk T, Lysenko V, Barbier D (2005) Fractal nature of porous silicon nanocrystallites.
APS J Phys Rev B 71:115402
Ouyang H, Christopherson M, Fauchet PM (2005) Enhanced control of porous silicon morphology
from macropore to mesopore formation. Phys Stat Solidi (a) 202(8):13961401
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Roura P, Costa J (2002) Radiative thermal emission from silicon nanoparticles: a reversed story
from quantum to classical theory. Eur J Phys 23:191203
Scherer WG, Smith DM, Stein D (1995) Deformation of silica aerogels during characterisation.
J Non Cryst Solids 186:309315
Smith RL, Collins SD (1992) Porous silicon formation mechanisms. J Appl Phys 71, R1
Tondare VN, Gierhart BC, Howitt DG, Smith RL, Chen SJ, Collins SD (2008) An electron
microscopy investigation of the structure of porous silicon by oxide replication. Nanotechnology 19:225301
Torres-Costa V, Martin-Palma RJ (2010) Application of nanostructured porous silicon in the field
of optics. A review. J Mater Sci 45:28232838
Valalaki K, Nassiopoulou AG (2014) Thermal conductivity of highly porous silicon in the
temperature range 4.2 to 20K. Nano Res Lett 9, 318
Microscopy of Porous Silicon

Raul J. Martn-Palma and Vicente Torres-Costa
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Transmission Electron Microscopy Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Scanning Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Atomic Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Other Microscopies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
413
414
416
417
418
420
420
Abstract
The use of microscopy in the structural characterization of mesoporous silicon

has been widespread with the most popular techniques being several electron
microscopies, Raman, and atomic force microscopy. The general field is
reviewed including other techniques such as luminescence and multiphoton
microscopy to study the optoelectronic properties, and acoustic microscopy to
study the mechanical properties.
Introduction
The complex structure of porous silicon (PS) provides this material with many interesting physicochemical properties, among which visible luminescence can be highlighted.
Additionally, the possibility of controlling its morphology on the micro- and nanoscales
makes PS a very versatile material for its use in many different applications in a broad
diversity of fields (Canham 1997; Lehmann 2002; Sailor 2011, and many other
R.J. Martn-Palma (*) V. Torres-Costa

Departamento de Fsica Aplicada, Universidad Autonoma de Madrid, Cantoblanco, Madrid, Spain
e-mail: rauljose.martin@uam.es
DOI 10.1007/978-3-319-05744-6_41
413
414
R.J. Martn-Palma and V. Torres-Costa
examples throughout this book), including optics (Torres-Costa and Martn-Palma

2010) and biomedicine (Martn-Palma et al. 2010). But the particular structure of
porous silicon is itself a matter of study, given its inherent complex surface, bulk, and
interface morphology. Besides, there are many different forms of porous silicon,
which makes the analysis of its structure even more complex. In all, detailed
structural characterization is a key factor to improve our understanding of the
physical mechanisms responsible for the very different behavior of PS with respect
to bulk Si and to improve the overall behavior of PS-based structures.
Within this context, researchers have performed over the years studies on the
morphology of porous silicon, with notable implications in applied research and the
further development of devices. Aiming at precisely determining its intricate
structure, a host of different microscopy characterization techniques have been
used over the years. From these, (high-resolution) transmission electron microscopy (HR)TEM, (high-resolution) scanning electron microscopy (HR)SEM, and
atomic force microscopy (AFM) can be highlighted. Other experimental techniques
discussed in this chapter include cathodoluminescence (CL), scanning tunneling
microscopy (STM), photoluminescence (PL), micro-Raman spectroscopy, confocal
scanning beam microscopy, near-field scanning optical microscopy (NSOM),
multiphoton microscopy, and acoustic microscopy.
The main advantage of most microscopy techniques is that they allow the direct
characterization of the morphology at the micron- and nanoscale and thus are not
based in indirect results to determine, for instance, the typical nanocrystal or pore
size. Also, many of these techniques are nondestructive and can be combined for
the study of a given sample. In the following sections, a non-exhaustive review of
the most notable uses of different microscopies applied to the study of porous
silicon is presented.
Transmission Electron Microscopy Studies

Transmission electron microscopy (TEM) and its high-resolution version
(HRTEM) (Goodhew et al. 2001) have been used by several researchers for the
characterization of porous silicon at the nanoscale, which allow resolving very
small regions. Furthermore, the combination of TEM/HRTEM with image
processing constitutes an extremely powerful technique to accomplish detailed
morphological analysis at the nanoscale. Moreover, the combined use of TEM
with energy-dispersive X-ray spectroscopy (EDX or EDS) or energy-filtering
TEM (EFTEM) allows the determination of the chemical composition of the
structure of PS with a very high degree of precision.
HRTEM studies have allowed determining the lattice parameter, crystallite size,
as well as orientation of the silicon nanocrystals present in PS (Cole and Harvey
1992; Cullis and Canham 1991; Munder et al. 1992; Lehmann et al. 1993; Frohnhoff
et al. 1995; Martn-Palma et al. 2002, 2004; Pascual et al. 2005; Wijesinghe
et al. 2009). Pore size and nanocrystal arrangement and distribution have been
found to enormously depend on the particular fabrication technique and parameters.
415
Fig. 1 (Left) Morphology of nanostructured porous silicon, consisting in an amorphous matrix

with Si crystallites embedded in it with no preferential orientation. This material shows a
polycrystalline diffraction pattern. (Middle) Image processing allowed studying the structure of
the individual Si nanocrystals. (Right) The size of the individual Si crystallites, interplanar
distance (d ), lattice parameter (a), total lattice expansion (a), and relative lattice expansion
(a/aSi) were directly determined
Fig. 2 (Left, middle) Interface between PS and bulk Si. (Right) Dislocations are usually found at
the PS/Si interface
Under the appropriate fabrication conditions, the electrochemical etch of Si results in

PS layers composed of Si nanocrystals with no preferential orientation embedded in
an amorphous matrix (Martn-Palma et al. 2002), as shown in Fig. 1. Furthermore, the
lattice parameter of the Si nanocrystals which compose PS has been found to increase
with respect to that of bulk Si. This effect is also shown in Fig. 1.
Additionally, TEM techniques allow the analysis of cross sections of porous
silicon. As an example, HRTEM has been commonly used to study the transition
region between PS and the underlying Si substrate. In this regard, HRTEM crosssectional images (Fig. 2) show that both the thickness and roughness of the
Porous Silicon
60 nm
SEI
160 nm
5.0kV X13.000 1m WD 14.7mm
416
100 nm
uam
Bulk Silicon
uam
SEI
5.0kV X13.000
1m
WD 14.0mm
Fig. 3 Cross-sectional TEM (left) and SEM (middle) images of a PS-based optical interference
filter. (Right) Microcavity
transition region between PS and the substrate are generally small. As such, the
PS/Si interface has a very small effect on, for example, the optical behavior in the
visible wavelength regime of PS optical devices. In Fig. 2, a strong strain contrast
between the PS layer and the Si substrate is observed, which is likely caused by high
stress at the PS/Si interface (Martn-Palma et al. 2004). It has been found that the
stress at the PS/Si interface is caused by a high density of dislocations and latticematching occurs through pairs of edge dislocations (Fig. 2).
TEM has also been used to analyze the in-depth porosity profile of PS-based
multilayer stacks. An example is shown in Fig. 3 (left).
Scanning Electron Microscopy

Scanning electron microscopy (SEM) and high-resolution SEM (HRSEM)
(Goodhew et al. 2001) have been extensively used to study the morphology of
porous silicon. It is virtually impossible to provide the reader with a complete list of
works in this field. In this regard, many SEM images of high quality can be found in
books, reviews (see, e.g., Canham 1997; Lehmann 2002; Sailor 2011), and even the
Web!
In addition to analyze the surface morphology, SEM allows studying cross
sections of porous silicon. Figure 3 shows two examples, consisting in a crosssectional SEM image of a PS multilayer stack (middle) and a microcavity (right).
From Fig. 3, it is observed that PS-based multilayers have indeed a notable lateral
and in-depth homogeneity, with well-defined and sharp interfaces between adjacent
layers. This results in good optical behavior (see chapters Color of Porous
Silicon, Optical Gain in Porous Silicon, Porous Silicon Photonic
Crystals, Porous Silicon Multilayers and Superlattices, and Refractive
Index of Porous Silicon).
Figure 4 shows top SEM images of a complex porous silicon-based structure,
consisting in square wells with dimensions in the micron range whose walls are
composed of multilayer vertical structures with feature sizes in the nanometer
range. Additionally, microporous silicon is observed at the bottom of the wells.
Effectively, these structures behave as three-dimensional photonic crystals
417
Fig. 4 SEM top views of a complex PS structure, consisting in a square pattern on the micron
scale and a multilayer stack on the nanometer scale (see the walls of the vertical structures)
(Recio et al. 2012 and chapters Porous Silicon Photonic Crystals and
Porous Silicon Phononic Crystals).
As in the case of TEM/HRTEM, image processing can be applied to the analysis
of images acquired by SEM/HRSEM with the objective of determining several
parameters of interest. These include porosity, specific surface area, pore size, and
pore size distribution (Ludurczak et al. 2009).
Atomic Force Microscopy

Atomic force microscopy (AFM) (Eaton and West 2010) is a technique which has
been widely used for the analysis of the surface structure of PS at the nanoscale.
Surface roughness is a factor of major importance for many different practical uses,
including optical and biomedical applications (chapters Cell Culture on Porous
Silicon, Drug Delivery with Porous Silicon, Porous Silicon and Tissue
Engineering Scaffolds, Porous Silicon in Brachytherapy, Porous Silicon in
Photodynamic and Photothermal Therapy, Porous Silicon Optical Biosensors,
Porous Silicon Optical Waveguides, and Porous Silicon Phononic
Crystals). In the case of optics, low roughness at the external surface and the
substrate interface is mandatory to achieve good quality optical layers.
To illustrate the use of this technique, Fig. 5 shows AFM images of low porosity
and high porosity PS surfaces. These surfaces may be considered optically flat for
practical purposes in the whole visible range (diffuse reflection at the blue end of
the visible spectrum is lower than 0.3 %).
A related technique, namely, scanning tunneling microscopy (STM), has also
been used to acquire topographic as well as photon emission maps of the surface of
porous silicon (Dumas et al. 1993). In this technique, a STM tip is used as a local
source of electrons to excite cathodoluminescence (CL), resulting in an image
resolution of around 1 nm. In this line, CL mapping of porous silicon can be
achieved by modifying a commercial SEM system, basically by adding a collecting
120.000 nm
120.000 nm
418
0.2
0.2
0.4
0.4
0.6
0.6
0.8
0.8
Fig. 5 Surface of two very different porous silicon surfaces determined by AFM
mirror and a photomultiplier to the SEM (Bruska et al. 1996), aiming at understanding the relationship between the structural and electronic properties in this
material.
A variation of STM, named scanning tunneling microscopy light emission
(STM-LE), allows the measurement of the visible spectra from individual protrusions on the surface of PS (Ito et al. 1995). Additionally, photoassisted STM has
been used to study the surface of porous silicon (Pavlov and Pavlova 1997). In this
particular case, electron-hole pairs are excited by light and STM is used to measure
the corresponding tunneling current of excited carriers.
Other Microscopies
Although TEM/HRTEM, SEM/HRSEM, and AFM have been widely and routinely
used to analyze its morphology and overall physicochemical behavior, porous
silicon has been studied using a number of other microscopy techniques. Among
them, photoluminescence can be highlighted given that initially the most attracting
property of porous silicon was its light-emitting capabilities in the visible wavelength regime at room temperature. As an example of the myriad of studies in this
area, luminescence from individual Si nanocrystals in PS has been spatially isolated
and detected (Mason et al. 1998). For this study, a combination of single-particle
spectroscopy and shear force microscopy was used. In a subsequent study, the
distribution of individual chromophores in porous silicon was analyzed by combining the previous techniques with fluorescence microscopy (Mason et al. 2001).
The experimental results link the number and size of quantum dots in PS with its
photoluminescence emission. In this line, photoluminescence and reflected light
images of porous silicon can be acquired by means of a confocal scanning beam
macroscope/microscope (Ribes et al. 1995). It is worth noting that confocal imaging allows reconstructing 3D profiles of porous silicon.
Raman microscopy has also been widely used to determine the structure and
overall properties of porous silicon at the nanoscale. In particular, parameters like
crystallite size, temperature, and stress in porous silicon have been studied by a
419
Intensity (arb. units)
10
15
20
25
30
PL
(a)
1.80
1.78
(c)
0.34
FWHM (eV)
PL Intensity
Energy (eV)
(b)
1.82
0.32
0.30
32
1.6
28
24
20
Dep
16
th (
12
m
)
2.4
-1
0(cm )
1.8
)
eV
2.0 gy (
r
2.2 Ene
Intensity (arb. units)
0.28
1.4
(d)
0
524
Raman
(e)
522
(f)
-1
r0(cm )
Raman Intensity
520
10
5
(g)
32
28
450
24
16
Dep
12
th (
m
)
550
4
0 600
an
am
-1
500
20
d (nm)
400
sh
if
c
t(
4
0
10
15
20
Depth (m)
25
30
Fig. 6 (Left) 3D view of microphotoluminescence (microPL) (a) and micro-Raman (b) spectra at
different layer depths along the cross section of a 61 %/86 % porous silicon multilayer (10 layers).
(Right) Depth dependence of the most relevant parameters from the microPL (ac) and the Raman
(dg) spectra. Gray vertical stripes mark high porosity layers (Reprinted from Manotas et al. 1999)
combination of micro-Raman and microphotoluminescence spectroscopies

(Manotas et al. 1999), as shown in Fig. 6. Besides PS layers and multilayers,
more elaborate structures such as microcapsules have also been studied by microRaman spectroscopy, aiming at evaluating stress and crystallinity (Naumenko
et al. 2012).
Additionally, near-field scanning optical microscopy (NSOM) has been successfully applied to the imaging of topography and locally induced photoluminescence
of porous silicon (Rogers et al. 1995). The experimental results are, as in previous
cases, consistent with the quantum confinement model.
420
Multiphoton microscopy is another technique applied to the study of the

nonlinear optical response in porous silicon (Palestino et al. 2009). As an example
of its use, two-photon-excited fluorescence (TPEF) emission and second harmonic
generation (SHG) from glucose oxidase (GOX) adsorbed on porous silicon were
detected simultaneously.
And, finally, acoustic microscopy, comprising high-frequency microechography, acoustic signature V(z), and acoustic imaging, can be used to investigate the elastic properties of PS in a nondestructive manner (Da Fonseca
et al. 1995). Among these properties, thickness, longitudinal wave velocity, density,
acoustic impedance, velocities of surface acoustic modes, presence of elastic
gradients, and surface and subsurface roughness and defects can be measured,
estimated, or, at least, qualitatively determined.
Concluding Remarks
The complex structure of porous silicon makes it a very versatile material which
can be used in a wide variety of fields. At the same time, characterizing the
morphology of PS is a complex task. Several microscopy techniques have allowed
over the years to precisely determine the morphology and many other properties of
PS, with typical feature sizes spanning the micro- to nanometric length scales.
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Toupance T, Verjus F (2009) Image processing for the characterization of porous silicon
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under H, Andrzejak C, Berger MG, Klemradt U, L
uth H, Herino R, Ligeon M (1992) A detailed
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Naumenko D, Snitka V, Duch M, Torras N, Esteve J (2012) Stress mapping on the porous silicon
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Pascual L, Martn-Palma RJ, Landa-Cnovas AR, Herrero P, Martnez-Duart JM (2005) Lattice
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Sailor MJ (2011) Porous silicon in practice. Weinheim, Wiley
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Jeffery L. Coffer
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analysis of Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analysis of pSi Multilayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analysis of Loaded/Infiltrated pSi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
424
425
426
427
428
428
Abstract
X-ray diffraction (XRD) is a useful, complementary tool in the structural

characterization of porous silicon (pSi), providing information not readily available from direct visualization techniques such as electron microscopies. This
review outlines key considerations in the use of diffraction techniques for
analyses of this material in both thin film form and freestanding porous Si
nano or microparticles. Examples of the range of content in the analysis of pSi
are provided, including formation mechanisms, layer thickness, extent of pSi
oxidation, and degree of crystallinity. Such properties influence practical properties of pSi such as its biodegradability. We also focus on selected key properties where XRD has been particularly informative: (a) strain, (b) the structural
analysis of pSi multilayers, and (c) an analysis of pSi loaded with small
molecules of fundamental or therapeutic interest.
J.L. Coffer (*)

Department of Chemistry, Texas Christian University, Fort Worth, TX, USA
e-mail: j.coffer@tcu.edu
DOI 10.1007/978-3-319-05744-6_42
423
424
J.L. Coffer
Introduction
X-ray diffraction (XRD) (Pecharsky and Zavalij 2009) is a complementary tool in
the structural characterization of porous silicon (pSi), providing useful information
not readily available from direct visualization techniques such as electron microscopies. This review outlines key considerations in the use of diffraction techniques
for analyses of this material in thin film form attached to its underlying Si substrate,
along with recent results applied to freestanding porous Si nano or microparticles.
In terms of instrumentation, a typical x-ray powder diffractometer used in the
analysis of pSi is illustrated in Fig. 1. Spectra of pSi in powder form with good
signal-to-noise ratios can be obtained using a Cu K source operating at 2530 kV
on sample sizes of 1025 mg. XRD has been utilized for a diverse range of scientific
content in the analysis of pSi, ranging from formation mechanisms (Chamard
et al. 2001) to layer thickness (Guilinger et al. 1995). Other examples include the
use of XRD as an informative probe of the extent of pSi oxidation (Ogata
et al. 2001; Buttard et al. 1996a; Pap et al. 2005) as well as the degree of
crystallinity (Lehmann et al. 1993); experimental modification of these two parameters strongly influences other unique properties of pSi such as its biodegradability
(Shabir 2014; Shabir et al. 2011). Representative examples of the range of information obtained from XRD on pSi are outlined in Table 1.
Fig. 1 Typical x-ray powder

diffractometer (Phillips XL
300). Key components are
identified, including the
transformer/power supply,
x-ray source, goniometer, and
detector
425
Table 1 Areas of pSi research served by XRD

Fundamental topic/application
Formation mechanism
Layer thickness
Oxidation
Crystallinity/amorphization
Thermal expansion
Wetting by liquids
Structural form (film,
membrane, particle)
Interfacial roughness
Homoepitaxy
Strain
Porosity gradients/multilayers
Loading/infiltration
Reference
Chamard et al. (2001)
Guilinger et al. (1995)
Ogata et al. (2001), Buttard et al. (1996a), Pap et al. (2005)
Lehmann et al. (1993), Deb et al. (2001)
Faivre et al. (2000)
Bellet and Dolino (1994)
Milita et al. (2001), Buttard et al. (2002), Russo et al. (2011)
Lomov et al. (2000)
Liu et al. (2003)
Barla et al. (1984), Young et al. (1985), Bensaid et al. (1991),
Bellet et al. (1992), Lehmann et al. (1993), Bellet and Dolino
(1996), Lopez-Villegas et al. (1996), Buttard et al. (1999),
Abramof et al. (2006), Wijesinghe et al. (2009)
Buttard et al. (1996b, 1998)
Henschel et al. (2008, 2009), Berwanger et al. (2009),
Henschel et al. (2010), Wang et al. (2010), Ge et al. (2013)
We subsequently focus below on three key properties where XRD has been
particularly informative: (a) strain, (b) the structural analysis of pSi multilayers, and
(c) an analysis of pSi loaded with small molecules of fundamental or therapeutic
interest.
Analysis of Strain
The most detailed scrutiny has emerged from studies of pSi samples obtained from
anodization of p and p+ wafers; traditional high-resolution diffraction (Ogata
et al. 2001; Pap et al. 2005), along with double (Buttard et al. 1996a; Young
et al. 1985; Lopez-Villegas et al. 1996) and triple diffraction measurements
(Wijesinghe et al. 2009), has been evaluated. In the standard diffraction experiments
of this type of pSi, two features are observed in the 2631o region: a sharp peak
associated with the <111> reflection (~28o) and a broad diffuse peak (Ogata
et al. 2001; Young et al. 1985). Experiments to date suggest that the relative contributions of each are a function of HF electrolyte concentration (Ogata et al. 2001) and
wafer resistivity (Ogata et al. 2001; Buttard et al. 1996a). Importantly, with thermal
annealing up to 450 C, the intensity of the sharp feature disappears (Fig. 2) (Ogata
et al. 2001). Subsequent detailed concurrent XRD, transmission electron microscopy
(TEM), and electron diffraction have shown that the broad diffuse peak is not
associated with amorphous material, but likely rather a consequence of a random
distribution of nanopores (Bensaid et al. 1991). This is not without some controversy,
however, as some groups propose the possibilities of strained microcrystallites
(Lehmann et al. 1993) or pSi oxidation contributing to this phenomenon.
426
J.L. Coffer
Fig. 2 XRD spectra

demonstrating a shift of (111)
peak of a p+ pSi film after
annealing at (a) as prepared,
(b) 350 C, (c) 400 C, and
(d ) 450 C (Adapted from
Ogata et al. 2001)
Pragmatically, it should also be noted that for a freestanding, oriented pSi

membrane, the Bragg condition is only satisfied for the <400> peak near 70o
(Ogata et al. 2001).
Quantitative analysis of strain (typically by standard Hall-Williamson plots
(Williamson and Hall 1953)) for a number of different sample types has led to an
establishment of the following useful trends for pSi:
Strain is present in the form of lattice expansion perpendicular to the sample
surface (Barla et al. 1984; Young et al. 1985; Bellet and Dolino 1996; LopezVillegas et al. 1996), with typical a/a values in the range of 1.49 10 3 to
2.2 10 3 (Lopez-Villegas et al. 1996).
Significantly, strain increases with increasing porosity (Barla et al. 1984; Bellet
and Dolino 1996).
Strain increases with surface oxidation brought about by thermal annealing
(and correlates with dangling bond concentration) (Ogata et al. 2001; Buttard
et al. 1996a; Pap et al. 2005).
These trends provide complementary insights into changes in the fundamental
structure of pSi that accompany its common manipulation in the laboratory.
Analysis of pSi Multilayers

The extensive number of studies of pSi-based biosensors fabricated in multilayer
form (of alternating porosities) has provided strong motivation for analyses by
XRD (Thust et al. 1996; Lin et al. 1997; Dancil et al. 1999; Chan et al. 2000).
Related handbook chapters are Porous Silicon Multilayers and Superlattices,
427
and Porous Silicon Optical Biosensors. Results for this type of pSi sample have
been reported from double diffraction experiments, with data typically presented in
the form of so-called rocking curves. One of the most detailed investigations has
been reported by Bellet and coworkers for a structure of alternating porosities of
36 and 60 % for 10 periods (Buttard et al. 1996b, 1998). The most unique result of
such investigations is the appearance of prominent satellite peaks in the /2 plots
and their analysis by detailed simulations. Excellent agreement between experiment and simulation is found when a linear gradient transition layer (in terms of
both porosity and lattice parameter) is employed between layers, with a width of
14 nm for this layer providing optimal results (Buttard et al. 1996b, 1998).
For pSi superlattice multilayers of high quality, it is also possible to correlate the
observed fringes in the low-order satellite peaks with the total number of periods in
the pSi film (Buttard et al. 1998). This is viewed as strong evidence of lateral
homogeneity of the entire superlattice film thickness overall.
Analysis of Loaded/Infiltrated pSi

One of the interesting fundamental questions associated with a nanoporous material
concerns the effect of the nanopore on the structure and associated properties of a
loaded or infiltrated substance. For the case of pSi films still attached to its
underlying Si substrate, this question has been addressed for a range of simple
organic molecules, ranging from alkanes (such as hexane (Henschel et al. 2009)) to
alcohols of various sizes (from as small as ethanol (Henschel et al. 2010) to a
19 carbon linear chain alcohol (Henschel et al. 2008; Berwanger et al. 2009)). In
such studies, the size of the pore clearly has a strong influence on the structure of the
infiltrated species. For example, mesoporous silicon with a 15 nm pore diameter
results in the formation of lamellar bilayer structure, as evidenced by the appearance of a discrete Bragg reflection associated with this type of structure. In contrast,
mesopores with a 10 nm diameter lack these layering reflections (Henschel
et al. 2008). In the long term, it is believed that investigations of this sort may
provide useful information concerning the use of mesoporous silicon matrices for
inducing nucleation for the crystallization of protein solutions.
Recent developments have also shown the ability of freestanding porous Si
particles to act as stand-alone carriers for drug delivery (Anglin et al. 2008; Salonen
et al. 2008), in vivo imaging (Park et al. 2009), and sensing (Sailor and Link 2005).
In addition to ideally providing information regarding relative particle size (from a
Scherrer analysis of linewidth) (Patterson 1939), for drug-loaded pSi materials,
x-ray diffraction can also reveal details regarding the influence of pore structure on
the crystallinity of the drug upon infiltration.
For example, recent reports have shown that the crystalline antibacterial drug
triclosan can be readily infiltrated into mesoporous SI via a straightforward meltloading procedure (Wang et al. 2010). These studies have shown that a significant
broadening and/or loss of triclosan-associated peak intensity in the 2030 range of
2 takes place, depending on pSi porosity and loading method. Such changes are
428
J.L. Coffer
a 5000
1400
Triclosan-loaded
mesoporous (81%)Si
Triclosan
1200
X-Ray Intensity
X-Ray Intensity
4000
3000
2000
1000
1000
800
600
400
200
20
22
24
26
2 (degrees)
28
30
20
22
24
26
28
30
2 (degrees)
Fig. 3 X-ray diffraction spectra for (a) crystalline triclosan and (b) triclosan-loaded mesoporous
Si (81 %) (Adapted from Wang et al. 2010)
associated with nanostructuring or amorphatization of the loaded drug within the

mesopores. To illustrate this effect, typical XRD patterns for crystalline triclosan
and a pSi sample of 81 % porosity exposed to molten triclosan at 90 C for 35 min
are illustrated in Fig. 3. Significant loss of intensity in the crystalline triclosan
reflections near 24 and 25 are clearly observed.
Conclusions
The above x-ray diffraction studies of pSi clearly demonstrate the level of sensitive
structural information that this technique can provide. Given the increasing importance of this matrix in biosensing and drug delivery, along with emerging areas in
energy relevant to battery technology (e.g., Li storage and cycling (Ge et al. 2013)),
ample motivation for expanded use of XRD is in place.
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Gas Adsorption Analysis of Porous Silicon

Armando Loni
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Main Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Application to Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Origin of Hysteresis in Non-interconnected Mesopores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determination of Effects Associated with Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
432
432
433
434
434
436
436
Abstract
Pore volume and surface area of porous silicon are key parameters to consider
when developing applications that rely on the capacity to carry a payload, such
as drug delivery, or that are dependent on the degree of reactivity, such as
sensing or energetics. The ability to define and tune surface areas and pore size
distributions is a necessity for clinical use of the material. Herein, the historical
assessment of these physical parameters by gas adsorption is reviewed, the
methodology behind the measurements is described, the limitations are
highlighted, and data related to its use in determining the effects associated
with different anodization parameters and post-anodization processing is
presented.
A. Loni (*)
DOI 10.1007/978-3-319-05744-6_43
431
432
A. Loni
Introduction
Increasingly, porous silicon is being evaluated for the delivery of therapeutic
agents, such as hydrophobic drugs, proteins, and peptides (see chapter Drug
Delivery with Porous Silicon). Surface area is particularly important for the
optimization of large-molecule monolayer adsorption, while pore diameter is
particularly important when loading proteins.
Pore volume is related to porosity (see chapter Pore Volume (Porosity) in
Porous Silicon) and is generally described in terms of open volume (ml) per unit
weight (g) of material, while surface area is defined by the exposed internal surface
(m2) per unit weight of material; these parameters can be measured using gas
adsorption-desorption analysis (Gregg and Sing 1982). As well as surface area
and pore volume, information on pore size and shape can also be surmised.
Main Principles
The gas adsorption-desorption technique relates to the adsorption of nitrogen (or,
less commonly, carbon dioxide, argon, xenon, and krypton), at cryogenic temperatures, via adsorption and capillary condensation from the gas phase, with subsequent desorption occurring after complete pore filling. An adsorption-desorption
isotherm is constructed based upon the relationship between the pressure of the
adsorbate gas and the volume of gas adsorbed/desorbed. Computational analysis of
the isotherms based on the BET (Brunauer-Emmett-Teller) (Brunauer et al. 1938)
and/or BJH (Barrett-Joyner-Halenda) (Barrett et al. 1951) methods, underpinned by
the classical Kelvin equation, facilitates the calculation of surface area, pore
volume, average pore size, and pore size distribution.
A variety of instruments designed specifically for gas adsorption-desorption
analysis are commercially available. Common to all is the sample preparation
and measurement methodology (International Organization for Standardization
2006a): a portion of the porous material to be analyzed (typically > 150 mg) is
placed in a glass sample tube, dried/degassed (taking care to avoid thermal modification of the structure), and weighed; after attaching to the instrument, the sample
tube is evacuated and the free space volume measured by dosing with helium; after
evacuating the helium, the tube is immersed in cryogenic fluid (77 K for nitrogen
adsorbate) and the adsorbate gas dosed to the tube in incremental volumes, with the
pressure (P) being measured in situ relative to the saturation vapor pressure (PSV) of
the gas; multilayer adsorption onto the pore walls occurs initially, followed by
capillary condensation as the relative pressure is increased; dosing continues
until the isotherm reaches a plateau, signifying that the pores are completely filled
(P/PSV 1); thereafter, the pressure is incrementally reduced such that the
liquid starts to desorb, the porous structure eventually becoming empty once
again (P/PSV 0).
Surface area is obtained relatively quickly from the adsorption portion of the
isotherm (in the region of low relative vapor pressure) and follows the complete
H1
H2
433
b
H2
H2
Pore Blocking
Vad
Vad
Cavitation
Amount odsorbed
Delayed
Condensation
0.2
H3
0.4
0.6
H4
0.8
1.0
Delayed
Condensation
0.2
Meniscus
0.4
0.6
0.8
1.0
W>Wc
W<Wc
Meniscus
Relative pressure
Fig. 1 (a) IUPAC classification of hysteresis loops from gas adsorption-desorption; (b) schematic
illustration of pore morphology effects that give rise to type H2 hysteresis curves (From Thommes
2010)
coverage of the pore walls by one monolayer of the adsorbate (knowing the dose
volume and average molecular area); pore volume is obtained after complete filling
(which takes significantly longer, depending on the quantity and porosity of the
sample), the calculation being based on the density of the liquid adsorbate (and
knowing the total quantity adsorbed).
The kinetics of the adsorption and desorption processes are generally dissimilar;
both depend on, among other things, the nature of the pore (diameter, shape, etc.)
and the surface tension of the gas-liquid interface and can therefore give rise to
hysteresis within the isotherm. The width of the hysteresis loop provides a measure
of the pore size distribution and average pore diameter. A classification scheme
(Fig. 1a) exists that describes the various types of isotherm and hysteresis loops
(Gregg and Sing 1982; International Organization for Standardization 2006a; Sing
et al. 1985); the most common loop seen for porous silicon prepared by electrochemical etching is type H2, where effects like cavitation, pore blocking, and
percolation are often invoked (Fig. 1b).
Application to Porous Silicon

The gas adsorption technique was originally used to measure pore size and pore size
distribution in layers prepared by anodization of heavily doped (111) p-type wafers
(Bomchil et al. 1983). For essential background reading, the reader is referred to
more detailed follow-up work published for layers prepared on (100) wafers of
different types and resistivities and using a variety of electrochemical processing
conditions (electrolyte composition, current density, time) (Herino et al. 1987),
together with a review of the subject area published some 10 years later
(Herino 1997).
434
A. Loni
Origin of Hysteresis in Non-interconnected Mesopores

A detailed study (Coasne et al. 2001) on the nature of the isotherm obtained for the
ideal structural model of mesoporous silicon namely, an ordered network of
parallel, straight mesopores with no lateral interconnection revealed an asymmetric type H2 hysteresis loop (Fig. 1), unexpectedly similar to that typically
observed for highly interconnected mesoporous media. Identical adsorption isotherms were obtained (Naumov et al. 2008; Coasne et al. 2002) irrespective of
whether the pores were open at one or at both ends, in contrast with predictions
based on the modified Kelvin equation (Cohan 1938). Further, the pore size
distribution obtained from analysis of the adsorption and desorption branches was
not in accord with transmission electron microscopy data (Coasne et al. 2002),
bringing into question the validity of the Barrett-Joyner-Halenda method when
applied to mesoporous silicon. Subsequent work (Grosman and Ortega 2008a)
proposed that, while the mesopores were not connected, there existed between
them a physical coupling that accounted for the unexpected hysteretic behavior.
This led to theoretical work estimating adsorption-induced deformation (Grosman
and Ortega 2008b; Gor and Neimark 2011). An alternative proposal attributed the
anomalous behavior to the effects of a combination of pore diameter variation along
the pore length (Naumov et al. 2008) and the surface roughness and chemical
heterogeneity of the pore walls (Naumov et al. 2009).
Determination of Effects Associated with Processing

As a characterization tool for porous silicon materials and devices, gas adsorptiondesorption analysis has proved to be extremely useful, particularly so for process
development.
As an example, Fig. 2 shows the pore size distribution of both low- and
high-porosity layers (detached from substrate) and illustrates the effect of
post-anodization thermal oxidation, with the key parameters listed in Table 1.
Much higher surface area and pore volume and larger pore size are concomitant
with the higher porosity. In general, the value of porosity calculated from the total
pore volume (and knowing the density of both silicon and air) agrees very closely
with that obtained from gravimetric measurements; however, very high-porosity
material (>90 %) may be subject to pore collapse during air-drying (see
chapter Drying Techniques Applied to Porous Silicon), and this would yield
a comparatively lower pore volume (as well as lower surface area) and therefore
porosity. With regard to thermal oxidation, while the classical model implies there
is a continual shrinkage of pore size due to the associated volumetric expansion of
the crystal lattice (Sailor 2012), in practice, the average pore size actually
increases; this is accompanied by a shift in the pore size distribution and
significant reductions in both surface area and pore volume, probably due to
sintering (see chapter Sintering of Porous Silicon) (Loni and Canham 2013).
435
Pore Size Distribution : Anodised & Oxidised pSi
Cumulative Pore Volume (ml/g)
2.5
1.5
0.5
0
0
100
200
300
S1: 66% porosity
400
500
600
700
Average Pore Diameter ()
S2: 86% porosity
800
900
1000
S2: Oxidised (800C, 85 min)
Fig. 2 Pore size distributions for low- and high-porosity porous silicon (also showing the effect of
thermal oxidation)
Table 1 Parameters obtained from gas adsorption-desorption analysis after low- and highcurrent-density anodization and after static thermal oxidation in air (porosity calculated gravimetrically and from total pore volume; authors data)
Description
S1: anodized
(66 % gravimetric)
S2: anodized
(86 % gravimetric)
S2 then oxidized
(800 C, 85 min)
BET surface area

(m2/g)
287
Pore volume (ml/g)

0.789 (64 % porosity)
Average pore size

(nm)
10.9
495
2.267 (84 % porosity)
18.3
238
1.199 (75 % porosity)
20.1
Nitrogen annealing has been shown to increase pore size through coalescence
(Bjorkqvist et al. 2006), similar to oxidation, and also results in an overall reduction
in pore volume (and therefore payload capacity) (Limnell et al. 2007), while
chemical derivatization of pore walls has been shown to have very little effect on
the surface area and average pore size (Buriak et al. 1999). The technique has also
proved useful in the characterization of optical grating-type waveguides (Radzi
et al. 2012) as well as in the study of low-temperature solid-state interactions in
nanoporous silicon (Khokhlov 2008) and in the characterization of other forms of
porous silicon including etched silicon powders (Loni et al. 2011), silicon microassemblies (Bao et al. 2007), and silicon aerogels (Chen et al. 2012).
436
A. Loni
Limitations
Gas adsorption-desorption analysis becomes problematic for materials with low
surface area (Yanazawa et al. 2000; Suzuki and Oosawa 1997) and with pore sizes
>100 nm (Klobes et al. 2006). For mesoporous silicon with porosity less than 50 %
(equivalent pore size <8 nm), the measured surface areas are anomalously high in
comparison with small angle X-ray scattering measurements (Salonen et al. 2000).
In common with other types of microporous material (International Organization
for Standardization 2006b), the adsorption isotherm for microporous silicon (see
chapter Microporous Silicon) is very different to that of mesoporous silicon
(see chapter Mesoporous Silicon); with rapid adsorption of nitrogen at very
low relative pressure and no hysteresis upon desorption, the extraction of an
accurate pore size distribution is difficult (International Organization for Standardization 2006a; Sing et al. 1985) more so if micropores and mesopores are present
simultaneously, since the addition of micropores causes only very small changes in
both the isotherm shape and some of the BET constants (Gregg and Sing 1982).
References
Church BC, Kang Z, Abernathy HW, Summers CJ, Liu M, Sandhage KH (2007) Chemical
reduction of three-dimensional silica micro-assemblies into microporous silicon replicas.
Nature 446:172175
Barrett EP, Joyner LG, Halenda PH (1951) The determination of pore volume and area distributions in porous substances. I Computations from nitrogen isotherms. J Am Chem Soc
73:373380
Bjorkqvist M, Paski J, Salonen J, Lehto V-P (2006) Studies on hysteresis reduction in thermally
carbonized porous silicon humidity sensor. IEEE Sens J 6:542547
Bomchil G, Herino R, Barla K, Pfister JC (1983) Pore size distribution in porous silicon studied by
adsorption isotherms. J Electrochem Soc 130:16111614
Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multi-molecular layers. J Am
Chem Soc 60:309319
Buriak JM, Stewart MP, Geders TW, Allen MJ, Choi HC, Smith J, Raftery D, Canham LT (1999)
Lewis acid mediated hydrosilylation on porous silicon surfaces. J Am Chem Soc
121:1149111502
Chen K, Bao Z, Shen J, Wu G, Zhou B, Sandhage KH (2012) Freestanding monolithic silicon
Coasne B, Grosman A, Dupont-Pavlovsky N, Ortega C, Simon M (2001) Adsorption in an ordered
and non-interconnected mesoporous material: single crystal porous silicon. Phys Chem Chem
Phys 3:11961200
Coasne B, Grosman A, Ortega C, Simon M (2002) Adsorption in non-interconnected pores open at
one or at both ends: a reconsideration of the origin of the hysteresis phenomenon. Phys Rev
Lett 88(25):256102
Cohan LH (1938) Sorption hysteresis and the vapor pressure of concave surfaces. J Am Chem Soc
60:433435
Gor GY, Neimark AV (2011) Adsorption-induced deformation of mesoporous solids: macroscopic
approach and density functional theory. Langmuir 27:69266931
Gregg SJ, Sing KSW (1982) Adsorption, surface area and porosity. Academic, New York,
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Grosman A, Ortega C (2008a) Capillary condensation in porous materials: hysteresis and interaction mechanism without pore blocking/percolation process. Langmuir 24:39773986
Grosman A, Ortega C (2008b) Influence of elastic deformation of porous materials in adsorptiondesorption process: a thermodynamic approach. Phys Rev B 78(8):085433
Herino R (1997) Pore size distribution in porous silicon, Chapter 2.2. In: Canham LT
(ed) Properties of porous silicon, vol 18, EMIS datareviews series. INSPEC/IEE, London, pp
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International Organization for Standardization (2006a) Pore size distribution and porosity of solid
materials by mercury porosimetry and gas adsorption Part 2: analysis of mesopores and
macropores by gas adsorption. ISO 15901-2:2006(E)
International Organization for Standardization (2006b) Pore size distribution and porosity of solid
materials by mercury porosimetry and gas adsorption Part 3: analysis of micropores by gas
adsorption, ISO 15901-3:2006(E)
Ph.D. thesis, University of Leipzig. Available on-line at http://uni-leipzig.de/~valiu/index.
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Klobes P, Meyer K, Munro RG (2006) Porosity and specific surface area measurements for solid
materials, NIST recommended practice guide. Special Publication 960-17 (Sept 2006)
Limnell T, Riikonen J, Salonen J, Kaukonen AM, Laitinen L, Hirvonen J, Lehto VP (2007)
Surface chemistry and pore size affect carrier properties of mesoporous silicon microparticles.
Int J Pharma 343:141147
Loni A, Canham LT (2013) Exothermic phenomena and hazardous gas release during thermal
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condensation and hysteresis in porous silicon: network effects within independent pores.
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Naumov S, Khokhlov A, Valiullin R, Karger J, Monson PA (2009) Understanding adsorption
and desorption processes in mesoporous materials with independent disordered channels. Phys
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Radzi AASM, Yusop SFM, Rusop M, Abdullah S (2012) Structural and nitrogen gas adsorptiondesorption studies of Bragg grating waveguide fabricated on porous silicon nanostructure. IOP
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Sailor MJ (2012) Porous silicon in practice: preparation, characterization and applications,
Section 5.4. Wiley, Weinheim, pp 167170. ISBN 978-3-527-31378-5
Salonen J, Bjorkqvist M, Laine E (2000) Comparison of different methods in microstructural
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NMR Cryoporometry and Estimation of

Pore Sizes in Mesoporous Silicon
Rustem Valiullin
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Comparative NMR Cryoporometry and Gas Sorption Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Multilayered Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
439
441
442
446
Abstract
Nuclear magnetic resonance (NMR) cryoporometry is an experimental technique of structural characterization of mesoporous materials. In this contribution, different aspects of its application to study details of the pore structure in
mesoporous silicon are presented. In particular, the information obtained with
help of NMR cryoporometry is compared to that assessed using more conventional gas sorption techniques. The potentials of NMR cryoporometry to reveal
fine details of the pore structure in intentionally multilayered mesoporous silicon
are demonstrated.
Introduction
Assessing the pore structure information in porous silicon is important not only for
having control over its structure but also for understanding the mechanisms of its
formation. It can be done by a number of techniques operating on the basis of quite
different physical principles. One of the most widely used, powerful methods of
R. Valiullin (*)
e-mail: valiullin@uni-leipzig.de
DOI 10.1007/978-3-319-05744-6_44
439
440
R. Valiullin
structural characterization of porous, especially mesoporous, materials is gas

adsorption. By measuring the amount of physisorbed gas molecules as a function
of the gas pressure, which can be done gravimetrically, volumetrically, or by optical
means, one may obtain a wealth of information including the internal specific
surface, pore size distribution, and, under certain conditions, details of the pore
space geometry (Thommes 2010).
Recently, thermoporometry has emerged as an experimental approach for
structural characterization of mesoporous materials, complementary to gas
adsorption (Brun et al. 1977). In complete analogue to gas sorption methods,
where the shifts in capillary condensation or evaporation pressures are related
to the pore size, in thermoporometry the suppressions T of melting and freezing
transitions of confined liquids are related to the confinement size. The latter is
typically based on the GibbsThomson equation (Jackson and McKenna 1990)
T T 0 T x 4T 0 =x d H f k=x d,
(1)
where is the surface tension of the liquid, T0 the melting temperature of the bulk
liquid, T(x) the melting temperature of crystals in a pore with a linear dimension x,
Hf the specific heat of fusion, and the density of the frozen crystal. The length
parameter d takes account of the existence of nonfreezing layers (Valiullin and Furo
2002; Dash et al. 2006), adjacent to the pore walls. Assuming that , Hf, and are
temperature independent, they may be combined to the so-called cryoporometry
constant k. Notably, Eq. 1 is obtained under the assumption of perfect wetting of the
pore wall by the liquid.
NMR cryoporometry, one of the technical realizations of thermoporometry,
benefits from the ability of NMR to measure the temperature-dependent relative
fractions of liquid and crystalline phases formed in the pores at low temperatures
(Strange et al. 1993). Typical examples of the probe liquids include water and
cyclohexane, although more bulky molecules can be used to provide better
spatial resolution of the method (Vargas-Florencia et al. 2007; Schulz 2010).
The relative fractions in the liquid and frozen phases are readily determined by
NMR due to a substantial difference in their nuclear spinspin relaxation
times. Thus, by choosing an appropriate NMR protocol, the NMR signal from
the crystalline phase can be suppressed, and alone the signal of the liquid phase
is measured as a function of temperature. Because the NMR signal intensity is
proportional to the number of spins in the respective phases, by assuming that the
liquid density does not change appreciably with changing temperature, the
measured signal may be attributed to the volume occupied by the liquid
phase. By appropriately chosen model assumptions, in close similarity with
the various approaches used for the analysis of gas sorption data, the thus
obtained information can further be translated into pore size distributions
(Mitchell et al. 2008; Petrov and Furo 2009).
NMR Cryoporometry and Estimation of Pore Sizes in Mesoporous Silicon
441
Comparative NMR Cryoporometry and Gas Sorption Studies

Recently, NMR cryoporometry has been applied to study structural details of
mesoporous silicon (Dvoyashkin et al. 2008; Khokhlov 2009; Khokhlov
et al. 2007, 2008a, b). It is well known that different characterization techniques
may reveal different information. Therefore, comparative analysis of identical
samples using different approaches is beneficial not only for a better characterization but also for the understanding of the pros and cons of the techniques applied. In
this chapter, we provide such a comparative study of two selected mesoporous
silicon samples (see Table 1) using classical nitrogen gas sorption and NMR
cryoporometry techniques.
The samples were fabricated by electrochemical etching in an electrolyte using
two different silicon wafers with intermediate and high doping levels with the (100)
crystallographic orientation (Khokhlov 2009). For etching, an electrolyte composed
of an aqueous 48 % hydrofluoric acid solution and ethanol was used. The etching
process was carried out at room temperatures. For improving sample homogeneity,
a stop-etch method was used. Further details may be found in Khokhlov (2009).
Figure 1 shows nitrogen sorption isotherms measured at 77 K. Both samples
show hysteresis loops of type H2 according to the IUPAC classification (Rouquerol
et al. 1994), revealing developed mesoporosity with a substantial disorder in the
pore structure. With the use of model assumptions, the sorption isotherms can be
converted to the corresponding PSDs, some of which are exemplified in Fig. 2.
The primary quantities typically measured using NMR cryoporometry, to which
we here refer as melting curves, are shown in Fig. 3 for the two porous silicon
samples, with nitrobenzene used as a probe liquid. In PS1 melting occurs over a broad
range of temperatures, namely, from 210 to 250 K. This indicates the existence a
broad range of pore sizes, while sharp melting, as observed with PS2 around 240 K, is
associated with a narrow PSD. It is worth noting that the freezing branch is less
frequently considered, because it is anticipated that, in disordered porous material, it
is strongly affected by the so-called pore-blocking effect (Khokhlov et al. 2007;
Morishige et al. 2007), prohibiting any reliable PSD analysis.
The PSDs derived from the melting behavior are also shown in Fig. 2, for
comparison with PSDs obtained from gas adsorption. Interestingly, PSDs resulting
from intrinsically macroscopic approaches based on either the Kelvin equation
(triangles) in gas sorption or the GibbsThomson equation (squares) in
thermoporometry yield nearly identical information. At the same time, it is recognized
Table 1 Selected etching parameters and material properties for obtaining two mesoporous
silicon samples
Sample
PS1
PS2
Doping type
p
n
Resistivity, cm
12
(25) 103
Electrolyte HF:
C2H5OH
3:1
1:1
Etching current
density, mA/cm2
20
40
442
R. Valiullin
Fig. 1 Nitrogen sorption

isotherms for porous silicon
samples PS1 (a) and PS2 (b)
measured at 77 K
that conventionally applied NMR cryoporometry, which is based on the consideration

of the melting behavior, systematically delivers pore dimensions slightly lower than
that obtained using other techniques like gas sorption and SEM. It has recently been
shown that this effect originates from peculiarities of the melting process in disordered
pore systems, in which the interplay of two different melting mechanisms, namely, of
metastable melting associated with nucleation of liquid domains and of equilibrium
melting associated with growing of the already formed liquid domains, leads to an
underestimation of the pore sizes if the conventional methods of thermoporometry
data analysis are used (Kondrashova and Valiullin 2013).
Multilayered Porous Silicon

In this section we demonstrate the potential of NMR cryoporometry to reveal the
pore structure details in porous silicon materials with complex pore space geometries. Most simply, this can be done by preparing mesoporous silicon containing
443

functions derived from NMR
cryoporometry (squares) and
gas sorption data of Figure 1 a
and b, respectively. In the
latter case, the triangles refer
to BJH model with two
different methods for
assessing the nitrogen layer
thickness prior to capillary
condensation. By the circles,
the data obtained using the
model of Vonszombathely
et al. (1992) are shown
channel-like pores with the average pore diameter varying along the pore axes.
Such samples can be fabricated by using single-crystalline (100)-oriented p-type Si
wafers with a resistivity of 25 mcm, an electrolyte containing HF (48 %) and
ethanol in a ratio of 1:1, and by applying etching current densities of the order of
tens of mA/cm2. In this particular case, microstructuring was performed by a
temporal modulation of the etching current density j during the fabrication between
three values of j 20, 60, and 120 mA/cm2 (Kondrashova et al. 2011). This sample
will be referred to as PSm1. The time spans during which the current was kept
constant were chosen to yield a pore section length of about 1 m. The porous
silicon film thus fabricated contained many alternating sections etched with different currents, which defined the average pore sizes in the given sections. For a
dedicated review, see the handbook chapter Porous Silicon Multilayers and
Superlattices.
444
R. Valiullin
Fig. 3 Relative fractions of

liquid nitrobenzene measured
in porous silicon samples PS1
(a) and PS2 (b) upon
increasing temperature
Figure 4 shows the PSD obtained for this sample using NMR cryoporometry.
First of all, the occurrence of 3 well-resolved peaks in the PSD has to be noted. The
positions of the peak with the smallest pore size is found to coincide with that in the
sample obtained using a constant j 20 mA/cm2. The positions of the other two
peaks are slightly shifted to lower values as compared to the samples obtained with
the respective constant current densities. This finding is in agreement with the
discussion given in the previous section, conforming that melting in pore sections
with larger pore diameter is promoted by the contact with pore sections of smaller
diameter.
It turns out that assessing both melting and freezing branches in samples with
complex pore geometries may provide a more complete picture on the pore
structure. Thus, Fig. 5 shows the relative fractions of the liquid phase in two
complementary model samples determined upon cooling (freezing curve) and
upon subsequent heating (melting branch) (Khokhlov et al. 2007). The first sample
445

in mesoporous silicon PSm1
with modulated pore structure
Fig. 5 Freezing (rectangles) and melting (circles) transitions in porous silicon with ink-bottle
pore structure (a) and a mixture of two porous silicon materials with different pore sizes
corresponding to that in the ink-bottle system (b)
(PSc) contains a mixture of pieces of two different porous silicon materials etched
with different current densities, i.e., having different average pore diameters. Thus,
this sample represents a system of independent pores. The second sample (PSm2)
was fabricated by modulating the etching current to obtain the ink-bottle
446
R. Valiullin
configuration, i.e., the wider pores had access to the porous film surface only via the
narrower pores. The etching current densities used were j 20 mA/cm2 and j 80
mA/cm2; the other relevant parameters and Si wafer properties resembled those
used for PSm1.
These two samples, PC and PSm2, were designed to have identical PSDs. It is
not surprising, therefore, that the melting behaviors of nitrobenzene obtained with
these materials and shown in Fig. 5 are found to be almost identical. The sole
consideration of the melting curves does thus provide very little information on the
microstructural organization. It may be most significantly complemented, however,
by studying the freezing behavior. In a system of independent channels, freezing is,
in line with melting, found to proceed independently in two steps upon cooling it
first occurs in the pores with the bigger pore size and later in the smaller pores. In
the ink-bottle sample, however, freezing is controlled by pore blocking, i.e.,
freezing of larger pores is delayed to temperatures corresponding to freezing in
the smaller ones. Thus, combined freezing and melting experiments can be used to
get deeper insight in structural organization of nano-patterned porous silicon. An
alternative approach developed recently for the analysis of more complex structures
is referred to as NMR cryodiffusometry (Kondrashova et al. 2011; Perkins
et al. 2008).
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consequences. Rev Mod Phys 78(3):695741
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mesopores. J Chem Phys 129(15):154702154706
Jackson CL, McKenna GB (1990) The melting behavior of organic materials confined in porous
Khokhlov A (2009) Nanoporous silicon: structural characterization using nmr and applications.
University of Leipzig, Leipzig
Khokhlov A, Valiullin R, Karger J, Steinbach F, Feldhoff A (2007) Freezing and melting
transitions of liquids in mesopores with ink-bottle geometry. New J Phys 9(8):272
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simultaneously monitoring the low-temperature phase equilibria and diffusion of intrapore
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Rep 461(1):136
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Morishige K, Yasunaga H, Denoyel R, Wernert V (2007) Pore-blocking-controlled freezing of

water in cagelike pores of KIT-5. J Phys Chem C 111:94889495
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Characterization of Porous Silicon by

Calorimetry
Jarno Salonen
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
Calorimetry in Porous Silicon Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
Abstract
Thermal analysis and calorimetry offer versatile possibilities to study different

physical and chemical changes in materials. Calorimetry gives accurate and
valuable information on phase transitions of nanostructured materials and is
therefore very useful in studies of mesoporous materials. The use of calorimetry
in porous silicon research focusing on drug delivery applications and pore
morphology determination is reviewed.
Introduction
The term calorimetry denotes a variety of measurement methods which involve a
measurement of the heat of physical or chemical changes in a sample. One of the
most commonly used calorimetric methods is differential scanning calorimetry in
which the difference in the heat flow rate to a primary sample and a reference
sample is measured, when both are subjected to the similarly alternating temperature. Usually this is done in a specified, controlled atmosphere. In isothermal
calorimetry the measurement temperature is kept as constant as possible, and,
J. Salonen (*)
Department of Physics and Astronomy, Laboratory of Industrial Physics, University of Turku,
Turku, Finland
e-mail: jarno.salonen@utu.fi
DOI 10.1007/978-3-319-05744-6_45
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450
J. Salonen
Fig. 1 Picture of a DSC

instrument cover opened. A
sample press to seal
hermetically Al sample pans
is on the right side of the DSC
instead of temperature alternation, the other environmental parameters such as gas

atmosphere, relative humidity, light exposure, etc., are alternated.
Thermal analysis is closely related to calorimetry. The definition of thermal
analysis formulated by International Confederation for Thermal Analysis and
Calorimetry (ICTAC) is the following (Hemminger and Sarge 1998): Thermal
Analysis (TA): a group of techniques in which a property of the sample is monitored
against time or temperature while the temperature of the sample, in a specified
atmosphere, is programmed. In the other words, almost all the calorimetric techniques are also included in the definition of thermal analysis. Only the methods which
are performed at ambient temperature without any temperature control are not
included in thermal analysis. In addition to calorimetric methods, thermal analysis
includes a wide variety of different methods and is a much larger group of techniques
than calorimetry. Many of the thermal analysis methods are very close to calorimetric
methods, like Differential Thermal Analysis (DTA), in which, instead of heat flow, a
temperature difference between the sample and reference is measured. In certain
cases it is very difficult to define the difference between the methods. For example, in
Simultaneous Thermal Analysis (STA), Thermogravimetry (TG) and Differential
Scanning Calorimetry (DSC) (Fig. 1) are combined in a single instrument, and both
measurements are performed simultaneously.
Although thermal analysis and calorimetry offer versatile possibilities to study
different physical and chemical changes in materials, it is not frequently used in
materials research excluding pharmacy and certain branches of chemistry (Garbett
and Chaires 2012; Baird and Taylor 2012; Landry 2005). Partly this is because of
traditions, but also because the methods are not familiar to scientists working in the
field of materials research. In the case of porous silicon research, thermal analysis
and calorimetry have been used more frequently than usually in material research.
Some of the studies in which these methods are used will be described in the
following chapter.
451
Calorimetry in Porous Silicon Research

Calorimetry was used in porous silicon (PSi) research already in 1992 in order to
study pore size and hydrophobicity of as-anodized microporous silicon (Canham
and Groszek 1992). Later in the 1990s, calorimetry was used in studies of structural
processes in differently doped p-type PSi (Budaguan et al. 1996) and in different
oxidation studies (Salonen et al. 1997a, b; Salonen et al. 1999a, b). In the oxidation
studies, calorimetric methods were proved to be beneficial and diverse covering
different oxidation processes from room temperature to photo-oxidation including
oxidation in aqueous and other liquid solutions. In 1999, Faivre et al. used the
so-called thermoporometry to study the pore size and morphology of PSi for the
first time (Fig. 2) (Faivre et al. 1999b). The method is based on the GibbsThomson
equation, which describes how the phase transition temperatures change when the
material is confined in small curved space, e.g., melting occurs generally at lower
temperature than that of the bulk material. This is a very interesting phenomenon.
Practically it means that even the smallest grains and crystallites, which have
already ordered structure, can be detected by calorimetric methods making them
much more sensitive compared to x-ray diffraction methods to detect crystallized
nanoparticles in a sample.
In the case the material is confined in small, nanoscale pores, there is an
additional factor affecting the phase transitions. This is a thin disordered layer
(-layer) between the material inside the pore and the pore wall which does not
undergo phase transitions. The thickness of the layer depends on the interactions
between the pore wall and the material, and also on the molecular structure and size
of the material, but not on the pore size. This phenomenon has been used to study
the interaction of ibuprofen and different surface chemistries of PSi (Riikonen
et al. 2009). By combining TG and DCS and using samples with a similar surface
chemistry but different pore sizes, it was possible to determine the thickness of
Fig. 2 DSC measurement with increasing and decreasing temperature scans of the solidliquid
transitions of dodecane confined in (a) A p+-type PSi (porosity 60 %) and (b) A p -type PSi
(porosity 65 %). Dodecane confined in the pores gives rise to a broad peak shifted to lower
temperatures, while a bulk liquid outside the pores gives a narrow intense peak at the bulk
transition temperature (Faivre et al. 1999a) (Reprinted with permission from Springer)
452
J. Salonen
ibuprofen -layer in as-anodized, thermally oxidized, and thermally carbonized

PSi. The observed variations in the -layer thickness from 1.2 to 2.2 nm demonstrate the importance of the surface chemistry on the processes in nanoscale pores.
In 2005, two articles related to a determination of drug load in porous silicon
were published (Salonen et al. 2005b; Lehto et al. 2005). Due to the increased
interest and activity in drug delivery applications of PSi, it became necessary to find
a fast and simple method to characterize the drug loaded in PSi, i.e., its amount,
crystallinity, and how much of it is inside the pores and how much on the external
surface of PSi. Using a combination of TG and DSC, all those parameters can be
determined. In a TG measurement, the drug loaded in PSi decomposes and desorbs
usually completely at temperatures below 700 C, and the weight decrease is a good
estimation of the total drug load. If the decomposing drug reacts chemically with
the PSi carrier before or during the decomposition, the TG results could underestimate the real loading degree. Even in that case, the estimate could be accurate
enough if only small fraction of decomposed drug remains attached on the
pore walls.
The physical state of the drug loaded can be determined with DSC. In order to
increase a dissolution rate of poorly soluble drugs, it is preferred that the drug
loaded in the pores is in an amorphous form. This means that any melting peak
should not be detected in a DSC measurement. If a sharp melting peak close to the
melting temperature of bulk drug is detected, there is some crystalline drug on
the external surface of PSi carrier, but if the melting peak is broad and below the
melting temperature of the bulk drug, it indicates formation of crystallized
nanoparticles inside the pores (Salonen et al. 2008). Because the total drug load
can be determined with TG and the crystalline fraction of the drug can be quantified
from the melting peaks using a melting enthalpy of the drug, also the amorphous
Table 1 Different calorimetric techniques used in PSi research
Aim
Thermal oxidation
Photo-oxidation
Reactivity in solution
Method
DSC
Isothermal
microcalorimeter
(IMC)
IMC
Modification of
surface chemistry
Thermoporometry
DrugPSi interaction
DSC
Drug load
determination
Heat of wetting
Explosive properties
DSC
DSC
DSC, IMC
Flow calorimetry
DSC, bomb
calorimetry
Study example
Salonen (Salonen et al. 1997b, 1999a, 2002)
Salonen (Salonen et al. 1999b)
Salonen (Salonen et al. 1997a, 2001),

Riikonen (Riikonen et al. 2012)
Salonen (Salonen et al. 2003)
Faivre (Faivre et al. 1999a)
Salonen (Salonen et al. 2005a), Riikonen
(Riikonen et al. 2009)
Salonen (Salonen et al. 2005a, b), Wang
(Wang et al. 2010)
Canham (Canham and Groszek 1992)
Plummer (Plummer et al. 2008), Becker
(Becker et al. 2010)
453
fraction of the drug in the sample can be calculated relatively accurate (Salonen
et al. 2005a). This makes the combination of TG and DSC a fast and simple method
to estimate the amount and physical state of the drug loaded. Examples of the use of
different calorimetric techniques in PSi research are gathered in Table 1.
References
Baird JA, Taylor LS (2012) Evaluation of amorphous solid dispersion properties using thermal
analysis techniques. Adv Drug Deliv Rev 64(5):396421. doi:10.1016/j.addr.2011.07.009
Becker CR, Currano LJ, Churaman WA, Stoldt CR (2010) Thermal analysis of the exothermic
reaction between galvanic porous silicon and sodium perchlorate. ACS Appl Mater Interfaces
2(11):29983003. doi:10.1021/am100975u
Budaguan BG, Aivazov AA, Sazonov AY (1996) Calorimetric investigation of structural processes in porous silicon. J Non-Cryst Solids 204(2):169171. doi:10.1016/s0022-3093(96)
00403-6
Canham LT, Groszek AJ (1992) Characterization of microporous Si by flow calorimetry
comparison with a hydrophobic SiO2 molecular sieve. J Appl Phys 72(4):15581565
Faivre C, Bellet D, Dolino G (1999a) Phase transitions of fluids confined in porous silicon: a
differential calorimetry investigation. Eur Phys J B 7(1):1936. doi:10.1007/s100510050586
Faivre C, Bellet D, Dolino G (1999b) Phase transitions of fluids confined in porous silicon: a
differential calorimetry investigation. Eur Phys J B Condens Matter Phys 7(1):1936
Garbett NC, Chaires JB (2012) Thermodynamic studies for drug design and screening. Expert
Opin Drug Discov 7(4):299314. doi:10.1517/17460441.2012.666235
Hemminger W, Sarge SM (1998) Chapter 1 Definitions, nomenclature, terms and literature. In:
Michael EB (ed) Handbook of thermal analysis and calorimetry, vol 1. Elsevier Science B.V.,
Burlington, pp 173
Landry MR (2005) Thermoporometry by differential scanning calorimetry: experimental considerations and applications. Thermochim Acta 433(12):2750. doi:10.1016/j.tca.2005.02.015
Lehto VP, Vaha-Heikkila K, Paski J, Salonen J (2005) Use of thermoanalytical methods in
quantification of drug load in mesoporous silicon microparticles. J Therm Anal Calorim
80(2):393397
Plummer A, Cao H, Dawson R, Lowe R, Shapter J, Voelcker NH (2008) The influence of pore size
and oxidising agent on the energetic properties of porous silicon. In: Voelcker NH, Thissen
HW (eds) Smart materials V. Proceedings of SPIE. Spie-international society for optical
engineeringBellingham, vol 7267. 72670 p, doi: 10.1117/12.810453
Riikonen J, Makila E, Salonen J, Lehto VP (2009) Determination of the physical state of drug
molecules in mesoporous silicon with different surface chemistries. Langmuir 25(11):
61376142. doi:10.1021/la804055s
Riikonen J, Salomaki M, van Wonderen J, Kemell M, Xu W, Korhonen O, Ritala M, MacMillan F,
Salonen J, Lehto VP (2012) Surface chemistry, reactivity, and pore structure of porous silicon
oxidized by various methods. Langmuir 28(28):1057310583. doi:10.1021/la301642w
Salonen J, Lehto VP, Laine E (1997a) The room temperature oxidation of porous silicon. Appl
Surf Sci 120(34):191198
Salonen J, Lehto VP, Laine E (1997b) Thermal oxidation of free-standing porous silicon films.
Salonen J, Lehto VP, Bjorkqvist M, Laine E (1999a) A role of illumination during etching to
porous silicon oxidation. Appl Phys Lett 75(6):826828
Salonen J, Lehto VP, Laine E (1999b) Photo-oxidation studies of porous silicon using a microcalorimetric method. J Appl Phys 86(10):58885893
Salonen J, Lehto V, Bjorkqvist M, Laine E, Niinisto L (2001) Chemical stability of thermallycarbonized porous silicon. Mat Res Soc Symp Proc F14.19. 638:1116
454
J. Salonen

acetylene. J Appl Phys 91(1):456461
Salonen J, Laine E, Niinisto L (2003) Thermal analysis of hydrosilylation of 1-dodecene on porous
silicon surface. Phys Status Solidi A 197(1):246250
Hirvonen J, Lehto VP (2005a) Mesoporous silicon microparticles for oral drug delivery:
loading and release of five model drugs. J Control Release 108(23):362374
Salonen J, Paski J, Vaha-Heikkila K, Heikkila T, Bjorkqvist M, Lehto VP (2005b) Determination
of drug load in porous silicon microparticles by calorimetry. Phys Status Solidi A-Appl Mater
Sci 202(8):16291633
applications. J Pharm Sci 97(2):632653
Wang F, Hui H, Barnes TJ, Barnett C, Prestidge CA (2010) Oxidized mesoporous silicon
microparticles for improved oral delivery of poorly soluble drugs. Mol Pharm 7(1):227236.
doi:10.1021/mp900221e
Magnetic Characterization Methods for

Porous Silicon
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Magnetometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
MFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Magneto-optical Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Magnetic Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analysis of Magnetization Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
456
456
457
459
459
460
461
461
Abstract
Characterization methods for magnetic materials, especially nanostructured

ones such as mesoporous silicon, are reviewed. Besides magnetometers, which
are one of the most important instruments to investigate magnetic properties,
magnetic force microscopy and magneto-optical microscopy are briefly
outlined. Magnetometers measure in an integrative way over the entire sample,
whereas magnetic force microscopy and magneto-optical methods probe the
magnetic properties of a local region or an individual nanostructure. With
magnetometers in general, field- and temperature-dependent measurements
can be performed; magneto-optical microscopy can be used to get knowledge
about the domain structure, and with magnetic force microscopy, the magnetization reversal of, e.g., a nanowire, can be studied.
K. Rumpf (*) P. Granitzer

e-mail: klemens.rumpf@uni-graz.at
DOI 10.1007/978-3-319-05744-6_46
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456
Introduction
Due to nanostructuring of materials and the ability to fabricate nanosized objects,
the requirements for their characterization are increasing, and the resolution of the
various techniques has to be improved continuously. Concerning the investigation
of the magnetic properties of nanomaterials on the one hand, the employed technique has to be sufficiently sensitive in the case of a small amount of material, and
on the other hand it has to be appropriate to provide information about nanosized
objects, e.g., about the arrangement on surfaces or in 3-D templates. Magnetization
measurements can give evidence about the coupling mechanism, especially in
combination with structural investigations. For the characterization of magnetic
materials, many methods are suitable to gain information about the magnetic status,
wherein magnetometers play a key role, especially concerning the investigation of
nanomaterials. Such instruments enable measurements of magnetization dependence on applied external magnetic field and temperature. In general the magnetic
behavior strongly depends on these parameters, as, for example, superparamagnetic
particles offer a magnetic phase transition, whereas this transition temperature is
correlated with the particle size and the arrangement of the particles (Gubin 2009).
The two most employed types of magnetometer for nanomaterial investigations are
superconducting quantum interference devices (SQUID) and vibrating sample
magnetometers (VSM), but also alternating gradient field magnetometers
(AGFM) are used. Further techniques to get knowledge about the magnetic properties of a sample are, for example, scanning techniques such as scanning probe
microscopy (Hubert and Schafer 1998), magneto-optical methods (Thiaville
et al. 2005), ferromagnetic resonance (Baberschke 2011), scattering methods such
as electron scattering (Zhu 2005) or X-ray scattering (Zhu 2005) or neutron
scattering (Zhu 2005). Porous silicon with embedded magnetic nanostructures,
which have been discussed in the other handbook chapters, has been investigated
magnetically mainly by SQUID and VSM. Further applied methods to get information about the magnetic status of such specimens are magneto-optical or magnetic force microscopy. Thus, in this review, such techniques as SQUID, VSM,
magnetic force microscopy, and magneto-optical microscopy will be introduced.
More details about these techniques can be found elsewhere (Czichos et al. 2006).
Magnetometer
A magnetometer commonly measure samples in an integrative manner, integrating
the magnetic moment over the entire volume in contrast to, e.g., magneto-optical
methods which give more local information about the specimen. The method is in
general noninvasive.
The most sensitive instruments are SQUID magnetometers (Fig. 1) which in
general allow to measure signals down to a range of 10 8 emu. They are equipped
Magnetic Characterization Methods for Porous Silicon
457
Fig. 1 Image of a
Superconducting Quantum
Interference Device (SQUID)
MPMS XL 7, Quantum
Design. Magnetic field range:
7 T, temperature range:
1.7400 K (Institute of
Physics, Karl-FranzensUniversity Graz)
with superconducting pickup coils and a superconducting quantum interference

device as flux detector.
Vibrating sample magnetometers measure the magnetic moment in the presence
of a static or slowly changing external magnetic field. Most setups are employed
with fixed pickup coils, and the sample is vibrating between them. The measured
signal depends not only on the magnetic moment but also on the amplitude and the
frequency of the vibrations. The sensitivity of such systems is in the range of
10 6 emu.
An alternating gradient field magnetometer is a modification of the Faraday
balance, and this instrument measures the force on a magnetic dipole caused by a
magnetic field gradient. The sensitivity which can be reached is comparable to the
one of a SQUID.
For all magnetometers, the sample size is normally limited to a few square
millimeters (25 mm across), and thus the magnetization signal can be weak,
depending on the type and amount of contained magnetic material, which necessitates a sufficient high sensitivity of the employed instrument.
MFM
Further possibilities to investigate magnetic samples are scanning techniques as, for
example, an atomic force microscope equipped with a magnetic tip (Saenz
et al. 1987), a so-called magnetic force microscope which can be used to investigate
especially the domain structure and even the domain walls of magnetic samples
458
(Hsieh et al. 2005). This method utilizes the magnetic interaction between magnetic
tip and sample which is recorded. In general a spatial resolution of about 20 nm can
be achieved. The resolution is determined by the geometry of the tip, the distance
between sample and tip and also the sensitivity of the instrument. By optimizing all
factors, also structures in a lower nanosize regime can be monitored, e.g., magnetic
nanoparticles in the range of 10 nm by using special prepared tips (Koblischka
et al. 2003). To record individual nanoparticles, the distance between the particles
has to be sufficiently large to guarantee an image with excluding a convolution of
the tip with the particle and also the effects of magnetic coupling (e.g., local
ordering) on the image have to be kept in mind. A precondition for porous samples
to be investigated is low surface roughness of the specimens. MFM has been
successfully employed in porous alumina templates with deposited magnetic
nanowires to figure out the direction of magnetization of the individual wires
(Kalska-Szostko et al. 2009) and also to investigate their magnetization reversal
(Sorop et al. 2003). In the latter case, an external magnetic field has to be applied
during the investigations. In the case of porous silicon with embedded magnetic
nanostructures, the investigation of the magnetization of the precipitates with a
MFM is quite difficult. In scanning the surface, the roughness has to be taken into
account, and the pores have to be completely filled up to the surface. The image
depends on the magnetic polarization direction of the tip, out-of-plane or in-plane,
in relation to the scanned surface. Standard tips are polarized out-of-plane. This is
important in scanning cross-sections of porous samples with embedded magnetic
nanostructures because the stray fields of the deposits depend on their geometry
(e.g., spherical particles or elongated structures). An MFM image of a porous
silicon sample filled with quite densely packed spherical Ni particles can be seen
in Fig. 2. All these limitations are often not met, and thus other characterizing
methods are more suitable for porous media.
b 0.5
1 mm
Magnetic Phase ( )
3 m
0.4
0.3
0.2
0.1
0.0
0.1
0
6
8
10
Distance (m)
12
14
Fig. 2 (a) MFM measurements performed in magnetic mode showing the abrupt change between
silicon (right) and Ni-filled porous silicon (left). (b) The sharp contrast of the magnetic phase
between nonmagnetic and magnetic material can be seen (Granitzer et al. 2010)
459
Magneto-optical Microscopy
A further local method to investigate magnetization processes as well as domain
nucleation is the exploitation of the Faraday and Kerr effect. Magneto-optical
techniques are very sensitive and allow the investigation of only monolayer thick
magnetic films and nanostructure arrays (Ganshina et al. 2005; Gonzalez-Diaz
et al. 2007). In layered systems consisting of noble metal/ferromagnetic metal
multilayers, an increase of the magneto-optical effects is observed due to surface
plasmon resonance of noble metals.
In general magneto-optic imaging is based on the rotation of the plane of
polarization of linearly polarized light after interacting with a magnetic sample,
whereas the reflected beam is detected (Kerr microscopy) (Giergiel and Kirschner
1996). The magneto-optical Kerr effect is physically based on the magnetic circular
dichroism. This effect is used for magnetic imaging using an optical microscope
setup. If the diameter of the light beam is larger than the domain size, magnetization
curves can be observed (Beaurepaire et al. 2006). The spatial resolution of this
method is only limited by the optical resolution.
A further optical method to investigate magnetic domains and magnetization
reversal processes is based on transmission electron microscopy whereat the
Lorentz force affecting the electrons is exploited and used for magnetic imaging.
Thus, this technique is called Lorentz microscopy (Petford-Long and Chapman
2005). The direction of the electrons after transmission through a sample is deflected
in different directions depending on the direction of the local magnetization.
Both techniques, which give local information about the magnetic behavior of a
sample, are adequate to investigate porous materials (Pathak and Sharma 2012;
Korolev et al. 2007), whereat in the case of transmission electron microscopy the
sample preparation of porous materials, especially with embedded deposits, is
tricky and can influence and modify the sample. For example, in using focused
ion beam preparation, amorphization of porous silicon at the pore walls or
sputtering of the metal deposits can occur.
Magnetic Characterization
As discussed in a separate handbook chapter Ferromagnetism and Ferromagnetic Silicon Nanocomposites, the ferromagnetic signal of bare porous silicon
samples is very weak and 23 orders of magnitude smaller compared to porous
silicon with magnetic precipitates. The magnetic status of bare porous silicon
depends on the surface treatment and the occurrence of dangling bonds. Due to
the weak and difficult observable magnetic signal, the measurements have to be
carried out with a sufficiently sensitive magnetometer. The ferromagnetic magnetization signal of a bare porous silicon sample is in the range of 10 6 emu, and thus
a VSM is already operating in the upper limit wherefore a SQUID is more suitable
to figure out the magnetization curve which in general is superimposed by a strong
diamagnetic contribution.
460
In the case of porous materials such as porous silicon with embedded ferromagnetic nanostructures, the choice of the magnetometer is not so important due to the
sufficient high magnetization, and thus all types of magnetometer allow the magnetization of the sample to be ascertained. MFM enables the magnetization status of
small regions to be derived, in general in the range of a few 10 nm of the sample and
thus even individual nanostructures. The porous structure and the involved rough
surface, especially caused by the metal deposition process (Granitzer et al. 2009a),
constrain the potential of this method.
Representative magnetization measurements were performed using Ni precipitated in needlelike structures of an aspect ratio up to 100, Co deposited in
almost spherical particles with a maximum length of 100 nm and NiCo incorporated in granular elongated structures with a length up to 500 nm (Rumpf
et al. 2010). MFM investigations of the cross-section of samples, using an outof-plane polarized tip, do not give magnetic information in the case of elongated structures because the magnetic easy axis is along the pores. Spherical
particles and not perfect cylindrical wires offer stray fields which lead to a
usable signal.
Analysis of Magnetization Measurements

From magnetization measurements, not only the magnetic status of a sample can be
acquired, but it can be also concluded if particles magnetically interact or about the
geometry and size of nanostructures.
Measuring the magnetization of porous silicon with embedded nanowires in
both magnetization directions, perpendicular (easy axis) and parallel (hard
axis), to the sample surface results in a magnetic anisotropy which not only
gives information about the shape of the ferromagnetic structures but also
correlates with the interaction of the ferromagnetic metal nanostructures
(Granitzer et al. 2012). The coercivities can also be used to obtain information
about the magnetic interactions of the metal structures considering such ones of
same size and shape.
The coercivity of nanowires depends mainly on contributions due to the shape,
magneto-crystalline and magnetoelastic anisotropy (Skomski and Coey 1999).
Shape anisotropy affects the strength of the demagnetizing factor, and magnetocrystalline anisotropy depending on the crystal symmetry of the metal structures
can be neglected if the crystalline orientation of the deposits is randomly distributed
(Granitzer et al. 2009b; Bertotti 1998). Magnetoelastic anisotropy which is usually
induced by an external stress is caused on the one hand due to magnetostrictive
effects but also in relation with the lattice mismatch between deposited metal and
silicon skeleton. Magnetic interaction takes place due to dipolar interactions
between the nanostructures, but exchange interactions cannot be excluded in case
of a dense metal structure distribution.
461
Conclusion
For magnetic investigations of porous silicon and porous silicon nanocomposites,
various magnetic characterization techniques are available. The choice of technique
depends on the necessary sensitivity and also on the desired magnetic information.
Magnetometers measure in an integrative way over the entire sample, whereas
magnetic force microscopy and magneto-optical methods investigate the magnetic
properties of a local region or even individual nanostructure of the sample. Magnetometers generally allow measurements of dependence on magnetic field and
temperature and from the data, not only the magnetization of the sample but also
indications of, e.g., the structure and magnetic coupling between nanoparticles can
be ascertained. Magneto-optical methods with their local character allow determination of the domain structure of a sample. MFM can be used to figure out
magnetization reversal processes if an external magnetic field is applied and also
to see the direction of the magnetization, e.g., in the case of a nanowire. Using
MFM, also the sample preparation plays an important role because the nature of the
surface can influence the gained results. The abovementioned methods are both
noninvasive and nondestructive to the examined specimen.
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range using MFM ambient conditions. Mater Sci Eng C 23:747
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Magnetic microscopy of nanostructures. Springer, Berlin
Rumpf K, Granitzer P, Polt P (2010) Synthesis and magnetic characterization of metal-filled
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HR, Guentherodt HJ (1987) Observation of magnetic forces by the atomic force microscope.
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Zhu Y (ed) (2005) Modern techniques for characterizing magnetic materials. Springer/Kluwer,
Boston
Chemical Characterization of Porous Silicon

Mihaela Kusko and Iuliana Mihalache
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
Chemical Composition of Electrochemically Etched Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . 468
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
Abstract
We provide a literature survey of a number of classical techniques used to

quantify the chemical composition of porous silicon, highlighting their general
merits and potential limitations with the material. Much of the early literature
was focused on photoluminescent material, but increasingly there are studies on
nanocomposites where chemical composition analysis is required to assess the
degree and uniformity of impregnation or surface attachment.
Introduction
The chemical composition of porous silicon (PS) plays an important role in determining its properties (see Part II of this Handbook) and applications (see Part V of
this Handbook). This review surveys five classical techniques used in this regard,
highlighting their general merits and potential issues with porous silicon, their
application to different chemical forms of porous silicon, and their use in development of structures for diverse applications. Both electron and ion spectroscopies
are classic methods of in-depth and surface chemical analysis at the nanoscale.
Therefore, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron
M. Kusko (*) I. Mihalache
Laboratory of Nanobiotechnology, National Institute for Research and Development in
Microtechnologies (IMT Bucharest), Bucharest, Romania
e-mail: mihaela.kusko@imt.ro
DOI 10.1007/978-3-319-05744-6_47
463
464
M. Kusko and I. Mihalache
Table 1 Evaluation of chemical characterization methods by analytical capabilities for PS

samples
Method
EDX
XPS
AES
SIMS
RBS
Advantages
Quantitative without
reference samples
Used in conjunction with
electron microscopy (T)SEM
Chemical binding state ID and
elemental composition
(surface concentrations and
the chemical shifts)
Can reveal the chemical

composition of the silicon
surface during the etching
process
Some organic molecules can
be identified
Smallest volume of any
analytical technique, depth
profiling analysis
1050 nm lateral spatial
resolution
Elemental composition, phase
transition, and some chemical
state ID
Depth resolution 0.5 nm

The atomic ratio H/Si in PS
Ultimate detection limit ppb
for B in Si
Molecular specificity
polymers
Fast analyzing method
Nondestructive
Elemental composition and
depth profiling of individual
elements (220 nm
resolution)
Quantitative without
reference samples
Investigate changes in
porosity
Disadvantages
No chemical state ID
Reference
Garratt Reed and
Bell (2003)
No chemical depth profile

Samples for XPS must be
compatible with the ultrahigh
vacuum environment
It probes only the very outer
surface, not the huge internal
surface
Cannot detect H or He and
consequently the ratio of
elements in the sample that is
not entirely accurate
Only a lateral resolution of a
few to 100 m can be reached
Surface may be damaged by
the incident electron beam
Surface electrostatic charging
Quantitative analysis depends
on the element (light
elements >0.1 %, heavier
elements >1 %); typical
accuracy 10 %
Destructive method
Quantification needs very
similar standards
Calibration is critical
Heide (2011),
Watts and
Wolstenholme
(2003)
Watts and
Wolstenholme
(2003),
Thompson
et al. (1985)
Vickerman
et al. (1989)
No chemical state ID
No chemical structure
No organic analyses
Only a lateral resolution of
~ 1 mm
The chemical composition of
PS can change during ion
beam (RBS) analysis
While it is very sensitive for
heavy elements (ppm), it
has a low sensitivity for light
elements
Kimura (2006)
465
Table 2 Compositional analysis contributing to PL mechanism elucidation

Type of PS
Asprepared
Investigation
techniques
XPS
AES
SIMS
RBS
Passivated
surface PS
EDX
XPS
AES
RBS
Oxidized
PS
XPS
AES
SIMS
RBS
Motivation for using technique

The presence of a multiphase system,
amorphous and crystalline, directly
evidenced by XPS, is responsible for
visible PL
The electron structure of the chemical
bonds and defects that might influence PL,
like the oxygen role
Composition of the silicon surface during
porosification in fluorohydrogenate ionic
liquids
Thickness of thin films and elemental
composition (quantitative AES)
The presence of H and H2 bonds on the Si
surface atoms; the character of the confined
energy states in PS vs. crystalline silicon
Reveals that some oxidation occurs as part
of the etching process or as a result of
exposure to atmospheric oxygen
PS porosity beam effect strongly depends
on the porosity of the sample
The porosity profile of the PS multilayer
structure five low/high porosity bilayers
Detailed information on the nature of the
surfaces, the extended defects, the amount
of hydrogen passivation, and their
oxidation state
The effect of plasma fluorination used for
surface passivation on PL tuning of
optical and dielectric properties
Quantitative depth profiling of the Si, O, N,
and S elements concentration distribution
The existence of Si, O, and C has been
evidentiated in different PS samples, which
is consistent with the XPS results
Study the various oxidation states present
before and after aging of PS and the effect
upon the optical properties
Fraction of oxidized layer (SiO2 present)
over the cross section of PS samples induced
by electrochemical oxidation in H2SO4
Comparison of SiO2/Si (bulk) and SiO2/PS
interfaces shows characteristic oxygen
depletion in the last case after thermal
oxidation
Refractive index change and the PL blue
shift observed are explained as features of
aging-induced oxidation
Ref.
Perez
et al. (1992)
Domashevskaya
et al. (1998)
Raz et al. (2010)
Galiy
et al. (1998)
Dorigoni
et al. (1996)
Collins
et al. (1992)
Kotai
et al. (2000)
Torres-Costa
et al. (2004)
Yu et al. (2005)
Pan et al. (2004)
Xiong
et al. (2001)
Feng
et al. (2006)
Thogersen
et al. (2012)
Salem
et al. (2006)
Cwil
et al. (2006)
Beresna
et al. (2007)
PS modification
RBS
Lanthanide-doped mesoPS
Er, Fe ions incorporated in PS
Infrared PL of Er-doped PS
Impregnation with different
elements (Ni, Cu, Au, Pt, In, Fe)
Compact low resistivity silicide
contacts on Si
Long-time stabilization of CHxmodified PS PL properties

Thin metallic layer analyses
SIMS
Metal (Ag, Cu, Au) deposition
Passivated luminescent PS based on

organic monolayers covalently
attached
Selenization treatment
Ultrathin metallic films (Au/Ti/Ni

thermal evaporation, Ti electron
beam evaporation)
Electroplated PS with Fe and Co; Fe,
Co, and Ni galvanic deposition from
sulfate salts
XPS
Optoelectronics
AES
Analysis
Applications
Henley et al. (2000), Herino (2000),

Ramos et al. (2000)
Mahmoudi et al. (2007), Stewart and

Buriak (2001), Kleps et al. (2000),
Gaponenko (2001), Bondarenko
et al. (2003)
Vdovenkova et al. (1997, 1999),

Hamadache et al. (2003),
Domashevskaya et al. (2012)
Reference
Boukherroub et al. (2001), Lin
et al. (2011), Hong et al. (2010), Harraz
et al. (2002)
Results and comments

Control of different organic molecules (alkenes and
nonconjugated dienes) attachment process to the surface
through Si-C bonds
Passivation and origin of the PL intensity enhancement
achieved by Se bonding on Si surface
Clarify the reaction mechanism and quantify the metal
deposition; PL enhancement by Au film deposition is
attributed to the oxidation inhibiting effect of the Au film
Chemical composition and electronic structure (electron
concentration in the conduction band close to the surface
of PS and at Si-Ti Si-Au interfaces)
The particle size was calculated using static dielectric
constant;
Chemical composition of PS surface and layer depth
profile; modifications of line shapes evidence metal
reaction
Surface passivation by coating with CHx layer or Lewis
acid-mediated hydrosilylation
Penetration of the metallic layer into the PS pores and
effect on EL
Optical activation of lanthanides within the whole area
Analysis of in-depth Er and Fe concentrations
The Er depth distribution in the PS is not influenced by
annealing up to 1,000 C, although it strongly influences the
oxygen content of the Si skeleton and the Er IR PL intensity
The deposition homogeneity through the whole thickness
of the layer and the effect on the PS optical properties
Table 3 Utilization of the compositional analysis for novel applications development
466
Biomedicine
Energy
Sensors
PS particles for drug delivery
Pt incorporation within the calcium

phosphate layers on PS
SIMS
Functionalization with catalysts
Photoelectrochemical system for

water splitting
NO gas sensor based on PS

Electrocatalytic activity of metalporous Si nanoassemblies
PS surface passivation for crystalline
Si solar cell
PS nanostructures as hydrogen
reservoirs
EDX
SIMS
XPS
RBS
EDX
Surface functionalization by alkynes

and alkenes
SIMS
DNA hybridization sensing
PS surface functionalization with

organic layers for biosensing
EDX
XPS
Clarifies that the amount of hydrogen produced by Si-H

bond reaction with OH is limited by the Si-O and Si-F
bonds formed during electrochemical etching
Predicts the treatments necessary to accelerate the
photooxidation of nano-silicon by water for hydrogen
production
PS matrix impregnated with transition metal-mediated
dehydrogenate silanes (zirconocene and titanocene)
Calibration of impregnation process of PS particles with
Fe2O3
Diffusion studies of Pt complex-based antitumor
compounds
XPS confirms the preliminary functionalization steps and

presence of thick protein film covering the PSi surface
Mechanism of grafting PEG monolayers; optimization of
silane deposition and further surface modification with
aldehyde and PEG
Presence of reactive functional groups grafted on the PS
surface (amine from APTS molecules or carboxylic
functions from acrylic acid)
Monitorization of Lewis acid-mediated hydrosilylation,
consistent surface functionalization down the length of the
pore
Using mesoPS for in situ synthesis significantly increases
the quantity of DNA probes attached
Study of DC-sputtered Au distribution in the pores
EDX confirms the presence and the uniformity
distribution of Pt particles on/into PS layers
Finding of an efficient surface passivation of a PS surface
Kleps et al. (2010), Li et al. (2000)
Miu et al. (2010), Bilyalov et al. (2000),

Zhan et al. (2011), Bahruji et al. (2009),
Li and Buriak (2006)
Jia et al. (2010), Guo et al. (2009),

Arroyo-Hernandeza et al. (2003),
Fang et al. (2006), Buriak et al. (1999),
Lawrie et al. (2009), Baratto
et al. (2000)

467
468
spectroscopy (XPS), Auger electron spectroscopy (AES) on one hand, and secondary
ion mass spectroscopy (SIMS) and Rutherford backscattering spectroscopy (RBS) on
the other hand have been generally used to analyze the porous layers, mainly to
determine their compositional profile. Each of them has advantages and disadvantages which represent critical factors in deciding the most appropriate one for
achieving the information of interest and are briefly presented in Table 1.
Chemical Composition of Electrochemically Etched Porous Silicon

The as-prepared PS layers were firstly investigated with these complementary
methods in order to achieve a complete image of the large internal area chemical
map where about 20 % of the silicon atoms are located, looking forward to
accomplish a general model for porosification process and also a mechanism for
the most renowned property of this material, photoluminescence (see chapter
Photoluminescence of Porous Silicon). Table 2 provides example of the
compositional studies of freshly prepared and passivated/oxidized PS.
While the associated analyses have been dedicated mainly to understand the role
of the surface states on PL, including the time instability, and to find physicalchemical methods for stabilization and/or enhancement, the extension of the application areas towards nanocomposites and the attachment of complex molecules has
given more importance to these methods (see, e.g., chapters Ferromagnetism
and Ferromagnetic Silicon Nanocomposites, Porous Silicon Optical Biosensors, Porous Silicon Immunoaffinity Microarrays).
Table 3 contains examples of applications where the corresponding assay analysis methods represented a key process to certify formation of more complex
structures on the surface through both introduction of functional groups and
implantation/deposition of metallic ions and the consequent development of hybrid
devices based on the PS matrix. It is notable that the compositional analyses
performed to study the surface oxidation process and its influence on the luminescence properties demonstrated also the higher chemical reactivity of the PS layers
possessing higher porosity, mainly because higher porosity means a larger internal
surface.
Acknowledgements The authors thank M. Simion, A. Bragaru, and T. Ignat for assistance in
conducting literature searches and L. Canham for valuable suggestions.
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Infrared Spectroscopy
Yukio H. Ogata
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sample Preparation and Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrogen-Terminated Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxidation of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
IR Measurement Using Methods Other Than the Transmission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
474
474
474
475
476
478
478
Abstract
The surface of electrochemically etched porous silicon is passivated with hydrogen just after preparation. The surface is gradually oxidized under ambient
atmosphere, and the rate depends upon the ambient condition. The chemical
and physical changes affect the properties of porous silicon-based devices.
Proper understanding of the surface is important, and infrared (IR) spectroscopy
is an effective and easy tool for monitoring and/or characterizing the surface
state. Silicon is almost transparent to IR light, and hence the convenient transmission measurement is applicable to films and membranes of porous silicon.
The measurement technique is first described, and then assignments of absorption bands in the spectra are given for the hydrogen-terminated and oxidized
surface. The prevention of oxidation and the functionalization of porous silicon
surface are important for many practical uses, where IR measurements can be
used to monitor the surface. In addition, methods other than the transmission
mode are briefly introduced.
Y.H. Ogata (*)

Institute of Advanced Energy, Kyoto University, Uji, Kyoto, Japan
e-mail: ogata.yukio.34m@st.kyoto-u.ac.jp
DOI 10.1007/978-3-319-05744-6_48
473
474
Y.H. Ogata
Introduction
A silicon surface is stabilized with hydrogen termination with the hydrofluoric acid
(HF) treatment or during the porosification in solution containing fluoride (Trucks
et al. 1990; Searson and Zhang 1990; Gerischer et al. 1993). The surface states,
SiHx, influence the properties. The passivated surface undergoes oxidation on putting
it in an environment, where some oxidants are present; the oxidation rate depends
upon the type of oxidant or the oxidizing ability. The oxidation also affects the
properties. Silicon surface is often modified with organic species in order to stabilize
the surface against its oxidation and more to give new functionality (Sailor 2011).
Understanding of these chemical states of the silicon surface is indispensable for the
study on porous silicon. There are many analytical methods to access the chemical
information. Among them, infrared spectroscopy (IR) is a powerful tool to analyze
the atomic bonding in a molecule (Gunzler and Gremlich 2002; Tolstoy et al. 2003;
Settle 1997; Stuart 2004) and is widely used. In this chapter, only basic IR response of
porous silicon itself is described, but the technique is widely utilized in such as
characterization/quantification of materials loaded in pores like proteins or drug
molecules, special inhomogeneity, oxide nature, free carrier concentrations, and
degree of derivatization. The reader may find some examples in the other chapters.
Sample Preparation and Instrumentation

IR measurement is usually based on the transmission mode. It is the easiest way of
the measurement. Silicon is almost transparent against infrared light, whereas it
absorbs visible light to some extent. Moderately or lightly doped silicon enables the
transmission measurement of a porous silicon layer. Porous silicon has a large
surface area (Herino et al. 1987), and the transmission IR provides a good quality of
the spectrum. A silicon wafer after dipping in dilute HF can be used as the reference
for the IR measurement. Highly doped silicon or degenerate silicon (n+ or p+ Si)
exhibits some absorption, especially at high-frequency region due to the high
impurity concentration. Even in the case, the transmission IR becomes possible if
the layer is detached from the substrate by applying high current after formation of
a porous silicon layer and the free-standing porous silicon layer is measured.
These days, almost all IR measurement uses Fourier transform IR (FTIR), which
is superior to the dispersive IR in the sensitivity, sampling time, and resolution.
Measurable wavenumber region depends upon the detector used: the most popular
detectors are TGS (triglycine sulfate), 3507,800 cm1, and semiconductor-type
detector MCT (HgCdTe), the low detection limit around 650 cm1.
Hydrogen-Terminated Porous Silicon

Silicon is tetravalent, and the crystal has a tetrahedral structure. Hydrogen molecules can bond with silicon in the crystal as SiHx (x 13). An example of the
spectra prepared from p-type silicon (100) is shown in Fig. 1a. Three absorption
Characterization of Porous Silicon by Infrared Spectroscopy
b
p-Si (100) PS oxidized
p-Si (100) PS as-prepared
SiHxstr
Absorbance
SiH2, SiH
deform
Absorbance
475
SiH2 scis
Meas.
Si-O-Si
Si-O-Si
OnSi-Hx
Cal.
2500
2000
1500
1000
Wavenumber / cm1
500
2500
2000
1500
1000
500
Wavenumber / cm1
Fig. 1 IR spectra of porous silicon prepared from p-type silicon (100): (a) as prepared and the
results of vibrational analysis by the molecular orbital calculation, (b) oxidized in dry air at 333 K
for 50 days
bands are clearly observed in three frequency regions: 2,0902,150 cm1, ~920
cm1, and 620700 cm1. A broad band in the 1,0001,300 cm1 region is
sometimes found in some spectra. This is caused by post-oxidation during the
sample drying procedure. The peak assignment had been performed comparing
with the spectra of the related materials, amorphous hydrogenated silicon (a-Si:H)
(Lucovsky et al. 1979; Knights et al. 1978) and HF-treated silicon (Burrows
et al. 1988; Chabal and Raghavachari 1984). Porous silicon and a-Si:H resemble
with each other except the crystallinity. Their FTIR spectra are basically similar.
HF-treated silicon is of course monocrystalline and measured by the reflection method.
The spectrum is exactly that of porous silicon. The only difference between them is the
azimuth. The monocrystalline surface is uni-oriented, and the orientation gives different
spectra between p and s polarizations when the incident beam is polarized. Pores in
microporous silicon are randomly oriented, and the polarized beam gives similar spectra.
On the one hand, mesoporous silicon with a few branching and macroporous silicon are
expected to show the difference when using differently polarized incident beam.
The assignment of the absorption bands appearing in porous silicon is investigated experimentally and theoretically (Unagami 1980a; Gupta et al. 1988; Kato
et al. 1988; Ito et al. 1990; Ogata et al. 1995a, 1998; Gupta et al. 1991). The
theoretical or computational analyses such as ab initio molecular orbital calculation
can be the powerful tool for the assignment. An assignment of the vibration modes
is given in Table 1. The exact values of wavenumbers vary depending upon the
measurements, and hence, the small variations should not be reproachable.
Oxidation of Porous Silicon

Silicon is a very less noble element, and it is prone to be oxidized under ambient
atmosphere. The oxidation can be easily followed by FTIR (Kato et al. 1988; Gupta
et al. 1991; Unagami 1980b; Borghesi et al. 1994; Ogata et al. 1995b;
476
Y.H. Ogata
Table 1 Absorption bands appearing in as-prepared porous silicon

Wavenumber
(cm1)
2,142
2,108
2,087
916
667
626
Assignment
SiH3
stretching
SiH2
stretching
SiH stretching
SiH2 scissors
bending
SiH2 wagging
SiH bending
Remark
Dimer (SiH2)n bending also

participates
References
Kato et al. (1988), Ogata
et al. (1995a)
et al. (1995a)
et al. (1995a)
Gupta et al. (1988), Ogata
et al. (1995a)
Ogata et al. (1998)
Ogata et al. (1998)
Lucovsky 1979). Figure 1b gives an IR spectrum undergoing oxidation (Ogata

et al. 1995b). Many absorption bands appear due to the oxidation, and SiHx-related
bands still remain in some cases. The oxidation rate depends on the surrounding
environment. The sample put in dry air at ambient temperature is fairly stable
against oxidation, while the oxidation proceeds quite fast in saturated humidity
atmosphere and at high temperature (Ogata et al. 1995b). The possible assignment
to the vibrational modes is given in Table 2. The features are classified into three
frequency regions: (a) a broad absorption around 3,600 cm1 resulting from the
O-H stretching vibrations, (b) absorptions slightly higher than the SiHx stretching
(2,0802,150 cm1) attributed to the back-bond oxidation, and (c) a strongest
absorption at 1,0001,200 cm1 and many absorptions lower than 1,000 cm1
caused by Si-O-Si and deformational vibrations related to OnSiHx. Theoretical
calculation helps the assignment (Kato et al. 1988; Ogata et al. 1995b; Lucovsky
1979; Lucovsky et al. 1983) but partially. The assignment of vibrational modes
becomes complicated because many species are possible and the unoxidized SiHx
states remain. Some vibrations of OnSiHx, especially the deformational modes
appearing in the frequency lower than 1,000 cm1, are difficult to be assigned
with the computational analysis because of the presence of many modes and the
coupling. Some experimental verification is always necessary for the assignment.
IR Measurement Using Methods Other Than the Transmission

The surface of porous silicon is often modified with some materials in order to
stabilize it against oxidation or to give a new functionality (Sailor 2011; Buriak
2002; Boukherroub et al. 2002; Salonen et al. 2002). Modification with organic
materials is followed by FTIR. Porous silicon has a huge surface area, and the high
surface area enables a very high sensitivity of the adsorbed molecules on the
surface. It must be noted that the surface is sometimes involuntarily oxidized.
The FTIR can be performed using a porous layer formed on a silicon substrate
477
Table 2 Absorption bands appearing in oxidized porous silicon (except SiHx relating vibrations)
Wavenumber
(cm1)
3,660
3,600
2,256
Assignment
O-H
stretching
O-H
stretching
O3Si-H
stretching
2,200
O2Si-H2
stretching
2,160
OSi-H3
stretching
1,050
Si-O-Si
stretching
OnSiHx
deformation
870
800
708
470
OnSiHx
deformation
OnSiHx
deformation
Si-O-Si outof-plane
rocking
Remark
Sharp peak from an isolated
hydroxyl group
Broad absorption from
physisorbed water
Broad absorption with a

shoulder at 984 cm1
Si-O-Si symmetric stretching is
also possible in the region
700900 cm1
References
Gupta et al. (1991),

Borghesi et a. (1994),
Ogata et al. (1995b)
Borghesi et al. (1994),
Borghesi et al. (1994),
Lucovsky et al. (1983)
with the transmission mode and also the pulverized sample. For the latter, the
pulverized sample is mixed with KBr and then pressurized to make a pellet. The
diffused light is analyzed (diffuse reflectance FTIR). The absorption bands appear
in the same frequencies as the transmission spectroscopy, but the intensity is
different because of the difference in the optical path. The qualitative comparison
with the transmission spectroscopy needs the conversion with the use of the
Kubelka-Munk function.
The attenuated total reflection (ATR) is used to analyze the state of the very
surface collecting the evanescent light. This method uses a tight contact of the
sample with a prism with high refractive index such as ZnSe and KRS-5 (mixed
crystal of TlI and TlBr). The use of silicon replacing the prism for the ATR enables
the multiple internal reflection infrared spectroscopy (MIR-FTIR) (Rao et al. 1991;
Kimura et al. 2001). Two edges of a silicon sample are beveled with 45 and
polished. IR beam comes into the sample from the beveled edge and goes out to an
FTIR analyzer from the other edge after multiple reflections at the both surfaces.
The top surface is exposed to an electrolyte, and the spectrum provides the in situ
and almost instantaneous information of the surface. The method has been effectively utilized for the investigation of temporal change on silicon or porous silicon,
478
Y.H. Ogata
Table 3 Porous silicon-related absorption bands other than Si-H and Si-O
Wavenumber
(cm1)
2,8502,950
870
Assignment
Adventitious carbon
contamination from ambient
air
Si-Nx bending
812
770
Si-Fx stretching
Si-CHx stretching or rocking
680
610
Si-C stretching
Si-Si lattice vibration
Remark
Appearing in
aged sample
References
Observed
using
ATR-FTIR
Very weak
James et al. (2010)
TO + TA
combination
Ogata et al. (1995a)

Salonen et al. (2002),
Canaria et al. (2002)
Canaria et al. (2002)
Ogata et al. (1995a),
Johnson and Loudon
(1964)
such as the early stage of the porosification (Kimura et al. 2001) and the surface
change during the potential or current oscillation during anodic polarization
(Chazalviel et al. 1998; Kimura et al. 2003).
Finally, it may be useful to give some IR absorption bands found in porous
silicon other than listed in Tables 1 and 2 (Table 3).
Conclusion
IR is a powerful and easy-to-use technique to obtain the surface chemical state of
porous silicon. The convenience results from the transparency of silicon for IR light
and the high surface area. The basic features begin from the knowledge of the
bondings to hydrogen, Si-H, and to oxygen Si-O. The model calculations sometimes provide useful information in the assignment. It is true for the stretching
vibrations, which are isolated and appear in the frequency region of 2,0502,300
cm1, while vibrational modes appearing at the low frequencies attributed to the
deformational modes are often coupled and crowded, and hence the theoretical
analysis is often difficult. Additional experimental work often helps the assignment.
The assignment still remains some discussion, but the major understanding had
been achieved in the last century.
References
Borghesi A, Guizzetti G, Sassella A et al (1994) Induction-model analysis of Si-H stretching mode
in porous silicon. Solid State Commun 89:615618
Boukherroub R, Wojtyk J, Wayner D et al (2002) Thermal hydrosilylation of undecylenic acid
with porous silicon. J Electrochem Soc 149:H59H63
479
Buriak J (2002) Organometallic chemistry on silicon and germanium surfaces. Chem Rev
102:12711308
Burrows V, Chabal Y, Higashi G et al (1988) Infrared-spectroscopy of Si(111) surfaces after HF
treatment hydrogen termination and surface-morphology. Appl Phys Lett 53:9981000
Canaria C, Lees I, Wun A et al (2002) Characterization of the carbon-silicon stretch in methylated
porous silicon observation of an anomalous isotope shift in the FTIR spectrum. Inorg Chem
Commun 5:560564
Chabal Y, Raghavachari K (1984) Surface infrared study of Si(100)-(2x1)H. Phys Rev Lett
53:282285
Chazalviel J, da Fonseca C, Ozanam F (1998) In situ infrared study of the oscillating anodic
dissolution of silicon in fluoride electrolytes. J Electrochem Soc 145:964973
Gerischer H, Allongue P, Kieling V (1993) The mechanism of the anodic-oxidation of silicon in
acidic fluoride solutions revisited. Ber Bunsen-Ges Phys Chem 97:753756
Gunzler H, Gremlich H-U (2002) IR spectroscopy: an introduction. Wiley-VCH, Weinheim
Gupta P, Colvin V, George S (1988) Hydrogen desorption-kinetics from monohydride and
dihydride species on silicon surfaces. Phys Rev B 37:82348243
Gupta P, Dillon A, Bracker A et al (1991) FTIR studies of H2O and D2O decomposition on porous
silicon surfaces. Surf Sci 245:360372
Herino R, Bomchil G, Barla K et al (1987) Porosity and pore-size distributions of porous silicon
layers. J Electrochem Soc 134:19942000
Ito T, Yasumatsu T, Watabe H et al (1990) Effects of hydrogen-atoms on passivation and growth
of microcrystalline Si. MRS Symp Proc 164:205210
James TD, Parish G, Musca CA et al (2010) N2-Based thermal passivation of porous silicon to
achieve long-term optical stability. Electrochem Solid-State Lett 13:H428H431
Johnson F, Loudon R (1964) Critical-point analysis of phonon spectra of diamond silicon and
germanium. Proc R Soc Lond A 281:274290
Kato Y, Ito T, Hiraki A (1988) Initial oxidation process of anodized porous silicon with hydrogenatoms chemisorbed on the inner surface. Jpn J Appl Phys 27:L1406L1409
Kimura Y, Kondo Y, Niwano M (2001) Initial stages of porous Si formation on Si surfaces
investigated by infrared spectroscopy. Appl Surf Sci 175:157162
Kimura Y, Nemoto J, Shinohara M et al (2003) In-situ observation of chemical states of a Si
electrode surface during a galvanostatic oscillation in fluoride electrolytes using infrared
absorption spectroscopy. Phys Status Solidi A 197:577581
Knights J, Lucovsky G, Nemanich R (1978) Hydrogen-bonding in silicon-hydrogen alloys. Phil
Mag B 37:467475
Lucovsky G (1979) Chemical effects on the frequencies of Si-H vibrations in amorphous solids.
Lucovsky G, Nemanich R, Knights J (1979) Structural interpretation of the vibrational-spectra of
a-Si:H alloys. Phys Rev B 19:20642073
Lucovsky G, Yang J, Chao S et al (1983) Oxygen-bonding environments in glow-discharge
deposited amorphous silicon-hydrogen alloy-films. Phys Rev B 28:32253233
Ogata Y, Niki H, Sakka T et al (1995a) Hydrogen in porous silicon - vibrational analysis of SiHx
species. J Electrochem Soc 142:195201
Ogata Y, Niki H, Sakka T et al (1995b) Oxidation of porous silicon under water-vapor environment. J Electrochem Soc 142:15951601
Ogata Y, Kato F, Tsuboi T et al (1998) Changes in the environment of hydrogen in porous silicon
with thermal annealing. J Electrochem Soc 145:24392444
Rao A, Ozanam F, Chazalviel J (1991) Insitu Fourier-transform electromodulated infrared study of
porous silicon formation - evidence for solvent effects on the vibrational linewidths.
Sailor MJ (2011) Porous silicon in practice. Wiley-VCH, Weinheim
acetylene. J Appl Phys 91:456461
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Searson P, Zhang X (1990) The anodic-dissolution of silicon in HF solutions. J Electrochem Soc

137:25392546
Settle F (1997) Handbook of instrumental techniques for analytical chemistry. Prentice Hall,
Upper Saddle River
Stuart BH (2004) Infrared spectroscopy: fundamentals and applications. Wiley, Hoboken
Tolstoy VP, Chernyshova I, Skryshevsky VA (2003) Handbook of infrared spectroscopy of ultra
thin films. Wiley-VCH, New York
Trucks G, Raghavachari K, Higashi G et al (1990) Mechanism of HF etching of silicon surfaces a
theoretical understanding of hydrogen passivation. Phys Rev Lett 65:504507
Unagami T (1980a) Formation mechanism of porous silicon layer by anodization in HF solution.
Unagami T (1980b) Oxidation of porous silicon and properties of its oxide film. Jpn J Appl Phys
19:231241
Cell Culture on Porous Silicon

Nicolas H. Voelcker and Suet P. Low
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Early Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Surface Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Topography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Gradients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
481
482
483
488
490
493
493
Abstract
Cell culture is a powerful in vitro characterization technique to optimize the

properties of a biomaterial for in vivo biomedical use by conversely revealing
potential sources of cytotoxicity. A comprehensive literature survey of the range
of cell types cultured on porous silicon is given, together with a discussion of
how surface chemistry, topography, and porosity gradients affect cell behavior.
Introduction
Cell culture is often utilized to determine the biocompatibility of materials and
precedes or even replaces in vivo animal and human testing. The behaviour of cells
such as attachment, proliferation, morphological changes, metabolic changes, cytotoxicity, protein expression, and RNA expression are all important factors that have
to be taken into account when designing a biomaterial (Freshney 2005; Masters
2000). In this regard, many materials are being investigated for their suitability for
N.H. Voelcker (*) S.P. Low

Mawson Institute, University of South Australia, Adelaide, SA, Australia
e-mail: nico.voelcker@unisa.edu.au
DOI 10.1007/978-3-319-05744-6_50
481
482
N.H. Voelcker and S.P. Low
Fig. 1 Cells being cultured on porous silicon particles that have been compressed into a disk form
as part of a cell delivery platform (Low 2008)
the culture of cells or even to study cellular interactions. Porous silicon is a popular
choice for biosensor, bio-microelectromechanical systems (bioMEMS), biomaterials and tissue engineering applications. The porous structure, degradability, electrical conductivity, overall biocompatibility (see chapter Biocompatibility of
Porous Silicon), and ease of surface modification make this a fascinating platform
to investigate cell culture interactions. For example, porous silicon disks are being
developed for delivery of therapeutic ocular cells (Fig. 1).
Early Studies
A variety of mammalian cells have been successfully cultured onto porous silicon
surfaces. The first publications on this topic by Bayliss et al. demonstrated that
attachment of Chinese hamster ovary (CHO) cells proceeded on porous silicon
surfaces to a similar extent as on bulk silicon (Bayliss et al. 1997a, b). This was also
confirmed with the neuronal cell line B50 (Bayliss et al. 2000). Cell viability in
these studies was determined using two colorimetric assays, the MTT based on
enzymatic reduction of a tetrazolium salt to a purple formazan and the neutral red
uptake assay. B50 and CHO cells were cultured on bulk silicon, porous silicon,
glass, and polycrystalline silicon. Both viability assays suggested that the neuronal
cells showed preference for porous silicon above the other surfaces, while CHO
cells showed the lowest viability on the porous silicon surface (Bayliss et al. 1999,
2000). The surfaces of the porous silicon used in these early studies were not
modified post-etching, and it was not until a study utilized porous silicon surfaces
with an oxide layer for cell culture that surface chemistry was found to play a
crucial factor (Chin et al. 2001). Rat hepatocytes were cultured onto ozone-oxidized
porous silicon that was further modified by fetal bovine serum and collagen type I
coating. Here, the hepatocytes showed a preference for the collagen-coated surface
(Chin et al. 2001).
Viability assays such as MTT, XTT, MTS, or Alamar Blue are commonly used
to determine the suitability of a material as a support for the attachment and growth
of cells. These assays are based on the reduction of the tetrazolium dyes by cellular
enzymes to formazan dyes with characteristic color. In 2006, it has come to light
483
that porous silicon, even with an oxide layer, interferes with these assays by
reducing tetrazolium dyes (Laaksonen et al. 2007; Low et al. 2006). Passivating
the surface against hydrolytic attack reduces but does not completely remove the
interfering behavior (Laaksonen et al. 2007). Dye uptake viability assays such as
neutral red which make use of the ability of viable cells to incorporate the dye in the
lysosomes were found to be not compatible with porous silicon either, since the
neutral red dye can also ingress into the porous layer (Low et al. 2006). These
findings suggest that viability assays for cells in contact with porous silicon need to
be carefully evaluated for compatibility.
Surface Modification
Surface modification of porous silicon has been used to protect the surface against
hydrolytic attack in aqueous medium and stabilize or slow down surface degradation. It can also be used to promote or prevent mammalian cell adhesion (Low
et al. 2006; Faucheux et al. 2004). The changes in surface chemistry have long been
known to affect the attachment and proliferation of anchorage-dependent mammalian cells on materials featuring otherwise almost identical topography, where cell
attachment can be inhibited on very hydrophobic or hydrophilic surfaces (Groth
and Altankov 1996; Yanagisawa et al. 1989). This has been mainly attributed to the
amount of serum proteins (containing attachment factors) that is pre-adsorbed to the
surface (Faucheux et al. 2004), which in turn can mediate cell attachment (Webb
et al. 2000).
Freshly etched porous silicon (SiH) is rather hydrophobic, whereas ozoneoxidized surface (SiOH) is very hydrophilic. Attachment of proteins in cell culture
medium has been known to bind to moderately hydrophilic surfaces, leading to
greater cell attachment on those surfaces (Webb et al. 1998). Water contact angles,
qualitatively describing surface wettability for freshly etched and surface-modified
porous silicon surfaces, are shown in the table below (Table 1).
Arguably, the simplest method to stabilize the porous silicon surface is oxidation. A popular technique is to use ozone to rapidly generate a SiOH capped
surface with a thin oxide layer. Alternatively, thermal treatment in air (400800 C)
is used to generate thicker oxide layers (Pap et al. 2004). Surface hydroxyl groups
Table 1 Sessile drop water contact angle measurements for unmodified and surface-modified
porous silicon etched under the same conditions (Low et al. 2006)
Surface modification of porous silicon
Freshly etched
Amino silanized
Collagen coated
Polyethylene glycol silanized
Fetal bovine serum coated
Ozone oxidized
Contact angle
>99
56
32
26
10
<5
SD
3
3
8
2
1
1
484
can be further reacted with silanes, which can further stabilize the surface against
hydrolytic attack, as well as provide a means of attaching functional groups to the
surface. Alternatively, in hydrosilylation initiated through thermal or UV pathways,
the SiH moieties on the freshly etched surface are reacted with alkenes and
alkynes to generate SiC bonds (Buriak and Allen (1998) and chapter SiliconCarbon Bond Formation on Porous Silicon). To provide a high degree of protection against hydrolytic attack, thermal carbonization of the porous silicon surface to
form SiC has shown to offer considerable stability (Salonen et al. 2004, 2000).
Electrografting has emerged as a new method for porous silicon surface modification where organohalides or alkynes are electrochemically reduced on the freshly
etched porous silicon surface generating SiC bonds (Thompson et al. 2010). This
technique has proven particularly useful in the generation of chemical gradients, as
will be discussed later (Thompson et al. 2010; Clements et al. 2011).
Comparing different surface treatments in cell culture, we have studied the
attachment of rat pheochromocytoma (PC12) cells and human lens epithelial cells
(HLE) onto freshly etched, ozone-oxidized, amino-silanized, fetal bovine serumcoated, collagen-coated, and polyethylene glycol-silanized porous silicon surfaces
(Low et al. 2006). In the case of PC12 cells (Fig. 2), the greatest extend of cell
attachment was recorded on the collagen-coated porous silicon, followed by the
amino-silanized surface after 24 h in culture. In contrast, a greater number of HLE
cells were found on the amino-silanized surface. Both cell lines gave low cell
attachment on the ozone-oxidized and polyethylene glycol-silanized surface.
These results indicate that wettability alone is not the sole determinant of
Fig. 2 Difference in the morphology of cells cultured on various surface-modified porous silicon.
Top panel: PC12 cells cultured on (A) freshly etched porous silicon, (B) oxidized porous silicon,
and (C) amino-silanized surface (Low et al. 2006). Bottom panel: CHO cells cultured on (a)
oxidized porous silicon, (b) fluoro-silanized surface, and (c) amino-silanized surface (Yang
et al. 2010)
485
propensity for cell attachment. The moderately hydrophilic polyethylene glycol

chains prevent protein adsorption to the surface, thus preventing cells to attach via
mechanisms involving volume exclusion effects preventing protein attachment
(Alcantar et al. 2000; Cole et al. 2007).
A similar study compared the effects of a fluorinated surface on the attachment
of Chinese hamster ovary (CHO) cells. Cell attachment and morphology on this
surface was compared with oxidized and amine-presenting surfaces. The fluorine
surface was extremely hydrophobic with an average contact angle of 148 , while
the oxidized and amine surface had similar contact angles of 1 and 2 , respectively. They found that on the porous silicon surface, the morphology of cells
remained rounded, and the cells did not spread (Fig. 1), for both the oxidized and
fluorine surfaces; in contrast, the amine surface displayed cells that had spread and
formed strong focal adhesions (Yang et al. 2010). The surface charge produced by
the reactive amine groups is known to mediate attachment of proteins such as
vitronectin (Faucheux et al. 2004). This again shows that wettability alone does not
govern cell attachment.
Another study utilized hydrosilylation to form surfaces with undecanoic acid-,
dodecyl-, and oligo(ethylene glycol)-terminated surfaces (Alvarez et al. 2009).
Compared against an ozone-oxidized surface, the dodecyl surface was the most
hydrophobic, followed by the oligo(ethylene) glycol functionalized surface and the
undecanoic acid functionalized surface. Ozone oxidation generated the most hydrophilic surface. Primary rat hepatocytes were cultured on these surfaces for 24 h. It
was observed that the most hydrophobic surface, the dodecyl-terminated surface,
had the lowest number of cells attached. The oligo(ethylene) glycol also demonstrated low cell attachment, again most likely to volume exclusion effects of the
ethylene glycol strands preventing protein attachment. The undecanoic acidterminated surface and the ozone-oxidized porous silicon showed the best cell
attachment out of all the modified samples. The observation of good cell attachment
to the ozone-oxidized surface was in stark contrast to the earlier study with PC12
and HLE cells, suggesting the strong influence of cell type on attachment behavior.
The ability to chemically modify the surface to modulate cell attachment and
growth has inspired the utilization of patterning for cell screening studies. For
example, UV-initiated hydrosilylation was used to conjugate the protein fibronectin
to selected areas on the porous silicon surface. A secondary hydrosilylation of a
PEG alkene onto the remainder of the surface prevented nonspecific binding of
proteins in these regions. Neuroblastoma cells were successfully cultured within the
fibronectin-patterned areas of the surface. Such patterning strategies enable applications in cell microarrays or in culture systems where the porous silicon can
locally deliver bioactive molecules to the cells (Sweetman et al. 2012).
A comprehensive list of studies involving cells cultured on porous silicon is
shown in Table 2. It is apparent from this body of work that the functionality
presented on the porous silicon surface can moderate the behavior of attached cells,
including viability and morphology.
486
Table 2 List of cells cultured on porous silicon with different surface modifications and a
summary of the findings of these studies
Surface
modification
Untreated
Cell types
B50 hippocampal cells
(rat)
Primary mesenchymal
stromal cells (mouse)
Sciatic nerve tissue and

cells (rat)
Thermally
oxidized
Cancer cell lines:

Glioma U87, MDA-MB231
HeLA (human)
Human umbilical vein

endothelial cells
(HUVEC), mouse embryo
fibroblasts (3 T3-L1), and
human primary
neutrophils
Oxidized by
aging in
aqueous medium
Rat mesenchymal stem

cells (rMSC)
Outcome
Cells attached
preferentially to porous
surfaces
Porous silicon generated
by dry etching in XeF2.
Cells show good viability
on the porous silicon
surface
Implanted into the sciatic
nerve, neuronal tissue grew
preferentially on the
porous silicon in
comparison to flat silicon.
Especially when pore sizes
were within the diameter
range of 150500 nm
Cancer cell lines
proliferate and remain
viable on porous silicon
with pore sizes of <30 nm,
50 nm, 80 nm, and 110 nm.
Viability and growth
comparable to TCPS
Attachment of HUVEC
and 3 T3 to the porous
silicon membranes was
comparable to TCPS and
glass. Neutrophils
successfully used in
coculture using the porous
silicon membrane as a
divider
Porous silicon patterned
stripes were aged in PBS
to form SiOH surface.
rMSC preferentially attach
to flat Si, but straddled
20 m wide porous silicon
stripes with focal adhesion
sites on the flat silicon,
while nuclei remained over
porous area
Sapelkin
et al. (2006)
Hajj-Hassan
et al. (2011)
Johansson
et al. (2008,
2009)
Zeidman
et al. (2011)
Agrawal
et al. (2010)
Noval
et al. (2012)
(continued)
487
Table 2 (continued)
Surface
modification
Ozone oxidized
Silanized
Cell types
Neuronal aplysia (sea
hare)
Primary bone marrowderived dendritic cells

(mouse)
Chinese hamster ovary

cell line (CHO)
Neuroblastoma cell line

(SKNSH) (human)
Thermally
hydrosilylated
Human embryonic kidney

cell line (HEK293)
UV-induced
polymer grafting
Human breast cancer cell

line (MCF-7)
Outcome
Neurons survived on
porous silicon surface and
were able to retain their
action potential properties
Toll-like receptor ligand
conjugated to porous
silicon particles to promote
their cellular uptake.
Higher concentrations of
particles led to lower cell
viability due to increased
number of particles taken
up per cell
The study used plasmaoxidized porous silicon and
porous silicon silanized to
present amine or fluorine
groups and plasmaoxidized porous silicon.
CHO cells attached to the
amine and oxidized
surfaces but not the surface
containing fluorine groups.
Cells displayed rounded
morphology on the
oxidized and fluorinated
surface, but spread and
adhered well on the amine
surface
PEGsilane used to
prevent cell attachment.
UV laser ablation
generated cell-adhesive
regions
Fibronectin covalently
bound to the surface
allowed for cell adhesion
in the absence of serum.
Surface with no bound
protein showed low cell
attachment
Acrylic acid grafted onto
SiH terminated porous
silicon particles via UV
irradiation generated a
hydrophilic surface.
MCF-7 cells took up the
particles with no apparent
morphological changes
Ben-Tabou
de Leon
et al. (2004)
Meraz
et al. (2012)
Yang
et al. (2010)
Khung
et al. (2006)
Sweetman
et al. (2011)
Wang
et al. (2011)
(continued)
488
Table 2 (continued)
Surface
modification
Encapsulated into
polycaprolactone
(PCL)
Encapsulated into
polylactic-coglycolic acid
(PLGA) matrix
Thermally
carbonized
Cell types
Human embryonic kidney
cells (HEK293)
HUVEC
Human epithelial
colorectal
adenocarcinoma cell lines:
Caco-2, HT-29
Human gastric
adenocarcinoma cell line
(CRL-1739)
Macrophage (RAW
264.7) and HepG2 liver
cells
Outcome
Cells remained viable
when cultured with the
PCL sponge
Encapsulated porous
silicon particles not taken
up by cells when
encapsulated in PLGA.
Released drug is taken up
by cells
Hydrophobin Class II
protein conjugated to
porous silicon particles.
Cell viability maintained
and still able to allow drug
permeation from the porous
silicon particle to the cells
Stable in gastric fluid and
hydrophobin coating
allows it to attach to the
gastric cells
Protein-conjugated
particles showed better
biocompatibility with
RAW 264.7 cells than just
thermally hydrocarbonized
particles
Coffer
et al. (2005)
Fan
et al. (2012)
Bimbo
et al. (2012)
Sarparanta
et al. (2012a)
Sarparanta
et al. (2012b)
Topography
The topography of a surface is an influential parameter for the performance of a
biomaterial, particularly in the case of tissue engineering. Cells attach to a surface
via focal adhesion sites that are based on the presence of cellular attachment
proteins and factors (Curtis and Wilkinson 1997). Cell behavior will be heavily
influenced by the dimensions of a surface upon which attachment sites can be
formed and thus dictate the cell shape and migration (Von Recum and Van Kooten
1996). Topographical cues can therefore mediate cell orientation and migration
(Clark et al. 1991), cell differentiation (Schwartz et al. 1996), proliferation (Ito
1999), and protein expression (Chou et al. 1995). For porous silicon, pore size and
porosity are variables that affect topography at the micro- to nanoscale.
489
Meso- and macroporous silicon (Bisi et al. 2000) have been compared in their
ability to support cell attachment and growth. Osteoblasts were found to grow
preferentially on the macroporous surface, which had pore sizes of 1 m. This was
attributed to the wide areas of flat silicon in between the pores for the cells to attach
to. In contrast, the two types of mesoporous silicon, which had pore sizes between
50 nm and 15 nm, respectively, both gave low cell attachment (Sun et al. 2007).
In another study, neuroblastoma, human cortical neuronal cells, 3T3, and human
umbilical vein endothelial (HUVEC) cells were cultured onto two types of
mesoporous silicon with average pore sizes of 5 and 20 nm. Here, the porous
silicon was thermally oxidized but not pretreated to promote cell adhesion. The
four cell types proliferated and grew on the 5 nm porous silicon at a greater rate than
on the 20 nm porous silicon and flat silicon. The cells also displayed rounder
morphology on the silicon control in comparison to the porous silicon surfaces.
Confocal microscopy and Western blots confirmed that vinculin, the protein
involved in cellsurface interactions, was upregulated in cells cultured on the
5 nm porous silicon substrates, but not on the 20 nm porous silicon or the flat
silicon control (Gentile et al. 2012). This study demonstrated that even at the 5 nm
scale, cell behavior is influenced by topography.
The influence of porosity on cell behavior was also highlighted effectively in a
study using patterned porous silicon substrates (Johansson et al. 2005). Two types
of macroporous silicon with pore diameters around 1 m and 300 nm, respectively,
were patterned alongside flat silicon. Primary neurons from rat dorsal root ganglia
were cultured onto the surfaces, and it was observed that on large pore samples, the
neuronal axonal growth remained disordered, and there was no discernable difference
in the growth on both the porous or flat regions. In contrast, when the neurons were
cultured on the samples with smaller pores, the neurons preferentially adhered to the
porous region and showed guided axonal growth (Fig. 3). This strongly suggests that
porous silicon can be utilized to influence neuronal cell behavior, with many potential
applications for neurological-based devices.
A variant of porous silicon, nanoporous membranes, which are generated by
inducing crystal growth from an amorphous layer, has also demonstrated good cell
Fig. 3 Left: Nonspecific attachment and disordered axonal growth on large pores (1 m). Right:
Guided axonal growth on macroporous (300 nm) silicon (Johansson et al. 2005)
490
attachment with endothelial and fibroblast cells (Agrawal et al. 2010). Renal tubule
cells cultured on this platform were able to retain tight junction formation and
indicated the suitability of this material for the construction of a renal assist device
(Fissell et al. 2006). Although not a typical porous silicon assembly, it is porous and
has similar degradation properties to porous silicon, and its method of manufacture
has advantages over thickness and porosity control.
Gradients
Recently, the development of surface-bound gradients as a tool to screen cell
behavior on materials has generated significant interest (Genzer and Bhat 2008).
Chemical gradients of different functional groups can help establish the relationship
between surface chemistry and cell attachment and growth. While it has been
demonstrated that pore size can have different affects on cell adhesion with
different cells, a pore size gradient could help optimize pore size for certain desired
cell behaviors.
In the case of porous silicon, gradient of pore sizes can be generated using
variation of the standard anodization process which involves placement of the
platinum counter electrode at a 90 angle to the silicon surface during anodization
(Collins et al. 2002). In one study, gradients with pore sizes ranging from 5 to
3,000 nm were prepared and the surface was oxidized for increased stability in cell
culture medium. Neuroblastoma cells cultured on these surfaces revealed that these
cells did not attach well to a surface with a pore diameter between 50 and 100 nm
(Fig. 4). Higher densities of cells often featuring neuritic processes were observed
on the larger pore size (1,0003,000 nm) with numbers and their process length
decreasing as the pore size decreased until the pore diameter reached approximately
100 nm. This seemed to be a pore diameter where cells were unable to effectively
attach. When the pore size dropped beyond this range, cell attachment recovered
(Khung et al. 2008). Once again, cells were sensitive to nanoscale surface topography with feature sizes of <20 nm. The results of this study provide interesting
design principles for low-fouling surfaces. The authors also found that on the
porous surface, the cells were ovoid to ellipsoid in shape and were raised conspicuously above the substrate surface, in stark contrast to the flattened morphology on
nonporous silicon. Another study obtained similar results and suggested that this
may be due to the reduced surface area (essentially the top of the pores) to which
cells can establish adhesion contacts (Janshoff et al. 2010).
A report using primary mesenchymal cells (MSC) contradicted to some extent
the above results. A gradient of thermally oxidized porous silicon with pore sizes
ranging from 30 nm on one end to 300 nm at the other end of the gradient was
prepared. MCS adhered poorly on areas with small pore diameters with cell
attachment greatest at the pore region with pore sizes of around 300 nm (Fig. 5).
The large pore region, which featured lower ridge roughness values than the small
pore diameter region also encouraged differentiation of the MSC into bone-like
cells (osteogenesis). In contrast, pore size did not play a significant role in the
491
Fig. 4 SEM images of neuroblastoma cells cultured on a porous silicon porosity gradient. The
cells display different morphology dependent upon the pore size. (a) 1,0003,000 nm pores.
(b) 3001,000 nm. (c) 50100 nm and (d) 520 nm (Khung et al. 2008)
differentiation of the MSC into lipid-like cells (adipogenesis). Overall, a significant

increase in osteogenesis and adipogenesis was observed on porous silicon in
comparison to flat silicon, revealing an influence of topography on cell differentiation (Wang et al. 2012a). This could indicate that the porous topography enabled
better access for osteogenic or adipogenic factors to the cells. A larger cell surface
area would be exposed directly to the culture medium in the case of a porous
substrate. A follow-up study used rat and human bone marrow-derived mesenchymal stem cells (rBMSC and hBMSC, respectively) and primary human adiposederived mesenchymal stem cells (hASC) on a p-type porous silicon gradient that
yielded pore sizes of 2 m reducing to 10 nm at the other end (Wang et al. 2012b).
For all three MSC types, spreading was suppressed on the largest pore size region of
the gradient and spreading increased toward the other end of the gradient. MSC
attachment density on the other hand was pore size- and cell type-dependent. For
rBMSCs and hBMSCs, the attachment density was low on the porous silicon
gradient compared with flat silicon. For hASCs, a peak attachment density was
observed on the pore size region of around 330 nm.
This body of work confirms the earlier observation that the influence of topography on cell attachment, proliferation, and differentiation is dependent upon the
cell type and source and suggests that intrinsic differences between cells affect
cellmaterial surface interactions, justifying the high-throughput screening
approach with gradients.
A few recent studies have also demonstrated the fabrication of chemical gradients on porous silicon in order to screen cellsurface interactions. For example,
Fig. 5 MSC growth on a porous silicon gradient, starting from small pores (around 30 nm in size) at the 0 mm position to large pores (around 300 nm in size)
at the 12 mm position of the gradient. Cell attachment to flat silicon is shown on the right (Wang et al. 2012a)
492
493
plasma polymerization has been used to form plasma polymer gradients from a
hydrocarbon-like surface on one end to a carboxylic acid functional surface on the
opposite end of the gradient. These gradients were then used to investigate osteoblast cell attachment across the surface. Osteoblast MG63 cells attached and grew
on surfaces with a carboxylic acid concentration of 23 % (Michelmore et al. 2012).
Electrochemical grafting has also been used to generate chemical gradients on
porous silicon (Collins et al. 2002), and this approach was applied recently to
form a gradient of the cell-binding peptide (RGD) on porous silicon. The attachment propensity of rat mesenchymal cells (rMSC) correlated with increased RGD
concentrations (Clements et al. 2012).
With the ability to generate porous and chemical gradients, the next logical step
would be development of two-directional or two-dimensional (2D) gradients,
where each spot of the sample is characterized by two independent variables
often running perpendicular to each other. These variables can of course include
chemistry and topography. The use of the 2D gradient format facilitates the
investigation of the cooperative effect on the cell response. Recently, a porous
silicon pore size gradient (from 900 to 20 nm in diameter) was combined with a
cyclic RGD peptide ligand density gradient running perpendicularly. The fabrication of both surface gradients relied on a graded electrical field established during
electrochemical reactions (anodization and electrografting, respectively). A combinatorial study of mesenchymal stem cell attachment investigated the cooperative
effects of pore size and cyclic RGD ligand density. Surprisingly, the study revealed
that the cyclic RGD ligand density dominated the cell response (Clements
et al. 2012), suggesting that chemistry rather than topography is the main influence
in cell attachment behavior.
Summary
In conclusion, porous silicon can support the growth and proliferation of cells, but
this can be modulated through the use of various surface modification techniques.
Pore dimensions also play a crucial role in cell attachment and differentiation, and
individual cell types show different responses to surface features. Gradients of pore
sizes and surface chemistries can help assess the optimal pore dimensions and
surface feature to achieve a certain cell behavior. Finally, researchers studying cell
viability on porous silicon should pay careful attention to possible interferences
from the porous silicon substrate.
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Electronic Band Structure in Porous Silicon

ena-Martnez and Chumin Wang
Julia Tagu
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Theoretical Methods: For and Against . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Strain, Doping, and Surface Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
498
499
501
502
502
Abstract
This chapter summarizes the main theoretical approaches to model the porous
silicon electronic band structure, comparing effective mass theory, semiempirical, and first-principles methods. In order to model its complex porous
morphology, supercell, nanowire, and nanocrystal approaches are widely used.
In particular, calculations of strain, doping, and surface chemistry effects on the
band structure are discussed. Finally, the combined use of ab initio and tightbinding approaches to predict the band structure and properties of electronic
devices based on porous silicon is put forward.
J. Taguena-Martnez (*)
Instituto de Energas Renovables, Universidad Nacional Autonoma de Mexico, Temixco, Morelos,
Mexico
e-mail: jtag@unam.mx
C. Wang
Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Mexico,
Mexico
DOI 10.1007/978-3-319-05744-6_51
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498
J. Tag
uena-Martnez and C. Wang
Introduction
Porous silicon (pSi) at atomic scale is a crystalline material; however, it presents a
random porous distribution with branches of different morphologies and sizes, as
discussed along this book. The description of this disordered porous structure is one
of the main theoretical challenges. Due to the fabrication process, pSi presents
different surface saturations and internal structural strains, both should be adequately simulated. In addition, the inhomogeneity of pSi produces broadening of
the photoluminescence response that could be caused by a spread of local bandgaps
if there is only a partial interconnection between the nanostructures (Calcott 1977).
In order to attack this complex problem, it is necessary to make reasonable
simplifications. From a structural point of view, one approach is to create columnar
holes in a crystalline silicon matrix. Another possibility is to model pSi with
interacting silicon nanowires or with the presence of silicon quantum dots embedded in porous silicon. In other words, there are essentially two possible lines of
action: one is to study idealized Si nanowires (SiNW) (Ossicini 1997) and Si
nanocrystals (Delerue et al. 1997) to extend their results to pSi, and the second
one is to introduce an artificial periodicity usually by means of the supercell
technique (Cruz et al. 1999). In fact, in the freshly etched samples, the Si skeleton
shows undulating wire morphology, while aged samples present Si dots suggesting
a dimensionality transition from one to zero (Degoli et al. 2000). As an example of
nanocrystal modeling, Fig. 1 shows the size dependence of optical gaps calculated
Fig. 1 Size dependence of optical gaps of silicon nanocrystals calculated using quantum Monte
Carlo (QMC), time-dependent local-density approximation (TD-LDA), Hartree-Fock configuration
interactions (HF-CI), and semiempirical tight binding (TB). The inset shows schematically the
bandgap enlargement due to reducing the nanocrystal size
499
using quantum Monte Carlo (QMC) (Williamson et al. 2002), time-dependent

local-density approximation (TD-LDA) (Vasiliev et al. 2001), Hartree-Fock configuration interaction (HF-CI) (Baierle et al. 1997), and semiempirical tight-binding
(TB) (Wolkin et al. 1999) models. The inset in the figure schematically represents
the bandgap enlargement due to reducing the nanocrystal size.
From a general point of view, it is important to mention that since the discovery
of pSi luminescence in 1990, there have been great improvements in both computing capacity and algorithms. These achievements are reflected in the advances of
theoretical understanding and experimental verification. However, the use of
sophisticated computing programs should be combined with the physical understanding provided by simpler and more intuitive methods. The resulting theoretical
band structure of a material, within certain limits, is for an experimentalist like a
road map for the traveler.
Theoretical Methods: For and Against

The main theoretical methods can be classified in three groups: effective mass
theory, semiempirical methods, and first-principle studies.
1. Effective Mass Theory (EMT). Historically, the concept of effective mass
was very successful to understand the electronic behavior in semiconductors
and to design electronic devices. Nowadays, in the study of nanostructures,
the EMT is still useful to describe qualitatively the quantum confinement
effects, but it overestimates the quantitative results. For instance, when pSi is
modeled by SiNW, the bandgap (EG) as a function of its diameter (d) follows
EG(d) EG(1) + C(1/d), where C and are positive constants, and
EMT gives the upper limit of 2. This overestimation can be related to
EMT ignoring the electronic density fluctuations before the quantum
confinement.
2. Semiempirical Methods (SE). To go beyond EMT, one should introduce the
atomic arrangements and the symmetry of nanostructures. The simplest way to
do this is by means of SE methods. One group of them uses empirical pseudopotentials that soften the wave function within the atomic core. For example,
calculations of a thousand atom hydrogen-passivated Si nanostructures compared with EMT give a smaller in the bandgap vs. size relation (Zunger and
Wang 1996). Another group, so-called tight-binding approach (TB), is based on
the orthogonalized atomic orbitals or Wanniers functions. This approach uses
phenomenological parameters which include many body effects that could not
be considered in a first-principle calculation. In general, TB is the most natural
way to understand the formation of chemical bonds, and it is capable of treating
large nonperiodic systems (Delerue et al. 2001). When the bandgap vs. size is
calculated within TB, it gives close to that of EMT, regardless of the basis
set and the nanostructure connectivity chosen (Cruz et al. 1996; Zheng
et al. 2005). In addition, the calculated shift of the valence band top is bigger
J. Tag
500
than that of the conduction band bottom as a function of porosity (Cruz

et al. 1996; Yorikawa et al. 2004), in agreement with experimental observations
and with TB cluster calculations (Ren and Dow 1992). Any method based on
empirical parameters faces the challenge of scaling their value from the bulk to a
nanostructure.
3. First-Principles Studies (FP). One step further to perform a microscopic
study without fitting parameters is an FP or ab initio calculation. The density
functional theory (DFT) is perhaps the most efficient and popular FP method.
Besides the exchange interactions treated within the Hartree-Fock approximation, it also includes correlation effects through an exchange-correlation
functional. However, it gives bandgaps around 50 % smaller than the experimental ones. It is possible to improve DFT including self-energy corrections
within the GW approximation (G the Green function and W the screened
Coulomb interaction) and the excitonic states by solving the Bethe-Salpeter
equation, as done in reference Bruno et al. (2007) for SiNW simulating pSi.
In general, DFT results obtain a smaller than the EMT prediction and closer
to the experimental data (Bruno et al. 2007; Zhao et al. 2004). The FP
calculations are very time consuming, and they are usually used for studying
small nanosystems below approximately 3 nm, where quantum confinement
effects are important (Zhao et al. 2004). In order to overcome this limitation,
a linear number-of-atoms scaling DFT has been developed, which becomes
useful over 100 atoms and, for instance, it has recently been applied to more
than 1,000 atoms Si nanorods (Zonias et al. 2010). It is worth mentioning that
the quantum Monte Carlo technique has also been applied to the optical gap
of Si quantum dots, confirming the trends of quantum confinement effects
(Williamson et al. 2002).
With respect to optical properties, most calculations are limited to the
independent-electron approximation and the imaginary part of the dielectric function (e2) given by (Ossicini et al. 2003)
e2

4 2 e2 X 2
p v,k 2 Ec k Ev k ,
c
,
k
m 2 2 v , c, k V
where x, y, z, Ev and Ec denote the energies of the valence v,k and conduction
c,k band states at a k point, and V is a unit cell volume. This equation can be
written in terms of so-called oscillator strength, which is proportional to |hc,k|
p|v,ki|2 and increases as the system size reduces (Koga et al. 2002). One way to
introduce the structural disorder could be to include the vertical transitions in
k-space (Cruz et al. 1999). Another improvement on the e2 calculations can be
achieved by considering excitonic (Bruno et al. 2007) and local field effects (Onida
et al. 2002).
501
Strain, Doping, and Surface Chemistry

Strain is naturally present in pSi (Miu et al. 2011), and it could also be applied
externally. In particular, there are many studies carried out in SiNW observing, for
example, a piezoresistance several orders of magnitude greater than that of bulk Si
(He and Yang 2006). On the theoretical side, computational studies through semiempirical (Shiri et al. 2008; Stanojevic et al. 2010) and first-principle methods (Leu
et al. 2008; Hong et al. 2008) have been performed. Axial strain can be tensile or
compressive by axially increasing or decreasing the lattice constants. There is a
consensus that the bandgap diminishes in both strain directions and reaches a
transition from indirect to direct. Some possibilities are foreseen in strained
nanowires: modulation of spontaneous emissions (Shiri et al. 2012) and carrier
mobilities (Leu et al. 2008; Niquet et al. 2012), as well as charge separation
(Wu et al. 2009). All these results clearly depend on the SiNW orientation and
diameter (Hong et al. 2008).
Doping has been an important factor in pSi fabrication. However, it is also
relevant to engineer its electronic and optical properties. For instance, simultaneous
doping with boron and phosphorous enhances the photoluminescence intensity of Si
nanocrystals over the response of corresponding single-doped samples (Fujii
et al. 2004). This fact has been theoretically addressed with DFT calculations
showing that the formation energies of the codoped Si nanocrystals are always
smaller and their bandgaps are reduced, both with respect to the single-doped cases
(Ossicini et al. 2008). It has also been found that impurities segregate at the surface
of unpassivated codoped Si nanowires (Fernndez-Serra et al. 2006), as well as in
Se-doped samples (Petretto et al. 2012).
Surface is truly another fundamental issue in determining pSi properties, given
the very large surface-volume ratio in this material. Due to the electrochemical
fabrication process of pSi, the natural saturator of dangling bonds is hydrogen.
A DFT study carried out in columnar holes from a crystalline Si matrix shows a
structural expansion when its surface is saturated by hydrogen atoms, contrary to
the contraction observed in nanowire model (Vzquez et al. 2002). This expansion
was measured by high-resolution X-ray diffraction experiments (Buttard
et al. 1998). Beyond hydrogen passivation, pSi samples are oxidized in air. Firstprinciples calculations in small Si nanocrystals can explain the luminescent color
change observed in oxide samples (Zhou et al. 2003). Going further, other saturators can significantly modify the bandgap, complementing the quantum confinement effect. First-principles calculations have been applied to study the optical gap
of small Si nanocrystals with saturators as oxygen, sulfur, CH2, fluorine, chlorine,
and OH, finding small effects for single-bonded saturators and a clear reduction for
double-bonded ones, where the tetrahedral network is distorted (Puzder
et al. 2002a); Si-O-Si bridges also reduce the gap (Ossicini et al. 2008; Puzder
et al. 2002b). With respect to SiNW, saturators as OH and NH2 narrow the bandgap
for all wire orientations analyzed (Nolan et al. 2007). In Fig. 2 we show the
502
J. Tag
Fig. 2 Bandgap as a function

of [110] SiNW diameters with
data from Zhuo and Chou
(2013) for surface
terminations: H (open
circles), F (open squares),
and CH3 (open triangles),
which illustrates a strong
dependence of the band
structure on surface
chemistry, although the
absolute bandgap values are
known to be inaccurate
bandgap as a function of [110] SiNW diameters for various surface terminations

obtained by using DFT (Zhuo and Chou 2013). Note that hydrogen saturation produces the biggest gap, which is in fact smaller than the experimental data since the
bandgap of bulk c-Si in these calculations was 0.46 eV (Zhuo and Chou 2013).
Future Perspectives
As can be seen, most of the theoretical studies of pSi are carried out in SiNW and Si
nanocrystals, ignoring its topological complexity. However, with the advance of
nanolithography an ordered mesoscopic pSi should be available in the near future.
Regarding theoretical methods, there is an important effort to combine the advantages of first-principles and tight-binding techniques (Koskinen and Makinen
2009), which has been applied to large SiNW of different cross-section geometries
(Yao et al. 2008). This kind of approaches by matching methods usually applied to
different scales can make possible the design of new materials and devices.
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Roberto Koropecki and Roberto Arce
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Characterization Techniques Using Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Irradiation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photoirradiation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ion Irradiation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
505
506
507
507
511
513
513
Abstract
Besides the well-known effect of photoluminescence, the impinging of photons

and other kinds of particles such as electrons, ions, and muons on porous silicon
produces important effects. Some of these effects can modify the structure and
properties of the material, distorting the interpretation of data based on the use of
irradiation. Some of the irradiation effects are useful in different applications
such as photodynamic therapy or display applications. This work is a review of
the effects of irradiation on porous silicon.
Introduction
Electrons and ion beams, as well as photons with different energies, are usually
employed as probe in characterization techniques for the study of porous silicon
(PS) properties. The interaction between the different beams and PS is also present
in a variety of sensing devices and filters. These devices usually exploit the energy
R. Koropecki (*) R. Arce
Grupo de Semiconductores Nanoestructurados, Instituto de Fsica del Litoral, IFIS Litoral
(UNL-CONICET), Santa Fe, Argentina
e-mail: roberto.koropecki@ifis.santafe-conicet.gov.ar; rkoropecki@gmail.com
DOI 10.1007/978-3-319-05744-6_52
505
506
R. Koropecki and R. Arce
exchange between the incident beam and the porous silicon. As a result, some
structural or electronic changes occur, which may be reversible, metastable, or
irreversible. So it is important to know these effects in order to properly design the
devices and also to properly interpret the results of the analysis techniques. A
general textbook on the effects of radiation in solids can be found in reference
(Sickafus et al. 2007).
In this review, we deal with the effects of irradiation on porous silicon.
Characterization Techniques Using Irradiation

The luminescence of porous silicon (Canham 1990) discovered by Canham in 1990
was responsible for much of the rise and progress of silicon photonics. Originally, the
focus was on the potential use of its electroluminescence in optoelectronic devices,
but now it is mainly used for sensing purposes, in chemical sensors and biosensors,
and also in characterization techniques for the study of electronic defects and
recombination processes. The luminescence can be excited by irradiation with
photons having different energies (Cullis et al. 1997; Gardelis et al. 1996; Dalba
et al. 1998, 1999; Sham et al. 2000; Pettifer et al. 1995), with multiphoton excitation
(Diener et al. 1995), or with electrons (Maurice et al. 1995; Biaggi-Labiosa
et al. 2008; Timoshenko et al. 1996; Cullis et al. 1994; Hummel et al. 1995). Besides
the well-known UVVISNIR absorption spectroscopy and the FTIR spectroscopy, a
variety of spectroscopic techniques employed in PS characterization also use photons. Among them we can mention the following: Raman spectroscopy, ultraviolet
photoemission spectroscopy (UPS) (Aprelev et al. 1997), X-ray absorption spectroscopies (such as XAS, EXAFS, and XANES) (Dalba et al. 1998, 1999; Zhang
et al. 2000; Van Buuren et al. 1994; Schuppler et al. 1995), X-ray photoelectron
spectroscopy (XPS) (Frohnhoff et al. 1995; Dimova-Malinovska et al. 1995;
Thonissen et al. 1996; Kanungo et al. 2009; Matsumoto et al. 1997; Voss 1997;
Buzaneva et al. 2000; Debarge et al. 1998; Jarvis et al. 2012; Kanungo et al. 2010;
Zanoni et al. 1999; Harraz et al. 2008; Bolotov et al. 2012), and X-ray diffraction
(XRD) (Zanoni et al. 1999; Lee et al. 2005).
Other spectroscopies employed in porous silicon study use electron beams. This
is the case of Auger electron spectroscopy (AES) (Hummel et al. 1995; Schuppler
et al. 1995; Harraz et al. 2008; Bolotov et al. 2012; Lee et al. 2005; Thompson
et al. 1998; Pavesi et al. 1994; Wise et al. 1996; Kostishko et al. 2004; Bedikjan and
Danesh 1997; Xiong et al. 2001; Galiy et al. 1998; Baranauskas et al. 1999; Jin
et al. 2006), electron energy loss spectroscopy (EELS) (Cullis et al. 1994; Berbezier
et al. 1996; Vasin et al. 2011; Martn-Palma et al. 2006; Song et al. 2000), electron
microprobe spectroscopy (EDX) (Matsumoto et al. 1997; Zanoni et al. 1999;
Bolotov et al. 2012; Lee et al. 2005), and low-energy electron diffraction spectroscopy (LEEDS) (Li et al. 2000). Electron beams are used also in the morphological
characterization of PS, as in the case of scanning electron microscopy (SEM) (Zanoni
et al. 1999; Bolotov et al. 2012; Berbezier et al. 1996; Vasin et al. 2011; Chiboub
et al. 2010; Gorbanyuk et al. 2006), transmission electron microscopy (TEM)
507
Table 1 Characterization techniques associated to the different classes of probe beams

Class of probe
beam
Photons
Electrons
Ions (H, He, C,

O, P, Si, N, etc.)
Subatomic
particles
(positrons, muons)
Associated
characterization
techniques
Raman, UPS, XAS,
EXAFS, XANES, IR,
PL, XR
AES, EELS, EDX,
RHEED
CL, SEM, TEM, etc.
ERDA, RBS, SIMS,
DIOS-MS
PAS, SR
Related handbook chapters

Infrared Spectroscopy, Photoluminescence
of Porous Silicon, and X-Ray Diffraction in
Porous Silicon
Silicon
Chemical Characterization of Porous
Silicon
Silicon
(Lee et al. 2005; Martn-Palma et al. 2006; Song et al. 2000; Li et al. 2000; Chiboub
et al. 2010), and reflection electron diffraction. PS has also been investigated by using
ion spectroscopies, such as elastic recoil detection analysis (ERDA) (Jarvis
et al. 2012), Rutherford backscattering spectroscopy (RBS) (Jarvis et al. 2012),
secondary ion mass spectroscopy (SIMS) (Aprelev et al. 1997; Kanungo
et al. 2010; Zanoni et al. 1999; Thompson et al. 1998; Kempson et al. 2010;
Torchinskaya et al. 1997, 1998; Torchynska et al. 1999; Kleps et al. 1997, 1998;
Banerjee et al. 2008; Cwil et al. 2006; Fried et al. 1999), and desorption/ionization on
porous silicon mass spectrometry (DIOS-MS) (Wei et al. 1999; Li et al. 2005).
Subatomic particles as positive muons have been irradiated on porous silicon to
perform muon spin spectroscopy (SR) (Harris et al. 1997) and positrons to perform
positron and positronium annihilation spectroscopies (PAS) (Itoh et al. 1996;
Knights et al. 1995; Suzuki et al. 1994). The different characterization techniques,
and the link with the different chapters of this handbook, are resumed in Table 1.
In the following, we will review the main consequences produced by different
irradiation processes.
Irradiation Effects
Figure 1 shows a general scheme of different effects occurring in porous silicon
under irradiation.
Photoirradiation Effects
Many properties can be altered by irradiating porous silicon with photons. Photooxidation (Frohnhoff et al. 1995; Salonen et al. 1999; Fu et al. 1993; Tamura and
508
Fig. 1 General scheme of different effects of irradiation
Adachi 2009; Koropecki et al. 2004a, b, 2006, 2007; Aouida et al. 2006; Kovalev
et al. 2004; Zhang et al. 1995), generation of electronic defects associated to
dangling bond (Koropecki et al. 2007; Aouida et al. 2006; Arce et al. 2006) or
weak bonds, and photo-diffusion or loss of hydrogen from the PS surface
(Koropecki et al. 2007; Aouida et al. 2006; Collins et al. 1992; Frello and Veje
1997) are some of the photoinduced effects. Photoinduced changes manifest themselves in effects such as changes in energy or intensity of the photoluminescence
spectra (Koropecki et al. 2004a, b, 2006, 2007; Aouida et al. 2006; Arce et al. 2006;
Collins et al. 1992; Frello and Veje 1997; Xu and Adachi 2010; Fauchet 1996;
Mandal et al. 2004; Choi et al. 1995), changes in the electron paramagnetic
resonance signal (Koropecki et al. 2004a, 2007; Aouida et al. 2006; Collins
et al. 1992; Mandal et al. 2004; Timoshenko 2009a) mainly associated with
dangling bonds, changes in the effective dielectric function, changes in hydrophilicity (Tamura and Adachi 2009), and generation of singlet oxygen (Kovalev
et al. 2002, 2004, 2005; Timoshenko 2009a; Gross et al. 2003; Loponov
et al. 2010; Fujii et al. 2005, 2007; Gongalsky et al. 2011; Pikulev et al. 2006;
Konstantinova et al. 2007; Lee et al. 2007; Timoshenko 2009b), among others.
Depending on the preparation conditions, on the PL excitation characteristics,
and on the PL spectral region, the luminescence intensity increases or decays during
the photon exposure or multiple peaks with different behaviors (Koropecki
et al. 2004b; Fauchet 1996; Choi et al. 1995; El Houichet et al. 1997). The
enhancement and spectral shift of the PL spectra were reported for samples
irradiated with 60Co rays (Bhave et al. 1997). The behavior of the photoinduced
509
evolution may depend on the atmosphere in which the porous silicon is embedded
(Salonen and Laine 1996) and on the preparation conditions (Koropecki et al. 2007;
Aouida et al. 2006; Collins et al. 1992). It has been reported that irradiation with
60
Co rays also produces enhancement of the PL and radiation-induced recrystallization (Bhave et al. 1997). On the other side, there are reports of the degradation
of the photoluminescence signal induced by ray irradiation (Astrova et al. 1995;
Agekyan et al. 1999).
Many authors report on the photoinduced degradation of PL in porous silicon.
The nature of the degradation mechanisms is complex and involves different
processes (Cullis et al. 1997). Tischler et al. report that there are physicochemical
effects (Tischler et al. 1992) related with photooxidation which are mostly irreversible and partially recovered by immersion (Tischler et al. 1992) in hydrofluoric
acid. Illumination under nonoxidizing atmosphere produces a little although not
negligible degradation effect (Koropecki et al. 2007; Collins et al. 1992). Photoinduced loss of hydrogen from fresh PS in vacuum has been reported (Koropecki
et al. 2007). Non-radiative recombination paths are created and associated to
unsaturated dangling bonds (DB), which can be responsible for the luminescence
decay. A photoinduced increase of the DB density has been measured by electron
paramagnetic resonance (EPR) both for exposed (Koropecki et al. 2006, 2007;
Collins et al. 1992; Tischler et al. 1992) and for nonexposed samples to an oxidizing
atmosphere. Electron beam-induced hydrogen effusion was also reported with a
consequent increase of the DB density and decay of the cathodoluminescence
(Ruano et al. 2011).
Thermal effects might be responsible for hydrogen loss. However, there are
experimental evidences showing that the kinetics of the photoinduced decay of
luminescence and the decay of the cathodoluminescence as well as the kinetics of
hydrogen desorption during electron beam irradiation are not compatible with
thermal effects or direct exchange of energy between the radiation and the
hydrogen atoms. Instead, these kinetics are compatible with short-lived high-energy
fluctuations (SLEFs) occurring during bimolecular recombination of carriers
(Koropecki et al. 2007; Arce et al. 2006; Ruano et al. 2011). Whatever the
excitation be, which creates electron hole pairs, the densities of carriers within
the bands will be the result of the balance between generation and recombination.
The main recombination processes are non-radiative and occur mediated by defects
located in the hydrogenated surface layer of the nanostructure. The model considers
that during SLEFs some structural changes occur, involving diffusion of hydrogen
atoms and creation of dangling bonds, which act as recombination centers. As a
result, the carrier densities in the conduction and valence band change, and so the
bimolecular recombination rate. This process is self-limited resulting in a decay of
the luminescence following approximately a power law (Koropecki et al. 2006,
2007; Arce et al. 2006; Ruano et al. 2011) with exponent approximately 1/3. The
cumulative density of dangling bonds created during this process also follows a
power law (Koropecki et al. 2006) with exponent 1/3. In agreement, hydrogen
release with a rate which follows a power law (Ruano et al. 2011) with exponent
approximately 2/3 also occurs. Samples prepared under high level of
510
illumination, starting from high-resistivity silicon either n type (Arce et al. 2006) or
p type (Koropecki et al. 2006), show this behavior. However, there is experimental
evidence that this is only one of the irradiation-induced effects. In fact, there is
radiation-induced evolution of the luminescence related to photoinduced oxidation
of nanostructures. It has been reported that samples prepared in darkness or under
low illumination level using high-resistivity silicon have greater DB densities than
samples prepared under illumination (Koropecki et al. 2007). The PL spectra of
these samples show the increase of a high-energy band at the expenses of the
decrease of a low-energy band (Koropecki et al. 2004a, b, 2006, 2007; Arce
et al. 2006). There are experimental evidences supporting that these effects are
related to oxidation of the nanostructure and that also take place for samples
prepared under high level of illumination, although the intensity of the luminescence associated to this effect is negligible compared to that associated to the one
associated to the photoinduced quenching (Koropecki et al. 2007). For samples
prepared under high level of illumination, the PL photoinduced quenching in
vacuum shows the same time dependence as in air atmosphere, although the latter
is faster than the former. One of the photoinduced effects of porous silicon exposed
to molecular oxygen is the generation of reactive species. Molecular oxygen has the
triplet state 3 as ground state and two singlet excited states 1 and 1. The singlet
oxygen 1O2 is very reactive and has a lot of applications, mainly in photodynamic
therapy of cancer.
Direct optical excitations of O2 to its singlet excited states are forbidden by
selection rules of spin and parity conservation. However, 1O2 can be effectively
created in chemical reactions or under electrical discharges or by a process of
photosensitization in which a photoexcited molecule transfers its energy and spins
to a triplet ground state O2 molecule, which is then promoted to its singlet state
(Timoshenko 2009a). Porous silicon is an efficient photosensitizer due to its large
specific surface combined with the long radiative lifetime of excitons confined in
nanocrystalline silicon (Kovalev et al. 2002; Gross et al. 2003; Fujii et al. 2005).
See handbook chapter Porous Silicon in Photodynamic and Photothermal
Therapy for more details of its use.
Although direct photoinduced transitions in free molecular oxygen from the
triplet to the singlet states are forbidden by selection rules, these transitions occur
due to perturbations. Absorption and emission bands related to 3 and 1 transitions, which occur at 7,882 cm1 and 13,121 cm1, have been observed in the upper
atmosphere spectrum (Kearns 1971). The radiative lifetimes of 1 and 1 states are
2.7 103 s and 7.1 s (Kearns 1971; Huie and Neta 2002). The 1 state quenches
very rapidly to the 1 state (Timoshenko 2009b). As an example, the estimated
lifetime in water is about 1011 s so that it is not relevant in physiology. The 1
state has larger lifetimes; it goes from 2 s in water to 1 ms in CFCl3, so that it has
enough time to interact with other species in the solution (Huie and Neta 2002).
The photo-generation of singlet oxygen by photosensitization usually involves
photoexcitation of a light-absorbing substance, usually a die-like organic molecule,
named photosensitizer. The excitation of this energy donor to its first excited
singlet state initiates the energy transfer process to the energy acceptor
511
nonabsorbent oxygen triplet. Some of the energetic relaxation processes of the

singlet excited state of the photosensitizing result in the transference of energy and
spin to the energy acceptor by a Forster dipoledipole process (Timoshenko 2009b)
or an intersystem crossing process involving the decay of the donor to its lower
energy triplet state which interacts with the oxygen to produce singlet oxygen
(Timoshenko 2009b; Huie and Neta 2002; Derosa and Crutchley 2002). Due to
the indirect nature of silicon, the computed lifetime of confined excitons in the
nanostructure of porous silicon at room temperature is as long as 10100 s for the
triplet state, similar to the singlet configuration (Cullis et al. 1997; Timoshenko
2009a). Therefore, excitons in porous silicon have an electronic configuration similar
to that of dye molecules. The size distribution and consequently the energy gap of the
nanocrystalline structures allow the energy match of the singlettriplet splitting
energy of 3O2 molecules. This characteristic, combined with the large specific surface
of porous silicon, makes it an excellent photosensitizer (Gross et al. 2003).
The quantum yield of generation of 1O2 in porous silicon, measured by chemical
trapping, was (Xiao et al. 2011) 0.10 0.02 in ethanol and 0.17 0.01 in
H2O. Although the generation rates are lower and less effective than those obtained
with organic molecules employed in photodynamic therapy, porous silicon overcomes toxicity and degradation problems which are the main drawbacks of treatment with these organic molecules (Xiao et al. 2011). There is an extensive list of
works related to the generation of singlet oxygen using porous silicon as a photosensitizer energy donor (Kovalev et al. 2002, 2004, 2005; Timoshenko 2009a, b;
Gross et al. 2003; Loponov et al. 2010; Fujii et al. 2004, 2005, 2007; Gongalsky
et al. 2011; Pikulev et al. 2006; Konstantinova et al. 2007, 2011; Lee et al. 2007;
Xiao et al. 2011; Heitmann et al. 2004). There are also reports of the combination of
porous silicon and anilines as photosensitizers (Parkhutik et al. 2007).
Ion Irradiation Effects

The effects of porous silicon irradiation with ions have been investigated extensively. There are a large variety of studies of the effects of ion bombardment on
the photoluminescence spectrum of PS. Table 2 shows the effects of different
bombarding species.
The experiments include ions of different types and energies such as oxygen ions
with 14 MeV (Bhave et al. 1996, 1997, 1999), as well as H+, He2+, and Ne2+ with
35109 keV (Jacobsohn et al. 2006), 30 keV He+ (Baratta et al. 2004), and 10 keV
C+ (Liu et al. 2001). The suppression and subsequent recovery of the PL by 800 eV
Ar and N ion irradiation has been reported (Du et al. 2008). Similar behavior has
been published for 35 keV He+ and 42 keV H+ ion irradiation (Jacobsohn
et al. 2005, 2006) and for 250 keV Ne ion irradiation (Barbour et al. 1992).
Similarly, there are studies of the effect on the PL of low-energy (10 eV) oxygen
ions from a plasma generated by electron cyclotron resonance (OKeeffe
et al. 1996). The effects of plasma fluorination from CF4 (Freon 14) gas on PS
photoluminescence were studied (Pan et al. 2004). The effects of irradiation with
512
Table 2 Effects of different bombarding species on porous silicon

Bombarding
species
Si7+
Electrons
Energy/
characteristics
10 MeV
16 MeV
Effects
Increasing PL
Stabilization
O ions
14 MeV
Increasing PL
H+, He+,
Ne2+
35109 keV
Fluence-dependent damage
PL reduction, recovery in air
He+
30 keV
Fluence-dependent PL reduction
C+
10 keV
Ar, N ions
O ions
800 eV
800 eV
Ne
250 keV
Red PL emission reduction

Blue PL emission rising
PL suppression, recovery in air
PL spectrum shape changes
Subsequent PL decrease in air
PL reduction
O ions
10 eV (plasma)
CF4
(plasma)
Au7+
100 MeV
Ni ions
85 MeV
PL enhancement, fatigue
suppression
Gap expansion, dielectric function
reduction
PL enhancement, stabilization
PL degradation for high doses
PL suppression
He ions
2 MeV (prior to
porosification)
524 MeV (prior to
porosification)
2 MeV (prior to
porosification)
2 MeV (previous to
porosification)
Defect creation in bulk Si,

allowing 3D patterning
allowing 3D patterning
allowing tuning of PS properties
Control of reflectance in porous
silicon microcavities
Si ions
He ions
Protons
References
Bhave
et al. (1996,
1997)
Bhave
et al. (1999)
Jacobsohn
et al. (2005,
2006)
Baratta
et al. (2004)
Liu et al. (2001)
Du et al. (2008)
Du et al. (2008)
Barbour
et al. (1992)
OKeeffe
et al. (1996)
Pan et al. (2004)
Sehrawat
et al. (2004)
Mehta
et al. (1996)
Teo et al. (2004)
Punzon-Quijorna
et al. (2012)
Teo et al. (2007)
Mangaiyarkarasi
et al. (2007)
oxygen ions were compared with that of silicon ions (Bhave et al. 1999). Au+7
(Sehrawat et al. 2004) and Ni ion (Mehta et al. 1996) effects in the PL spectra of
porous silicon samples have been also studied.
Irradiation with ions was used on monocrystalline substrates prior to anodization, in order to manage the porous silicon properties. This allows technique of 3D
micromachining of silicon (Teo et al. 2004; Punzon-Quijorna et al. 2012). Tunable
color contrast of the emission of PS has been achieved by varying the dose of He+
ion irradiation (Teo et al. 2007). Images with different reflected colors have been
also obtained by irradiation of optical microcavities with 2 MeV protons
(Mangaiyarkarasi et al. 2007).
513
Helium ions from an electron cyclotron resonance source were used to

study the effects on the irradiation prior to anodization on the PL spectrum of
porous silicon, comparing them with the post-anodization effects (Yamauchi
et al. 2002).
Irradiation of ZnO-filled PS with 120 MeV Au heavy ions was reported to
produce a decrease in the photoluminescence associated with PS simultaneously
with an increase in the ZnO deep level related photoluminescence (Singh
et al. 2009).
It has been reported (Huang 1997) that positron irradiation produces a large
blueshift (~126 nm), followed by a two-peak generation in the PL spectrum of
PS. Although the exposure time employed was large, the result is important not
only because it is a potential tool for the porous silicon band structure engineering
but also to prevent modifications in positron annihilation spectroscopic experiments, as it is a characterization technique for porous silicon (Suzuki et al. 1994;
Itoh et al. 1993; Dannefaer et al. 1996; Biasini et al. 2000).
Muon states have been also implanted in porous silicon in order to perform SR
spectroscopy (Harris et al. 1997).
In general, the PL efficiency has been reported to increase or decrease,
depending on the interplay between altered oxidation level and defect creation
produced by irradiation with ions or photons. Other properties, such as the PS
electrical transport (Gokarna et al. 1999) and the electron-induced secondary
electron emission spectra from PS surface (Ruano et al. 2009a, b), have been
demonstrated to be modified by ion bombardment.
Conclusions
Summarizing, photoinduced and ion or electron beam effects include oxidation,
hydrogen release, dangling bond creation, and creation of reactive molecular
species. Ion bombardment can in addition introduce a variety of point defects in
the silicon skeleton. Highly focused beams, such as used in micro-Raman, can
cause thermally induced hydrogen exodiffusion, sintering, defect creation, etc. An
awareness of potential irradiation effects is important in both the characterization
and processing of porous silicon.
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Part IV
Processing
Typical Processing Steps with

Porous Silicon
Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process Flows . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microwave Processing of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Supercritical Fluid Processing of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Control of Porous Silicon Particle Size and Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Suspensions and Colloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
Porosified silicon wafers or powders from electrochemical etching often require

a series of additional processing steps, prior to use. These can include patterning,
drying, comminution, manipulation of surface chemistry, sintering, impregnation, or coating, in order to achieve the desired substrates, membranes, microparticles, or nanoparticles. Typical process flows are illustrated, giving examples
of where the choice and order of processing steps can be important. Examples
are also given of processing topics yet to be widely explored with porous silicon,
but which could become important for some of the emerging applications.
Introduction
This section of the handbook contains many reviews dedicated to particular
processing techniques for porous silicon. The primary objective of this short
introductory chapter is to show how each process links to others, as part of an
L. Canham (*)
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overall fabrication route toward realizing either porous silicon substrates, membranes, powders, or composites. Another objective is to highlight processing topics
that did not receive dedicated reviews but which nonetheless are likely to receive
more study in the future. Most of the individual reviews that follow relate primarily
to mesoporous silicon processing, so there are also two handbook reviews
(see Processing of Macroporous Silicon and Oxidation of Macroporous
Silicon) which deal exclusively and comprehensively with macroporous material.
Process Flows
Figure 1 shows typical processing sequences for electrochemically etched silicon
wafers. Similar diagrams can be assembled for porous silicon made by other routes,
such as through silica reduction, but there is less literature on these currently. A
number of general points will be made, highlighting how resulting properties of
mesoporous silicon can sometimes be improved by not only optimizing each
process step (see individual reviews) but also the ordering of those steps.
If we take drying of the wet-etched structure as a first example, then as shown in
Fig. 1, if one can impregnate the pores of the structure before the drying step, one
can sometimes process ultrahigh porosity silicon without having to resort to specialized drying techniques (see handbook chapter Drying Techniques Applied
Fig. 1 Common process flows for electrochemically etched (porosified) silicon wafers
Typical Processing Steps with Porous Silicon
525
to Porous Silicon). This can occur when the impregnating material improves
the mechanical strength and thereby reduces the effects of capillary forces. There
are dedicated reviews in the handbook on three methods of pore impregnation:
chemical, electrochemical, and thermal (see Porous silicon and electrochemical
deposition, Porous silicon and conductive polymer nanostructures via
templating, and Melt intrusion in porous silicon). A further important impregnation technique, reviewed elsewhere very recently (Lehto and Riikonen 2014), is
solvent-assisted loading. For some particle-based applications where suspensions
are required, one can also completely avoid the drying step by the use of pore liquid
exchange combined with sonication or wet milling, provided the resulting suspension has sufficient physical and chemical stability for long-term storage.
A second example concerns another common processing step chemical passivation of porous silicon surfaces, in particles or patterned wafers. There are three
dedicated reviews in the handbook that deal with this: Oxidation of mesoporous
silicon, Silicon-Carbon Bond Formation on Porous Silicon, and
Photoluminescent Nanoparticle Derivatization Via Porous Silicon. It can be
important to perform these passivation treatments after the particle sizing or
patterning process; otherwise freshly fractured or patterned porous silicon surfaces
will not be passivated. Note that for some applications one can also choose to
derivatize the pore walls during anodization (Mattei and Valentini 2003) rather than
the more common sequence to derivatize after, or even both during and after
anodization to get specific surface chemistries and spatially selective functionalization (Valentini et al. 2007).
A third example concerns choosing the optimum process route for a given target
structure and application area. Let us first consider porous silicon membranes (see
Fig. 1 and handbook chapter Porous Silicon Membranes). Depending on target
membrane thickness and handling requirements, one can choose to prethin all or
part of the silicon wafer to the desired membrane thickness, prior to porosifying
right through, or use the anodization-based lift-off technique to detach an already
porous layer from the underlying bulk silicon. Considering porous silicon composites (see Fig. 1 and handbook chapter Polymer - Porous Silicon Composites),
there are a multitude of processing routes, depending on whether the additional
material is inside or around the porous structure and on whether porous silicon
remains as a chip-based layer or is in membrane or particulate form.
A fourth example is patterning. Two comprehensive reviews of lithographybased patterning are provided: Photolithography on Porous Silicon and
Colloidal Lithography. The former is an established technique for porous
silicon where one can choose to pattern before or after etching; the latter is an
emerging, higher-resolution technique, where one tries to control pore nucleation
sites and thereby improve the regularity of the mesopore network. In contrast again,
the third review on patterning in the handbook ( Imprinting Porous Silicon) is a
new method where patterning is always performed after etching.
With the exception of most porous silicon membrane applications, external
coatings, caps, and microencapsulation are very often required for diverse uses.
There are two dedicated reviews on this topic within the handbook: a very
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comprehensive survey (see Functional Coatings of Porous Silicon) and an

interesting new process for drug delivery (see Electroencapsulation of Porous
Silicon). The use of capping to minimize storage effects and irradiation effects had
already been selectively reviewed (Loni 1997). The two types of epitaxial coating
(see Homoepitaxy on Porous Silicon and Heteroepitaxy on Porous Sili
con) both receive dedicated reviews for the first time. Controlling how the material
changes during the necessary thermal treatments (see Sintering of Porous
Silicon) is very important for both types of epitaxy.
Microwave Processing of Porous Silicon

An example of a materials processing technique yet to be explored much
with porous silicon is microwave processing (Bykov et al. 2001). Microwaves
have been used to control drying and accelerate impregnation and chemical
reactions in many other porous materials. The potential to selectively deposit
energy within pore adsorbates is particularly interesting. With porous silicon
processing, there are just isolated reports of its use for derivatization (Petit et al.
2008) and impregnation.
Supercritical Fluid Processing of Porous Silicon

Supercritical carbon dioxide is a benign solvent receiving increasing attention in
materials science (Cooper 2003, Duarte et al. 2009). With porous silicon
processing, it has primarily been investigated for drying (see chapter Drying
Techniques Applied to Porous Silicon), and there are only isolated reports of its
use for impregnation (Lin et al. 2006, Bleidiessel et al. 2008). However it would
appear to have other potential uses, such as in the purification of porous silicon
(Koynov et al. 2011) for high-value biomedical uses. The removal of etch residues
from small mesopores and micropores in silicon using such fluids could be a faster
process than with conventional solvent rinsing.
Control of Porous Silicon Particle Size and Shape

Comminution of porous silicon via milling is reviewed in this handbook (see
Milling of Porous Silicon Microparticles) but not by sonication (Heinrich
et al. 1992) nor ablation (Laiho and Pavolv 1995). Sonication is a popular route
to achieve porous silicon nanoparticles and microparticles (Park et al. 2009, Kale
et al. 2012, Thakur et al. 2012), and so methods to maximize yield would be an
important topic for the future. Laser ablation in liquids also looks an interesting
route for nanoparticle generation (Nakamura et al. 2014), but again yield and
throughput should be quantified (Intartaglia et al. 2014).
527
Are there high-throughput top-down techniques that can be used to improve the
monodispersity for both microparticles and nanoparticles? Are there techniques
to control particle shape at large batch size? Photolithography has been elegantly
used to generate monodisperse porous silicon microparticles of highly defined size
and shape, but throughput is once again limited (Chiappini et al. 2010). This could
hinder clinical and commercial development, even in low-volume, high-value
areas, such as cancer therapy (see handbook chapter Porous Silicon Application
Survey). Silicon is a difficult material to spheroidize due to its thermal properties
it expands as it solidifies, so standard industrial melting techniques for metals do not
work so well with silicon (Omae et al. 2006).
Porous Silicon Suspensions and Colloids

Novel uses of porous silicon in liquid-based products, like inks for printed circuits,
pastes for lithium battery anodes, sunscreens, toothpaste, shampoos, and beverages,
require the material to participate in suspensions or colloids that are uniform, stable,
and often complex with regard to having many constituents. Very little data is
available on the general behavior of porous silicon microparticles and nanoparticles
in liquids. Important examples include particle agglomeration, flocculation, flow,
and sedimentation rates. Kompan and co-workers utilized sedimentation to size
filter luminescent material (Kompan and Shabanov 1994). Repeated sedimentation
and centrifugation or filtration has been used to improve nanoparticle size selection
(Valenta et al. 2005). Matveeva and co-workers investigated the use of surfactants
to improve suspensions for biomedical use (Balaguer et al. 2008). Chao and
co-workers used derivatization to improve nanoparticle photostability in suspension (Wang et al. 2011). Timoshenko and co-workers utilized ultrathin biodegradable polymer coatings (Gongalsky et al. 2012) within nanoparticle suspensions.
Data on particulate zeta potentials and isoelectric points are also beginning to
appear (see handbook review Tunable Properties of Porous Silicon). Some
fundamental information on the liquid dispersibility of nonporous silicon powders
is available from the ceramic industry literature (Bleier 1983a, b, Kerkar
et al. 1990). This would appear to be an important area for much further research
within secondary processing.
Concluding Comments
A variety of processing steps have been utilized to achieve the desired physical
forms and surface properties with porous silicon. Judicious choice of their order and
overall process route can assist in optimization of properties for a specific use.
Further improvements in maximum surface areas and porosities are likely to come
from a combination of optimized etching, drying, and passivation steps. Improvements in chemical and mechanical stability are anticipated from optimized
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passivation and nanocomposite design, respectively. Improvements in control over

particle size and shape dispersion are desired, but the feedstocks need to be
inexpensive and the processing routes need to be scalable for maximum benefit.
Some of the secondary processing techniques developed with other highly porous
materials (see, e.g., Wen et al. 2001, Hollister 2005, Conde et al. 2006, Studart
et al. 2006) are likely to be utilized in the future.
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Adrian Keating
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photolithographic Methods to Pattern PS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
531
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Abstract
Methods to transfer a pattern into porous silicon using light are reviewed. These
methods can be applied before, during, or after the anodization processes. The
advantages and disadvantages of each method are noted and technical performance compared using the aspect ratio of the pattern transferred into the porous
silicon as a key metric. Based on this comparison, it is possible to group the
various methods in a manner that allows specific applications to use the most
appropriate patterning method.
Introduction
Patterning of porous silicon (PS) has been largely based on patterning before or
during anodization to avoid exposure to aggressive chemical processes after the
films have been formed. However, only macroporous silicon can achieve both highresolution and uniform porosity in thick layers using such techniques. Recently,
A. Keating (*)
The Microelectronics Research Group, School of Mechanical and Chemical Engineering,
The University of Western Australia, Crawley, WA, Australia
e-mail: adrian.keating@uwa.edu.au
DOI 10.1007/978-3-319-05744-6_54
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A. Keating
techniques which enable photolithographic patterning after the porous layer is

formed have received more attention as this approach allows highly uniform
mesoporous layers to be formed with high resolution.
Photolithographic Methods to Pattern PS

Photolithography has been significantly advanced by the microelectronics industry
to enable high-resolution patterning of structures into substrates. As a result, the
term photolithography is primarily associated with UV exposure of photoresists and
subsequent pattern transfer. This review uses the term photolithography more
generally with regard to porous silicon to include any methods that use light to
define patterns in the material. A previous review of patterning methods of PS
addressed methods of patterning based on localized anodization, etch stops, and
pattern transfer, (Canham 1997) and a variety of other patterning methods exist
including e-beam patterning (Borini et al. 2003), implantation (Schmuki
et al. 2000), stamping (Ryckman et al. 2010), and shadow masking (Kozlowski
et al. 1994; Martnez et al. 2008). This work focuses specifically on photolithography of PS, as photolithography-based patterning is essential for (to name a few) PS
integration with CMOS processes (Barillaro et al. 2010; Barillaro and Strambini
2008), development of micro-hotplates (Tsamis et al. 2003), patterning of biosensors (Sweetman and Voelcker 2012), waveguides/RF switches (Itotia and Drayton 2002), and micromachining (Steiner and Lang 1995). Relevant application
chapters in this handbook include Porous Silicon for Microdevices and
Microsystems, Thermal Isolation with Porous Silicon, Porous Silicon
Optical Biosensors, Porous Silicon Optical Waveguides, RF Electrical
Isolation with Porous Silicon, and Porous Silicon Micromachining Technol
ogy, Porous Silicon Diffraction Gratings.
Photolithographic approaches to patterning PS can largely be grouped into three
categories as illustrated in Fig. 1, namely, pre-patterning, in situ patterning, and
post-patterning.
Pre-patterning: Pre-patterning of the substrate prior to anodization is undertaken
by either patterning the underlying silicon or creating well-defined openings in a
protection layer covering the silicon surface. The protection layer prevents PS
formation except at well-defined openings in this masking layer. These openings
Fig. 1 Illustration of the

3 typical approaches which
leverage photolithography to
pattern porous silicon
533
can be made using standard photolithographically defined patterning of either a soft

mask (typically photoresist) or a hard mask (SiNx, SiC, metal). Photoresist is
relatively stable in HF, but post-exposure baking of the photoresist is an essential
step to ensure some degree of robustness of the photoresist mask during anodization. Post-bakes at standard temperatures (~105 C) do not densify the films
sufficiently, and the films become damaged after short anodization times (less
than 10 min (Kaltsas and Nassiopoulou 1998)). However, even post-bake temperatures of 150 C can only achieve an anodization duration of 30 min (Ohmukai
et al. 2005), restricting this approach to the formation of only thin PS layers.
Nevertheless, photoresist pre-patterning has been used to define various devices
including multilayer PS films for wavelength encoding of proteins (Cunin
et al. 2002), hot plates (Tsamis et al. 2003; Lucklum et al. 2013), bolometers
using PS as a sacrificial layer (Lang et al. 1994), and diffraction gratings (Golub
et al. 2010).
To form thick layers of PS through a mask layer window requires a layer which
is sufficiently robust (hard) to survive long anodization durations (Kaltsas and
Nassiopoulou 1998). SU-8 (MicroChem) is a commonly used negative photoresist
for MEMS processes and has been used for the direct patterning of both p-type (13
.cm) meso- and n-type (1525 .cm) macroporous silicons (Shapley and Barrow
2001). As SU-8 is a strong photoresist which can resist HF attack, anodization times
of up to 2 h were achieved. However, SU-8 is very difficult to remove once hard
baked. Fluoropolymers have a very high resistance to HF, allowing layers as thin as
150 nm to protect both n- and p-type PS during long periods of anodization
(Defforge et al. 2012). Patterning of fluoropolymers is achieved using a mask
layer deposited at low temperature (<200 C) such as PECVD-deposited silicon
dioxide, which itself needs to be patterned photolithographically. Once patterned,
the fluoropolymer protects the PS during photo-electrodissolution and can be
removed post-anodization using an oxygen plasma. Although no damage or oxide
was observed after O2 plasma treatment when analyzed using Fourier transform
infrared spectroscopy in the work by Shapley and Barrow (2001), O2 plasma
treatment has been previously shown to quench photoluminescence (Couillard
and Craighead 1994). While not strictly photolithographically defined, e-beamdeposited diamond-like carbon films as thin as only 1 nm have been shown to be
highly effective in localizing PS formation during anodization, suggesting only
very thin protection layers are required if they are sufficiently resistant to HF
(Djenizian et al. 2003).
Dielectric, semiconductor, or metal layers can also be used as the hard protection
layer, all of which require a two-step process to achieve pattern transfer, namely,
photolithographic patterning of the photoresist on the hard mask and then pattern
transfer into the layer using wet or dry (plasma) etching techniques. Suitable hard
marks are silicon nitride, polysilicon, polysilicon/SiO2, silicon carbide, gold, and
aluminum. Wang et al. observed that compressive stress in Si3N4 masks (50500 nm
thick) was essential to prevent mask cracking (Wang et al. 1995). Lehmann
et al. created circular 1 m diameter features at spacings of 4 m in Si3N4 and
534
A. Keating
SiO2 masks, with a density of 15,000 holes/mm2 (Lehmann and Foll 1990).
Extremely high aspect ratio features were obtained, with holes 42 m deep and 0.6
m in diameter. Similarly patterned silicon nitride masks have also been used to
create PS particles to improve the delivery of insulin (Foraker et al. 2003).
Polysilicon does not have issues with stress fractures during anodization and has a
very high etch selectivity compared to PS (Kaltsas and Nassiopoulou 1998). However, any small current passing through this semiconducting material leads to pore
formation under the mask. By depositing a thin layer of SiO2 with the polysilicon
layer, high electrical insulation and chemical robustness can be achieved allowing
thick PS layers to be created (Kaltsas and Nassiopoulos 1997, 1998). Amorphous
silicon carbide is inert in HF but requires patterning using CF4 plasma etching, which
also etches silicon (Steiner and Lang 1995; Wang et al. 1995).
Some compromise exists with all these methods. Wide undercutting is observed
on insulating masks during anodization of n-type silicon (Steiner and Lang 1995),
more than expected from an isotropic etch associated with the same masking on
p-type substrates (Ohmukai et al. 2005). This is due to an inversion layer formed on
n-type substrates under the mask resulting in a large number of holes that significantly increase the etch rate in this region. Metal masks on either n- or p-type
substrates prevent the inversion layer from forming and result in an undercut
equivalent to the etch depth. Silicon oxide masks are removed during anodization,
while removal of silicon carbide and silicon nitride masks is difficult without
degrading the porous layer formed (Defforge et al. 2012).
In situ patterning: In situ photolithography is a mask-less approach, illuminating
the surface either via holographic (Dalisa et al. 1970) or image projection
(Doan and Sailor 1992a), and can include both photo-electrodissolution and
photo-dissolution mechanisms. Dalisa et al. fabricated the earliest reported PS
device, a grating with 0.4 m pitch created using holographic photoelectrodissolution, combining both electrical bias and illumination (Dalisa
et al. 1970). Several groups later used this holographic illumination technique to
photolithographically pattern gratings. Doan et al. demonstrated pattern definition
by projection through a mask achieving a lateral resolution down to 20 m (Doan
and Sailor 1992a, b). Image projection during anodization was strongly dependent
on light intensity and wavelength, with lower wavelengths providing high resolutions but shallower patterns. Noguchi et al. subsequently observed that by using
light above the bandgap ( > 600 nm), optically induced porosity in n-type silicon
could be induced without externally applied current (Noguchi and Suemune 1993).
Wang et al. demonstrated an alternative in situ masking method, by demonstrating
that a uniformly deposited layer of SiC or Si3N4 could be made to form
photostrictive-induced microcracks by illumination of the layer/Si interface during
anodization (Wang et al. 1995). These cracks allowed electrolyte penetration to the
silicon layer, allowing 100 m features to be formed when an image was projected
onto the surface.
Achieving high resolution by photo-electrodissolution requires short wavelengths (UV) which have very short absorption depths (~0.4 m (Doan and Sailor
535
1992a)). In addition diffraction effects can lead to nonuniform depth profiles, and
Jia et al. (2007) found that bubble formation during photo-electrodissolution
limited the maximum porosity that could be achieved. However, Setzu
et al. proposed that 2D patterning of deep PS structures could be achieved by first
initiating pit formation using holographic projection during anodization for n-type
substrates (with the current off for PS on p-type substrates) and subsequently
performing photo-dissolution while the films remained unbiased in the HF electrolyte (Setzu et al. 2002). Light at 515 nm of intensity 4.4 mW/cm2 was used to form
an interferometric pattern on the surface, forming features of 4 m in n + type
substrates, 2.5 m in macroporous silicon (n-type).
Post-patterning: Post-patterning methods use light either to chemically alter the
PS surface or to transfer a photoresist pattern into the surface of the film. The key
advantage of these methods is that patterning is performed on highly uniform or
multilayered PS films, allowing well-engineered structures to be created. Methods
to achieve photoresist-free patterning of PS can avoid many of the chemical
incompatibilities and process typically associated with microelectronic photolithographic processes. Rea et al. patterned PS by using a laser to oxidize regions of PS,
which could then be removed in HF (Rea et al. 2009), achieving a resolution of
10 m. Using a similar method, Diesinger et al. achieved a high resolution of
200 nm using a tapered fiber tip to focus light at 632 nm, but the induced oxidation/
dissolution only achieved features 6 nm deep (Diesinger et al. 2003).
Patterning of PS using standard microelectronic photolithography based on
photoresist is difficult because the photoresists seep into the pores during/after
spin coating and depending on the photoresist polarity :
(1) For positive photoresists, the UV light does not penetrate deeply into the film
causing no change to the solubility of the photoresist deep in the layer (Ottow
et al. 1996). Unexposed positive resist is not removed by developer. It can be
removed by a stripper or solvent, but this also removes the patterned photoresist
layer. This restricts processes to only thin PS films or requires long exposure
times which leads to poor feature resolution.
(2) For negative photoresists, soft and hard bakes are required to ensure the films
are robust enough for subsequent processing. During baking the resist binds
strongly to the PS pore walls and cannot be easily removed by developer (Ottow
et al. 1996).
Photoresist seepage into the pores can be prevented by using passivating layer on
the PS film. Macroporous photolithographic processing with both positive and
negative resists was achieved using a 100 nm Si3N4 layer (Ottow et al. 1996)
followed by a polysilicon or Al capping layer. Astrova et al. simplified this patterning
process by defining the PS pattern on the backside of a thinned substrate followed by
wet etching (Astrova et al. 2004). Instead of Si3N4 a thick SiO2 passivation was used
to protect the macroporous silicon from alkaline (KOH) developers. More recently a
40 nm titanium layer was used to prevent photoresist seeping into mesoporous silicon
536
A. Keating
having pores ranging from 20 to 45 nm (Zhu et al. 2013). The patterned photoresist
layer could be transferred into the thin titanium layer by a short, 2 s HF dip, allowing
subsequent chemical functionalization of the exposed PS to a depth to 10 m. To
avoid the need for hard capping layers, Lai et al. first backfilled the pores with a
polymer (polyimide) which prevented photoresist seepage but was easily removed
after photolithography (Lai et al. 2011).
Couillard and Craighead (1994) showed that direct application of positive
photoresist could be achieved on a thick layer of macroporous silicon and that the
photoresist pattern could subsequently be transferred via an O2 plasma etch. The
photoresist was developed in a basic solvent (tetramethylammonium hydroxide or
TMAH). These developers rapidly dissolve high-porosity microporous silicon
features; however, PS formed from lightly doped n-type Si can survive this treatment. Positive photoresists and alkaline developers (typically containing metal ions
such as potassium borate) can be used directly on PS if the surface is first partially
oxidized by exposure to ozone. Features of 500 m diameter were fabricated in this
manner on a 60-cycle ruggate filter on p-type silicon (1 m.cm) (Sweetman and
Voelcker 2012). Similarly, a micro-hotplate was made by patterning photoresist
directly on oxidized porous silicon (Tsamis et al. 2003). The oxidized PS allows UV
penetration deeper into the PS films, allowing the positive photoresist in the pores to
be completely exposed. However, oxidation lowers the refractive index of the PS
which is unacceptable in many optical applications. Lai et al. demonstrated a
positive resist process on high-porosity mesoporous silicon by forming a thin
SiOxNy layer protecting the nanoscale pores (Lai et al. 2011). The protective
layer resulted in negligible change in the optical properties but enabled the use of
developers containing 1 % KOH.
Summary
The simplest methods to pattern PS photolithographically are those based on
pre-patterning, where standard microelectronic processing techniques can be
leveraged. However, the mask design and materials must be carefully chosen to
achieve the desired porosity in very small features due to the complex electric field
during anodization that can result. In situ patterning requires both the wavelength
and intensity of the light to be chosen carefully to achieve the desired porosity,
resolution, and depth of patterning. Highly uniform films can be achieved by postpatterning; however, passivation methods are required to protect the film from
aggressive developers, and backfilling/capping layers are required to prevent photoresist seepage into the pores.
Figure 2 summarizes the work on photolithography on PS, showing the relation
between the depth (d) and feature resolution (w) which define the aspect ratio (d/w) of
a patterning process. Quadrants (shaded regions) are loosely identified based on
technologies requiring different aspect ratios. While PS sensors currently have some
of the lowest requirements of feature size and layer thickness, this trend will shift as
patterning technologies for PS mature. An isotropic etch line is included results
537
Fig. 2 Comparison of the resolution (w) and PS depth (d ) resulting from photolithographic
patterning of PS. (a) Chronological reference list; (b) reported resolution/depth overlaid on loosely
assigned applicable fields along with a comparative 1:1 isotropic etch line (dashed line)
above this line suggest significant under etch of the mask or other mechanisms
limiting the aspect ratio. The challenges which remain for photolithographic
patterning of porous silicon are the ability to apply multiple photolithographic
masking steps to porous silicon films, to be able to independently pattern and define
the porosity of multiple layers, to achieve high-resolution patterning of thick microporous silicon layers, to maintain compatibility with CMOS processing (allowing
large-scale manufacturing of PS devices), and to maintain the optical, electrical,
chemical, and mechanical properties of the films throughout these patterning processes. Achieving these goals would significantly advance PS in sensing, photonic,
microelectronic, and micromachining applications.
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Barillaro G, Bruschi P, Lazzerini GM, Strambini LM (2010) Validation of the compatibility
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Colloidal Lithography
Luca Boarino and Michele Laus
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Self-Assembly of Nanospheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Supramolecular Self-Assembly: Formation of 2D Arrays of Colloidal Spheres . . . . . . . . . . . . .
Nanostructuration of Thin Films and Surfaces by Colloidal Lithography . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
542
542
543
543
548
Abstract
This chapter is a visual guide to the numerous approaches to nanolithography

nanofabrication on large area based on supramolecular self-assembly. A short
history of this recent scientific and technological field, an outline of the mostcited methods of self-assembly, and tables reporting different nanofabrication
methods are reported. Indications on requirements, advantages, and drawbacks
of the various approaches are also listed in the table. Thanks to the recently
developed metal-assisted catalytic etching (MACE), the colloidal patterns can
be easily propagated to silicon and other semiconductors opening a wide field of
morphology, nanostructures, and applications.
L. Boarino (*)
Nanofacility Piemonte, Istituto Nazionale di Ricerca Metrologica, Torino, Italy
e-mail: l.boarino@inrim.it
M. Laus
Dipartimento di Scienze e Innovazione Tecnologica (DISIT), Universit del Piemonte Orientale
A. Avogadro, INSTM, UdR Alessandria, Alessandria, Italy
DOI 10.1007/978-3-319-05744-6_55
541
542
L. Boarino and M. Laus
Introduction
Micro- and nanospheres were used in the past for phase separation processes,
cosmetics, electronics, calibration, microfluidics, environment applications, biotechnology, and life science applications including, among others, immunoassays,
cell isolation, biocatalysis, and nucleic acid technology. In recent years, thanks to
the pioneering work of (Deckman and Dunsmir 1982; Hulteen and Van Duyne
1995), micro- and nanospheres as well as nano-objects were employed as building
blocks to form self-assembled masks suitable for large area nanolithography
and nanostructuration of thin films and surfaces. This novel technique, colloidal
lithography, combines the supramolecular self-assembly of single nano-objects,
with thin film deposition, reactive ion etching, epitaxial growth, and
metal-assisted chemical etching. The term polymer colloid (Ottewill 1990)
refers to a dispersion of polymeric spheres in water of nonaqueous solutions
with diameters ranging from hundreds of nanometers to several micrometers.
The first material employed for nanosphere lithography was polystyrene, but a
fine tuning of the polymerization conditions allows for the synthesis of
different monodisperse polymer colloids such as poly(methyl methacrylate) and
other polyacrylates. The synthetic techniques for the preparation of colloids are
known as heterophase polymerizations (Antonietti and Tauer 2003) and include a
variety of different processes including suspension, dispersion, emulsion, as well
as seeded emulsion (Chern 2006) and nanoemulsion polymerizations (Solans
et al. 2005; Asua 2002).
Colloidal systems like silica and polystyrene nanospheres are available in
commerce as aqueous solutions typ. 510 % in volume, with a good control of
size and surface characteristics and functionalization.
Self-Assembly of Nanospheres
The word self-assembly means to build or putting together, without an external
contribution, small building blocks into a periodic structure in which these individual elements are arranged into regular registry. This process is one of the primordial
phenomena happening in nature during the parallel assembly of organic and
inorganic structures at different scales. Despite this remote origin, the interest of
scientists towards this mechanism is rather recent, mainly driven by the fundamental studies of Langmuir and Blodgett on the closed packed arrangements of amphiphilic molecules on liquids and solids (Langmuir and Blodgett 1935). In 1946,
Bigelow and coworkers (Bigelow et al. 1946) observed the dense packing of
monolayers of long chain alkylamines on platinum surfaces. In these systems,
even if it was not recognized at that time, self-assembly was clearly the core
mechanism. More recently, in 1983, Nuzzo and Allara (1983) introduced the
concept of self-assembled monolayers with close packing chemisorbed
alkanethiolate on gold surfaces. Today, it is clear that many driving forces
543
are able to lead to the self-assembly of atoms, molecules, polymers, particles, and
nano-objects. These forces include ionic, covalent, metallic, hydrogen, and coordination bonds but also weak interactions, like van der Waals, - and hydrophobic,
colloidal and capillary, convective and shear, magnetic, electrical, Casimir, and
optical forces. Nevertheless, at the base of the self-assembly, there is the selfrecognition mechanism that was fundamentally summarized by the medieval
alchemists in the sentence similia similibus solvuntur.
Supramolecular Self-Assembly: Formation of 2D Arrays

of Colloidal Spheres
Monodispersed colloidal spheres can be self-assembled into ordered 2D arrays
on solid supports or in thin films of liquids using a number of strategies
(Murray and Winkle 1987; Skjeltorp and Meakin 1988; Denkov et al. 1993;
Picard 1998).
Table 1 shows the main methods, requirements, advantages and drawbacks, and
reference to literature. At the present stage of development, all of these methods are
only capable of generating colloidal arrays built up by small domains, and the
largest single domain usually contains fewer than 10,000 colloidal spheres (Lazarov
et al. 1994). These methods form 2D hexagonal arrays in which the spheres are in
physical contact. To vary independently the lattice constant and the particle size, a
chemical reduction by dry etching is necessary. The self-assembly of nanospheres
is generally limited to 10080 nm. Under this limit, in fact, the synthetic processes
usually produce broad polydispersions, leading to highly defective packed arrays.
Remarkable exceptions are constituted by core-shell particles prepared by seeding
or self-seeding technique (Giani et al. 2003; Antonioli et al. 2012) and silica
particles prepared using TEOS and basic amino acids (Davis et al. 2006; Huang
and Pemberton 2011).
Nanostructuration of Thin Films and Surfaces by Colloidal

Lithography
Once the self-assembly is obtained, and the array of spheres packed, a quantity of
methods have been applied for the propagation of the colloidal mask to the
substrate. This variety of method can be roughly listed in the following categories:
shadow evaporation, growth, dry etching, and ion milling through the interstitial
sites, wet etching, and metal-assisted etching. In Table 2, some of the most-used
techniques of propagation of colloidal masks are shown. Under 50 nm, diblock
copolymers are reaching such a high scientific and industrial consideration to be
cited in the ITRS as a possible alternative to optical lithography for the 22 nm nodes
and for the future (International Technology Roadmap for Semiconductors 2009;
Cheng et al. 2004; Darling 2007; Daga et al. 2011; Andreozzi et al. 2011).
544
Table 1 Supramolecular self-assembly: main methods, characteristics, and reference to literature

Method
Air-liquid
interface,
Langmuir
Blodgett
Requirements
Spreading agent
(ethanol,
methanol),
control of particle
surface charge,
control of the
particle
immersion,
addition of
surfactant for
packing, control
of water Ph
Advantages
Large ordered
areas, applicable
to any surface,
no need of
surface
functionalization
Drawbacks
Only
floating
nanospheres
Slow
evaporation
Piranha
functionalization
of substrates, use
of different
solvents like F-oil
or mercury
Good packing,
large ordered
domains
Applicable
only to
idrophilic
surfaces,
presence of
double
layers
Spinning
Substrate
treatment with
wetting agent or
surfactant,
Piranha
functionalization
Solid electrodes,
polarization
50100 V/cm
Good packing,
reduced double
layers, large
ordered
domains, highly
industrializable
Assembly of
small metal
particles (under
50 nm)
Applicable
only to
hydrophilic
surfaces, no
order under
50 nm
Complexity
of setup,
limited
ordered
domains
Electrophoretic
Capillarity
Optical forces
Capillary setup,
micrometric slits
Laser-based
optical standing
wave pattern
Arbitrary 2D or
3D patterns
Complexity
of setup
Complexity
of setup
References
Hurd and
Schaefer (1985),
Horvolgyi et al.
(1994), Wickman
and Korley
(1998), Kondo
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Deckman et al.
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Lenzmann et al.
(1994), Fulda and
Tieke (1994),
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(1997), Siroktin
et al. (2010)
Nagayama
(Denkov et al.
(1992, 1993),
Dimitrov and
Nagayama
(1996), Velev
et al. (1993),
Dimitrov et al.
(1999), Lazarov
et al. (1994))
Deckman et al.
(1988), Hulteen
and Van Duyne
(1995)
Richetti et al.
(1984), Trau et al.
(1996, 1997), Yeh
et al. (1997),
Solomentsev et al.
(1997)
Sun and Yang
(2006)
Misawa et al.
(1992), Mio and
Marr (1999)
Scheme
Material
Silicon
Silicon dioxide,
silicon
Graphene
Metals, silicon
Building block
Carboxylate
polystyrene
nanospheres
Polystyrene
nanospheres
Polystyrene
nanospheres
Polystyrene
nanospheres
Table 2 Widely used techniques of colloidal lithography and relative literature references
Thermal evaporation,
tilted thermal
evaporation, e-gun,
sputtering
RIE
DRIE
Method
RIE
(continued)
Deckman and Dunsmuir

(1982); Haynes and Van
Duyne (2003); Kosiorek
et al. (2004); Patzig et al.
(2008)
Liu et al. (2011)
Cheung et al. (2006);

Li et al. (2007)
Reference
Chau and Melvin (2008)
545
Scheme
Table 2 (continued)
Glass
GaN
Polystyrene
nanospheres,
CdSe QDots
Polystyrene
nanospheres
GaN, ZnO
Si, SiO2, glass,

thin metal films,
Au, Si, Ni, Co,
Py, others
Polystyrene
nanospheres
Polystyrene
nanospheres
Si
Material
Silver, silicon
Building block
Polystyrene
nanospheres
RIE, thermal
evaporation, e-gun,
sputtering, ion
milling
Vapor-liquid-solid
MBE
Evaporation
templating
Method
Metal-assisted
etching
Tiberto et al. (2010, 2011)
Fan et al. (2006)
Bengoechea-Encabo et al.
(2012)
Fuhrmann et al. (2005)
Chen et al. (2009)
Reference
Huang et al. (2007);
Boarino et al. (2009, 2011)
546
N-type silicon
<111>, SiO2
PS, PMMA, other

polymers
Silicon, SiO2,
optical
photoresist
Polystyrene
nanospheres,
Fe, Ni, carbon
nanotubes
Silica
nanospheres
Polystyrene
and silica
nanospheres
UV exposure, UV
laser ablation
Heating of substrate
above polymer Tg
(glass transition
temperature)
Plasma-enhanced hot
filament chemical
vapor deposition
Wu et al. (2007); Grojo

et al. (2012)
Jang et al. (2008)
Huang and Carnahan

(2003); Xu et al. (2009);
Park et al. (2005)
547
548
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Imprinting Porous Silicon

Judson D. Ryckman and Sharon M. Weiss
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Substrate Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Achievable Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
552
552
554
557
Abstract
This chapter describes the capabilities of the direct imprinting of porous substrates (DIPS) technique for patterning and modifying the physical properties of
porous silicon films. DIPS can achieve very high-resolution two-dimensional
and three-dimensional patterning with feature sizes below 100 nm while
eliminating the need for intermediate masking materials and etch recipes that
complicate and increase the expense of other patterning techniques. The DIPS
process utilizes a reusable master stamp to imprint the desired pattern into
porous silicon by directly applying the stamp to the porous substrate with a
pressure on the order of 100 MPa. This process is performed in a matter of
seconds at room temperature. In addition to enabling the fabrication of patterned
porous silicon structures, DIPS also enables morphological control over material
properties including porosity, pore size, and refractive index. Examples of
designs fabricated by DIPS include grating-coupled wave guides, free-standing
particles, and curvilinear structures such as lenses.
J.D. Ryckman S.M. Weiss (*)

Department of Electrical Engineering and Computer Science, Vanderbilt University,
Nashville, TN, USA
e-mail: sharon.weiss@vanderbilt.edu
DOI 10.1007/978-3-319-05744-6_56
551
552
J.D. Ryckman and S.M. Weiss
Introduction
While several imprinting techniques have been established for polymers and other
soft materials (Sotomayor Torres 2003), imprinting has only recently been demonstrated as a high-fidelity, low-cost, and straightforward method for patterning
porous silicon and other porous materials including nanoporous gold, porous
titania, and porous alumina (Ryckman et al. 2011a). This process, referred to as
direct imprinting of porous substrates (DIPS), overcomes several key challenges
associated with applying conventional lithographic techniques to porous media.
First, traditional lithography strategies (e.g., electron-beam lithography (EBL) or
photolithography) are often expensive and limited by a trade-off between resolution
and throughput. Second, resists and thermoplastics are likely to infiltrate the pores,
potentially modifying the internal porous structure and often proving very difficult
to remove, especially in deep porous networks. Third, wet etching is not always an
option due to chemical incompatibilities, and dry-etching techniques can be expensive and require specific chemistries that must be appropriately characterized and
tailored for each unique porous material. As an imprinting process, DIPS can
achieve very high-resolution patterning while overcoming many of the aforementioned challenges through eliminating the need for intermediate masking materials
and etch recipes.
Figure 1a illustrates the DIPS process. Similar to nanoimprint lithography (Chou
et al. 1996), DIPS first relies on the fabrication of a reusable stamp. Silicon is a
convenient stamp material owing to its large material hardness (~10 GPa) and to the
large variety of imprintable patterns that can be readily fabricated through conventional lithographic techniques. Moreover, for patterning porous silicon films, using
a silicon stamp minimizes contamination issues, which is especially important for
nanoparticles designed for biomedical applications. After preparing the reusable
stamp, the porous material must be prepared on a solid substrate support, for
example, silicon, glass, or metal. For porous silicon, the parent silicon wafer is an
excellent natural support, although it is possible to lift-off porous layers for
anchoring to alterative substrates prior to or after performing DIPS. Imprinting is
then performed by directly applying the stamp to the porous substrate at a pressure
on the order of 100 N/mm2 (100 MPa). The straightforward process can be
performed in a matter of seconds at room temperature without the need for any
curing, developing, baking, or etching processes (which are often required in
nanoimprint lithography or soft lithographic techniques).
Substrate Characteristics
As a heterogeneous material, porous silicon offers unique and tunable mechanical
characteristics that can deviate quite dramatically from homogenous bulk solids
(see the other chapters in this handbook Tunable Properties of Porous Silicon
and Mechanical Properties of Porous Silicon). For mid- to high-porosity
mesoporous films (~5080 %), imprinting results in localized and permanent
553
1.
2.
Reusable stamp
Lithography
RIE
Substrate support
(glass, Si, or metal)
Porous nanomaterial
(pSi, np-Au, etc.)
Porous nanomaterial
prepared on support
Bring stamp
into contact
3.
Apply
pressure
Remove
stamp
b
c
(nm)
100
5
0.75m
10
15
(m)
Fig. 1 (a) Illustration of the direct imprinting of porous substrates (DIPS) process. (b) Crosssectional SEM images (45 tilt) of unstamped and stamped regions of a 1-m-thick mesoporous
silicon film (the white arrows indicate highlighted typical pores). Following DIPS, a second layer
could be uniformly etched into the substrate. (c) AFM height image of a typical porous silicon
substrate film after performing DIPS (Adapted with permission from Ryckman et al. (2011a).
Copyright 2011, American Chemical Society)
554
mechanical deformation, enabling high-fidelity micro- and nanostructures to be

fabricated. Figure 1b shows the imprinting behavior of a ~1-m-thick porous
silicon film with pore diameters approximately 3040 nm. After imprinting with
a grating patterned stamp (area 9 mm2; grating pitch, 5 m) at a force of
~2 kN, as schematically illustrated in Fig. 1, the imprinted regions are compressed
to a thickness of approximately 615 nm, while the other regions remain untouched.
The mesoporous network accommodates the reduction in volume by bending and
compressing pores together. After imprinting, the sample was returned to the
electrochemical cell to demonstrate that ethanolic HF solution readily infiltrates
the imprinted porous silicon layer, enabling etching to be reinitiated where the
pores were previously terminated. SEM imaging (Fig. 1b) reveals that the etching
of a second porous layer (20 mA cm2, 30 s) proceeded uniformly in both the
imprinted and nonimprinted regions. This opens the possibility of fabricating
devices through a multistep approach, where further electrochemical etching can
be performed following DIPS.
Imprint depths ranging from only a few nanometers to the micron-scale have
been demonstrated using DIPS (Ryckman et al. 2011a). High-resolution control
over the imprint depth can be obtained by tuning either the applied pressure or a
variety of film properties including porosity, thickness, or conditioning methods
such as oxide growth. At imprint depths beyond approximately 10 % of the original
film thickness, the effective hardness of the film may be influenced by the underlying substrate, resulting in thickness-dependent hardness and imprint depths
(Ryckman et al. 2011a; Blau and Lawn 1986). Conditioning can significantly
impact thin film hardness and reduce the achievable imprint depth owing to
reducing porosity and strengthening the interconnected mesoporous network
(Fang et al. 2009). In most cases, the maximum imprintable film fraction is
approximately equal to the initial porosity, as volume reduction coincides with
reduction of the void fraction. Uniform imprinting over large areas, ~825 mm2, is
readily achievable with DIPS. However, technical challenges associated with
sample uniformity and leveling, long-range flexing of the stamp or substrate, and
uniform application of pressure need to be addressed to enable large-scale application of DIPS over wafer-sized areas. Step-and-repeat imprinting is one possible
approach, although increased complexity for proper alignment may be required.
Novel stamping configurations and alternative stamp or substrate materials merit
exploration, especially for improving stamp durability, sample yield, and large area
uniformity.
Achievable Structures
Figure 2 illustrates the variety of porous silicon structures that can be fabricated
using DIPS. By imprinting a pattern into a single layer of porous silicon and then
reinserting the sample into the etch cell for subsequent layer formation, as
discussed above, multilayer structures such as grating-coupled wave guides
(Fig. 2a) and 3D ridge wave guides (Fig. 2b) can be realized (see other chapter
555
Fig. 2 Example structures fabricated by imprinting porous silicon: (a) grating-coupled waveguide.
(b) Ridge waveguide operating at 1550 nm, (c) Vanderbilt text, (d) nanoscale grating, (e)
individual microparticle, (f) monodisperse photoluminescent particles, (g) gradient sloped blazed
grating, (h) AFM images of 3D digital Mario, and (i) curvilinear gradient refractive index bowl (af:
Adapted with permission from Ryckman et al. (2011a). Copyright 2011, American Chemical Society.
gi: Courtesy Judson D. Ryckman, adapted from work described in Ryckman et al. (2013))
556
in this handbook Porous Silicon Optical Waveguides) (Ryckman et al. 2011b;

Wei and Weiss 2011). In the case of waveguide formation, the porous silicon
multilayer provides out-of-plane optical confinement, while in-plane optical
confinement is provided by the patterned boundaries and the increased refractive
index of the densified porous region. High-fidelity patterning of complex patterns
with finely curved (Fig. 2c) or straight (Fig. 2d) features can be achieved simply
by using the appropriate stamp. Notably, the patterning resolution is primarily
limited by the pore size. Thus, DIPS can readily achieve feature sizes <100 nm in
a variety of porous substrates.
DIPS can also be used to fabricate micro- or nanoparticles with well-defined
shapes and sizes (Fig. 2e, f). After performing DIPS, free-standing particles are
produced by detaching the patterned structures from the substrate. This can be done
by using the combination of frictional and electrostatic forces that exist between the
stamp and the imprinted structure, performing ultra-sonication in an aqueous
solution, electrochemical lift-off, or by simply applying and removing an adhesive
such as carbon tape. Selected particles can exhibit highly desirable traits for use
in vivo that include efficient loading of therapeutics or imaging contrast agents,
distinctive photo-luminescence or other signatures, and biodegradability. Importantly, the DIPS process preserves the pore volume in the core of the particles
compared to milling techniques where sintering can occur. Figure 2f shows that
DIPS-fabricated microparticles maintain their photoluminescent properties and
show excellent size monodispersion.
DIPS is most commonly implemented using stamps with a binary 2D pattern,
where imprinting is performed at a uniform depth across the sample. However,
there is no fundamental limitation that would prohibit the fabrication of more
complex 3D structures by utilizing a pre-mastered 3D stamp. For example, through
the use of gray-scale electron-beam lithography and reactive ion etching, 3D silicon
stamps can be fabricated and then applied to fabricate 3D structures in porous
substrates. With this approach, blazed gratings, digital patterns, and curvilinear
structures have all recently been demonstrated in porous silicon (Fig. 2gi;
Ryckman et al. 2013). DIPS-fabricated blazed gratings, for example, could be
used to improve coupling efficiency in grating-coupled porous silicon waveguides
(Wei and Weiss 2011) or enhance diffraction efficiency in diffraction-based biosensors (Ryckman et al. 2010). Notably, the application of a 3D stamp enables not
only the fabrication of 3D structures but also enables morphological control over
material properties including porosity, pore size, and refractive index. Digital
patterns could be used, for example, to achieve complex optical structures, (i.e.,
for holographic applications) or to locally and discretely pattern a range of pore
sizes for size-selective sensing of small molecules on the same chip. Curvilinear
structures fabricated from porous silicon have the potential to serve as low-cost
micro-optic structures, such as lenses, while the ability to make a well-controlled
gradient refractive index could enable the straightforward fabrication of transformation optical devices.
557
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Drying Techniques Applied to

Porous Silicon
Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Air-Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Survey of Drying Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Supercritical Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
559
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Abstract
Wet-etched mesoporous silicon is normally dried in air, but this limits the range
of porosities and surface areas achievable, due to capillary force-induced collapse of the silicon skeleton. The various alternative drying techniques are
reviewed with particular attention paid to supercritical drying, a powerful
technique applicable to all physical forms of porous silicon.
Introduction
When porous silicon is fabricated via any route that uses liquids (see handbook
chapter Routes of Formation for Porous Silicon), it requires careful drying.
Drying stresses due to liquid surface tension are primarily responsible for the
changes that occur. Drying science and technology has at least two dedicated
journals, emphasizing its importance in materials science in general and
nanomaterials in particular (Wang et al. 2005; Pakowski 2007). The seminal
work of Scherer in the drying of highly porous silica from gels (Scherer 1990)
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_57
559
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L. Canham
clarified the interplay of fluid flow and differential shrinkage of the solid network
that can occur as a result of capillary stresses. This chapter first describes the
degradation of porous silicon films during air-drying that has been revealed and
then surveys the different methods of drying applied to date. Most attention is given
to pentane drying and critical point (supercritical) drying. The former technique
is easiest to implement and can significantly reduce but not eliminate dryinginduced changes. The latter technique has been shown to be the most powerful
technique for mesoporous silicon and is also now utilized by the silicon
micromachining community.
Air-Drying
An electrochemically etched mesoporous silicon film on a wafer can visually have
good macroscale uniformity when still wet (see handbook chapter Color of
Porous Silicon), but become crazed and sometimes even disintegrates as it dries in
air. Normal air-drying of films leads to progressively increasing and often dramatic
shrinkage, cracking, and peeling of the layer as the porosity and/or thickness is
increased (see Fig. 1 example). This is caused by the buildup of capillary forces that
arise from pore liquid evaporation. The maximum amplitude of the associated
stresses occurs when the menisci enter the pores. A variety of different dryinginduced morphologies can result (Wang et al. 2009; Xu and Wang 2009;
Skryshevsky et al. 2011; Wang et al. 2013). Bellet and co-workers have shown
that the Laplace equation can be used to quantify those stresses which are directly
Fig. 1 Shrinkage and crack development in a highly porous silicon film during air-drying,
as revealed by sequential wide-field photoluminescence imaging (Mason et al. 2002)
Drying Techniques Applied to Porous Silicon
561
proportional to the surface tension of the fluid and inversely proportional to the
radius of the meniscus and hence increase with decreasing pore size (Belmont
et al. 1996; Bellet 1997; Bellet and Canham 1998).
Whether or not a given porous silicon structure is degraded by those stresses
depends on its mechanical properties (see handbook chapter Mechanical Properties of Porous Silicon). Experimentally, for layers of fixed porosity and pore size
distribution, the onset of cracking and macroscopic deformation has been shown to
be strongly related to layer thickness. Below a critical value hcrit., cracking of the
air-dried film can be completely absent, as monitored by electron microscopy.
Drying-induced damage is thus much more prevalent for thick films and for
microporous and mesoporous films than for macroporous ones.
Air-drying effects on morphology and properties have received continuous study
(Gruning and Yelon 1995; Amato et al. 1996; DiFrancia et al. 2000; Lerondel
et al. 2000; Chamard et al. 2001; Lei et al. 2006; Qiu et al. 2008; Wang et al. 2009;
Gaev and Rekhviashvili 2012). In order to maintain the delicate nanostructures
created by wet etching, a number of drying techniques have been investigated and
these are surveyed in the next section.
Survey of Drying Techniques

A variety of strategies have been investigated to minimize fracture and shrinkage of
highly porous materials during drying or at least improve reproducibility of material properties. Table 1 lists various drying techniques available and indicates those
studies that used specific drying techniques on porous silicon structures to date. The
one technique listed which does not appear to have been used yet with mesoporous
silicon is microwave drying, although it has been utilized, for example, with
mesoporous silica (Bhagat et al. 2008).
Vacuum drying, derivatization with subcritical drying, slow controlled drying,
microwave drying, and spray drying do not avoid capillary forces; their merits lie
elsewhere. Pentane drying is a facile technique to significantly increase the critical
thickness h crit for layer cracking. Here water in the pores is replaced first by ethanol
and then pentane before drying in air, since pentane has a very low surface tension.
It reduces capillary forces but does not eliminate them.
Two established methods of avoiding the liquid/vapor interface during drying are
illustrated in Fig. 2, namely, freeze-drying and supercritical drying. Freeze-drying has
proved successful in foodstuff preparation but has not worked as well with mesoporous
inorganic materials. We therefore look in more detail at supercritical drying.
Supercritical Drying
Of the techniques listed in Table 1, supercritical drying appears the most powerful for achieving very high porosity or very high surface area silicon structures
(see handbook chapter Pore Volume (Porosity) in Porous Silicon). The fluid
562
L. Canham
Table 1 Drying techniques of relevance to highly porous silicon

Drying
technique
Atmospheric
drying
Vacuum drying
Freeze-drying
(lyophilization)
Supercritical
drying (critical
point drying)
Derivatization
and subcritical
drying
Pentane drying
Basis of technique
Pore fluid evaporates
into air
Transfer of wet
structure into
evacuated chamber
Pore fluid is frozen
then sublimed in
evacuated chamber
Pore fluid is removed
after conversion into a
supercritical state
Slow controlled
drying
Chemical surface
modification prior to
atmospheric drying
Pore fluid is replaced
by liquid pentane
which is then allowed
to evaporate in air
Evaporation rate is
controlled and lowered
Microwave
drying
Evaporation rate is
increased
Spray drying
Very useful for

nanocomposite
particle formation or
microencapsulation
Advantage
Convenience
Use with porous silicon

The vast majority of studies
Avoids exposure
to air (oxygen)
Koizumi et al. 1996
Industrial process
in widespread use
Amato and Brunetto 1996,

Amato et al. 1997
Avoids capillary
stresses
Industrial process
Canham et al. 1994
Mechanical
strengthening of
network
Minimizes
capillary stresses
More
reproducibility of
capillary stress
effects
Industrial process
Lower drying
times
Industrial process
in widespread use
Frohnhoff et al. 1995

Von Behren et al. 1997
Xu et al. 1998
Kolasinski et al. 2000
Chang et al. 2011
Linsmeier et al. 1997
Bellet 1997
Oton et al. 2002
Pellegrini et al. 1995
Jung et al. 2013
used is normally carbon dioxide since its critical temperature (304.1 K) is

conveniently low (see Fig. 3). The HF-based electrolyte used in, for example,
anodization is first removed from the pores by extensive ethanol rinsing, and then
the alcohol is replaced by liquid carbon dioxide. This is then compressed and
heated in an autoclave beyond its critical point. After further flushing to remove
residual ethanol, it is then converted to a gas through pressure reduction at
constant temperature. The overall phase diagram path is shown by the red
arrow in Fig. 2.
Supercritical drying of porous silicon films on wafers has been particularly
successful (see references in Table 1) and should be applicable to other physical
563
Fig. 2 The phase transitions involved in water-air, ethanol-air, or pentane-air-drying (green

arrow); freeze-drying (blue arrow); and supercritical drying (red arrow) of wet porous silicon.
For air-drying, the liquid L in the pores immediately becomes a gas G via evaporation. For freezedrying, it is first solidified (S) and then becomes a gas via sublimation around the triple point.
For supercritical drying, it is taken around the supercritical point to become a gas
10,000
solid
supercritical
fluid
pressure
P (bsi)
1,000
liquid
100
critical point
10
triple point
gas
1
200
250
300
350
400
temperature
T (K)
Fig. 3 The phase diagram of carbon dioxide, the most popular supercritical solvent
forms such as membranes, microparticles, nanowire arrays, and nanoparticles.

Of particular relevance in this regard is that the silicon MEMS community also
utilizes this technique to avoid micromachined structure stiction, to clean
silicon surfaces, and to improve device yield (Kim et al. 1998; Jafri et al. 1999;
564
L. Canham
Fig. 4 Supercritical dryers, (a) benchtop system (Quorum Technologies Ltd, UK) for processing
stain-etched porous Si powders, (b) benchtop system (Quorum Technologies Ltd, UK) for
processing an anodized 150 mm diameter silicon wafer, (c) cleanroom-compatible automated
multiwafer system (Tousimis Corp., USA)
Namatsu et al. 1999). There are now commercially available systems for both
silicon powder and wafer batch processing (Fig. 4). Supercritical fluids could also
be utilized in the purification of porous silicon (Koynov et al. 2011).
Concluding Remarks
The uniformity and properties of wet-etched mesoporous silicon can be adversely
affected by how it is dried. Air-drying can lead to substantial loss of porosity and
surface area.
In a number of applications, the benefits of porous silicon scale with its surface
area, pore volume, or a combination of the two. In drug delivery, for example,
small molecule API payload can be increased by increasing pore volume; large
biomolecule payload can rely on large internal surface areas accessible by large
pores. Supercritical drying, rather than air-drying, adds expense to manufacture
but is likely to be important for material optimization in many high-value
applications.
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Amato G, Brunetto N, Parisini A (1997) Characterization of freeze-dried porous silicon. Thin
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Bellet D (1997) Chapter 1.5: Drying of porous silicon. In: Canham LT (ed) Properties of porous
silicon. IEE, London, pp 3843
Bellet D, Canham LT (1998) Controlled drying: the key to better quality porous semiconductors.
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Belmont O, Bellet D, Brechet Y (1996) Study of the cracking of highly porous p+ type silicon
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Canham LT, Cullis AG, Pickering C, Dosser OD, Cox TI, Lynch TP (1994) Luminescent silicon
aerocrystal networks prepared by anodisation and supercritical drying. Nature 368:133135
Chamard V, Pichat C, Dolino G (2001) Rinsing and drying studies of porous silicon by high
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Chang SW, Chuang VP, Boles ST, Ross CA, Thompson CV (2011) Densely packed arrays of
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DiFrancia G, Ferrara V, Lancellotti L, Quercia L (2000) Stress measurement technique to monitor
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Frohnhoff S, Arens-Fischer R, Heinrich T, Fricke J, Amtzen M, Theiss W (1995) Characterization
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Gaev DS, Rekhviashvili SS (2012) Kinetics of crack formation in porous silicon. Semiconductors
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electronic states and photoluminescence properties of porous silicon. Jpn J Appl Phys 35:
L803L806
Kolasinski KW, Barnard JC, Ganguly S, Koker L, Wellner A, Aindow M, Palmer RE, Field CN,
Hamley PA, Poliakoff M (2000) On the role of the pore filling medium in photoluminescence
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Koynov S, Pereira RN, Crnolatac I, Kovalev D, Huygens A, Chirvony V, Stutzmann M, deWitte P
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Homoepitaxy on Porous Silicon

Barbara Terheiden
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Epitaxy on A Sintered Porous Si Surface Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Homoepitaxy with Atmospheric or Reduced Pressure Chemical Vapor
Deposition (APCVD, RPCVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Homoepitaxy Applying LPCVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Homoepitaxy Applying Liquid Phase Epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Epitaxy on Non-Sintered Porous Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experiments of Homoepitaxy on Non-reorganized Porous Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Simulations of Homoepitaxy on Non-reorganized Porous Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Homoepitaxy Applying Ion-Assisted Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
Homoepitaxy on porous Si aims at producing monocrystalline thin silicon-oninsulator wafers or monocrystalline thin Si solar cells. There are two methods of
preparation of the porous Si layer for homoepitaxy: on the one hand, the porous
Si is reorganized at elevated temperatures to close the surface as a seed layer for
epitaxy, and on the other hand, the reorganization of the porous Si is avoided to
keep the open pore structure. For homoepitaxy on the porous Si layers, most
research has been reported on the usage of atmospheric pressure chemical vapor
deposition (APCVD). The quality of epitaxially grown Si layers, using different
deposition techniques and various types of porous silicon, was assessed by etch
pit density, minority carrier lifetime, Hall mobility, microscopy, and device
B. Terheiden (*)
Department of Physics, University of Konstanz, Constance, Germany
e-mail: barbara.terheiden@uni-konstanz.de
DOI 10.1007/978-3-319-05744-6_58
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B. Terheiden
performance. It can be concluded that APCVD is in combination with a closed

porous Si surface layer as a seed layer, the most promising approach to produce
high-quality epitaxial layers.
Introduction
Homoepitaxy on porous Si aims at producing monocrystalline thin silicon-oninsulator (SOI) wafers or monocrystalline thin Si solar cells. While Si epitaxial
layers for SOI wafers are in a thickness range of 100 nm, Si solar cells show mainly
layer thicknesses of 2050 m (see related application chapter in handbook
Porous Silicon and Solar Cells). Thin epitaxial solar cells based on
multicrystalline porous Si substrates have not been reported up to now.
There are two methods of preparation of the porous Si layer for homoepitaxy: on
the one hand, the porous Si is reorganized at elevated temperatures to close the
surface as a seed layer for epitaxy, and on the other hand, the reorganization of the
porous Si is avoided to keep the open pore structure. Therefore, thermodynamics
that drives a system to minimize its surface energy is the one mans meat but is
another mans poison. Historically epitaxy on non-reorganized porous Si was
demonstrated before epitaxy on closed Si surfaces (Unagami and Seki 1978).
These two approaches put very different constraints on the epitaxy process.
While the closed surface of the porous Si layer allows for high temperatures for
epitaxy to achieve a high-quality epitaxial layer, in contrast lower temperatures are
beneficial in case of the open structure of the porous Si layer. Both approaches are
able to generate monocrystalline Si epitaxial Si layers on the porous Si layer with
the same crystal orientation as the substrate wafer (Unagami and Seki 1978;
Brendel 1997).
All but one of the reported epitaxial layers was grown on porous Si that was
electrochemically etched. Terheiden et al. (2011) showed that an epitaxial Si layer
can be detached from chemically etched porous Si on a 150 mm wafer.
For homoepitaxy on the porous Si layers, the usual Si epitaxy methods are
applied. Most research has been reported on the usage of atmospheric pressure
chemical vapor deposition (APCVD). But also low-pressure CVD (LPCVD),
molecular (MBE) or electron beam epitaxy (EBE), liquid phase epitaxy (LPE),
and ion-assisted deposition (IAD) were applied.
A very different approach of combining an epitaxial Si layer and porous Si is the
engineering of tensile stress in thinnest Si layers by first epitaxially depositing a
very thin Si layer on a Si wafer and subsequently porosifying the Si wafer
(Boucherif et al. 2010).
In the following, the quality of epitaxial Si layers deposited either on an annealed
porous Si layer or on a non-annealed porous Si layer is discussed. The epitaxial
layer quality is evaluated by etch pit densities, defect densities, minority carrier
lifetimes, or solar cell efficiencies. Table 1 gives an overview on the main characteristics of the epitaxial Si layers on the different types of porous silicon layers, i.e.,
single or double layers.
569
Table 1 The main characteristics of the epitaxial Si layers on various types of porous silicon
layers
Double layer
Single layer
Annealed
Stacking faults 4,105/cm2
Point defects 6,230/cm2 (Tayanaka
et al. 2001) Etch pit density (100) Si
5 103/cm2 (Van Nieuwenhuysen
et al. 2012)
eff 100 s (10 m Si thickness)
(Tayanaka et al. 1999)
Leff 232 m (Petermann et al. 2012b)
Layer transfer successfully
demonstrated (chemically etched)
(Terheiden et al. 2011)
Non-annealed
Density of stacking faults (111) Si
9 109 cm2 to 4 107 cm2;
Etch pit density (100) Si 103104 cm2
(Krinke et al. 1999)
Defect density 3.5 108 cm2

(Jin et al. 2000)
Defect densities highly doped
substrate as low as without porous Si
layer lowly doped substrate 107108
cm2 (Oules et al. 1992)
Epitaxy on A Sintered Porous Si Surface Layer

The starting layer for epitaxy is generated by sintering the porous Si layer at
temperatures of 1,0001,200 C in hydrogen atmosphere as first published by
Labunov et al. (1986). They found that a pore-free layer, a crust, was built on the
porous Si layer. Therefore, a reorganized porous Si layer offers a sealed crystalline
Si surface as a seed layer comparable to a Si wafer surface. The pore-free layer
(Labunov et al. 1986) or sometimes also called dense surface layer (Jin
et al. 2000) is used for all applications nowadays. For a processing review in the
handbook dedicated to sintering, see Sintering of Porous Silicon.
Since the reorganized porous Si layer is high temperature, stable Si deposition
can be carried out at high temperatures of above 1,000 C allowing for a highquality Si layer. High annealing and epitaxy temperatures are beneficial for reducing the defect densities (Sato et al. 1996a). Crystal defect densities are determined
in most cases by counting etch pit densities on the epitaxial Si layer. The most
common etching solution to make the etch pits visible is based on Cr2O72 as
suggested by Secco dAragona (1972). Depending on the type of defect, different
shapes of pits become visible (Rauh 1989) depending also on the crystal
orientation.
There are different requirements in the crystal quality for the various applications. While for SOI wafers, lowest defect densities of not more than 10/cm2
(Hitchman and Jensen 1993a) for solar cells even 5,00010,000/cm2 are acceptable
for a wide range of efficiencies (Van Nieuwenhuysen et al. 2012). For SOI wafers,
the surface roughness needs to be very low to avoid device failures. In case of solar
cells, the surface is textured with a feature size of above 1 m.
For the application of such epitaxially grown, monocrystalline Si layers in the
field of photovoltaics, a reuse of the Si substrate and a high-throughput epitaxy
570
B. Terheiden
reactor is indispensible. Both topics may influence the crystal quality of the
epitaxial layers on porous Si: for the reuse of the substrate, the surface conditioning
after the liftoff of the epitaxial layer has to be considered, while a high-throughput
reactor might imply some constraints to process conditions and thus to the crystal
quality of the epitaxial Si layer. In case of using epitaxially grown layers for siliconon-insulator (SOI) processes, the throughput of the epitaxial reactor is not of that
great importance, but the reuse of the Si substrate is also desirable (Sakaguchi
et al. 1997). In addition, the constraints on the crystal quality are higher for SOI
wafers than for solar cells. Also any kind of dopant out-diffusion out of the highly
doped porosified Si substrate during epitaxy is for SOI wafer unwanted, but in
contrast it can be used to generate, for example, a pn-junction or a p+/p or n+/n
junction (Wolf et al. 2007) in solar cells.
Homoepitaxy with Atmospheric or Reduced Pressure

Chemical Vapor Deposition (APCVD, RPCVD)
Silicon-on-Insulator Wafers
Silicon-on-insulator (SOI) wafers became increasingly dominating in ultra largescale integration (ULSI) electronic circuits from about 1998 on (Celler and
Cristoloveanu 2003). Different approaches were followed, and only a few are
now in industrial production. The Epitaxial Layer Transfer (ELTRAN ) process,
a special Bond and Etch-back SOI process (BESOI), is the only one based on
transfer of an epitaxial Si layer using porous Si (Yonehara et al. 1994). While the
first approaches of ELTRAN included a removal of the seed wafer, further
developments led to a splitting along a high-porosity layer using a waterjet
(Yonehara and Sakaguchi 2002) which makes a reuse of the growth substrate
possible and thus the process much more cost-effective.
Using for SOI, an approach based on an epitaxial layer avoids defects in the
epitaxial layer as crystal originated particles. But dislocations and stacking faults can
occur. These defects can be made visible by Secco etching (Secco d Aragona 1972).
Including in addition to the hydrogen annealing of the porous Si, a preinjection of Si
during this anneal but before epitaxial layer deposition a defect density as low as
10/cm2 was achieved (Yonehara and Sakaguchi 2001). The preinjection of Si helped
to reliably close all pores before epitaxy. After epitaxy and attachment to the handle
wafer, the seed wafer is removed, and the porous layer is etched back wet chemically
(Sakaguchi et al. 1995) which is followed by a hydrogen annealing to smoothen the
surface (Sato et al. 1996b). On a 300 mm Si wafer, a thickness uniformity of
(147 1.6) nm was achieved (Yonehara and Sakaguchi 2002). The epitaxy was
carried out between 900 C and 1,000 C by APCVD or RPCVD.
Photovoltaics
Applying homoepitaxy on mesoporous Si after reorganization and detaching, these
layers from the Si substrate wafer were introduced by Tayanaka (Tayanaka and
Matsushita 1996; Tayanaka et al. 1998) and Brendel (1997). Both approaches use
571
the thin pore-free Si layer (Labunov et al. 1986) as a seed layer for homoepitaxy and
a high-porosity layer for separation of the epitaxial film from the substrate. Different Si deposition methods as APCVD (Brendel et al. 1998; Tayanaka et al. 1998),
LPCVD (Poortmans et al. 2000), and LPE (Nishida et al. 2001; Berger et al. 2001)
were investigated to grow the epitaxial Si layer on top of the pore-free surface layer.
The most reliable technique in terms of crystal and electronic quality of the
epitaxial layers is APCVD in reactors established in microelectronics (Hitchman
and Jensen 1993a). All techniques were applied on planar porous Si substrate.
However, Kuchler et al. applied APCVD for the first time also on porous Si surfaces
which were textured with random upright pyramids (Kuchler et al. 2000). The Si
film did not grow conformal to the surface but had a planar surface. After detaching
the film from the growth substrate, the surface of the epitaxial layer shows a replica
of the texture from the Si substrate wafer.
The quality of p-type B-doped epitaxial Si layer deposited by using APCVD
was investigated by Tayanaka et al. (2001) in detail in 2001. Epitaxial layers of
10 10 cm2 were defined on a 6 in. Si substrate after sintering the porous Si layers
for closing the porous Si surface. The epitaxy was carried out in an APCVD reactor
at 1,100 C using SiCl4 and B2H6 gas. Forty-eight solar cells were made on this
layer to directly correlate crystal quality with solar cell efficiency. The defects were
detected by optical microscopy. Stacking faults, point defects as well as small and
large circle defects were identified. The latter two were only found on the epitaxial
layers. It was assumed that those circle defects originate from particles lying on the
porous Si layer when the epitaxy started. Depending on where they were in the
porous layer, the deeper the particle in the porous Si layer, the larger the circle
defect radius. The particle lying on the porous Si layer led to a disturbed reorganization of the porous Si during hydrogen anneal that drives the particle deeper into
the porous Si layer. Depending on the exact position in depth either only the growth
of the epitaxial Si layer is hindered or if the particle dissolves into the porous silicon
layer below the high-porosity separation layer, the epitaxial Si layer cannot
be detached from the Si substrate wafer. In that solar cell batch, an average of
4,105/cm2 stacking faults and 6,230/cm2 point defects were measured. An average
of 3.9/cm2 small circle defects and 2.4/cm2 large circle defects were counted. Solar
cell efficiencies of up to 14.0 % on an area of 0.16 1 cm2 were achieved.
Tayanaka et al. (1999) also determined a minority carrier lifetime of up to 100 s
on a 10 m thick p-type Si layer.
As proven by Petermann et al. (2012b), the electronic and crystal quality of the
p-type B-doped Si layer is high enough to achieve a conversion efficiency of above
19 % applying an appropriate solar cell process. The effective diffusion length of the
minority charge carriers is above 232 m as determined from internal quantum
efficiency while from this a lower limit for the bulk diffusion length L > 100 m
and an upper limit for the effective surface recombination velocity Seff < 1,200 cm/s
results. The epitaxy deposition was carried out in an APCVD reactor at 1,100 C
at a rate of 1 m/min (Petermann et al. 2012a). An even higher efficiency of
(20.1 0.4)% on an area of 242.6 cm2 was published by (Moslehi et al. 2012;
Green et al. 2013).
572
B. Terheiden
n-type As-doped epitaxial layers deposited in a single wafer Epsilon2000 reactor

from ASM were investigated by van Nieuwenhuysen et al. in 2012 (Van
Nieuwenhuysen et al. 2012). In order to study layers as used for solar cells, the
epitaxial stack consisted of a p-type-doped emitter with a highly n-doped back surface
field and a n-type-doped base. All layers were grown at a temperature of 1,130 C. The
precursor was trichlorosilane (TCS), and as doping gases, B2H6 and AsH3 diluted in
hydrogen were used. The growth rate was 4 m/min for all layers. The density of etch
pits (Secco etching (Secco d Aragona 1972)) was found to be around 5 103 cm2,
which was comparable to the defect density of epitaxial layers grown on reference
substrates without a porous silicon layer. For minority carrier lifetime measurements,
free-standing epitaxial foils were fabricated consisting of a single n-type layer with a
doping concentration of 1016 cm3. At a minority charge carrier density of 1015 cm3,
an effective lifetime of around 100 s was measured. This corresponds for the n-type
layer to an effective diffusion length of around 300 m (Van Nieuwenhuysen
et al. 2012). Solar cell efficiencies for these layers were not reported.
A special APCVD reactor based on convection-assisted chemical vapor deposition (CoCVD) (Kunz et al. 2006) aiming at high throughput of wafers for the
application in photovoltaics was applied for the first time to porous Si layers in
2008 (Terheiden et al. 2008). The epitaxial Si layer showed a minority carrier
diffusion length in the bulk of the Si layer of (85 5) m. This led with a simple
solar cell process to a solar cell efficiency of 12 %.
Homoepitaxy Applying LPCVD

Low-pressure CVD allows the simultaneous growth of many wafers as is well
known for the production of polycrystalline layers for microelectronic devices. The
low pressure allows to grow uniform Si layers on many wafers in the same reactor
due to the low pressure which makes the reactive gases homogeneously distribute
over whole reactor volume. The deposition rate is much lower than for APCVD and
is typically between 10 and 100 nm/min depending on the growth conditions
(Hitchman and Jensen 1993b). Poortmans et al. developed a LPCVD reactor for
the purpose of deposition of epitaxial Si layers for thin film solar cells (Poortmans
et al. 2000). On nonporous Si substrates, dichlorosilane allowed epitaxial growth at
temperatures between 900 C and 1,050 C, while for using SiH4 temperatures
above 800 C were suitable.
For the application of this technique to sintered porous Si substrates, a sintering
step of 3 h in hydrogen in the LPCVD reactor was performed (Van Nieuwenhuysen
et al. 2005). The porous Si layer did not reorganize completely, and therefore the
surface showed open pores. During epitaxy at 1,000 C using silane as a precursor
gas and B2H6 as doping gas and a reduced pressure between 1 and 10 mbar, pore
filling occurred which resulted in defect densities of 6 107 to 8 108 cm2
which are too high for silicon solar cells. The reorganization of the porous layer in
hydrogen atmosphere is the crucial part for epitaxy with LPCVD. Processes for
reorganization using N2 or forming gas did not lead to reorganization at all.
573
Further investigations of growing epitaxial layers on porous Si by LPCVD

compared the growth on planar and textured substrates, which was carried out for
APCVD by Kuchler et al. (2000). The porous Si layers were annealed at 1,050 C
for 30 min in H2 atm at a pressure of 3 104 Pa for the heat up period at a heat up
slope of 10 C/min up to 1,100 C. Silane was used as a precursor gas and during
deposition the pressure was kept below 100 Pa. A textured epitaxial Si layer with a
weighted reflectance of 13.8 % was fabricated (Cai et al. 2010).
Homoepitaxy Applying Liquid Phase Epitaxy

Liquid phase epitaxy (LPE) is a growth method where the deposition of the Si is
driven by the Si supersaturated metal melt that is cooled down from above 1,000 C.
Epitaxial growth starts according to the metal Si phase diagram in equilibrium.
The melt is cooled down, and the liquid Si deposits onto the solid Si substrate.
The growth rate is in the range of 0.1 and 1 m/min.
Studies of the growth on (111) and (100) oriented sintered porous Si layers
using the well-known sliding boat technology (Berger et al. 2001) revealed that in
combination with a sintering step for the porous Si of 450 C for 15 min and
950 C for 2 h both in hydrogen atmosphere led on (100) surfaces to pyramidal
growth but on (111) surfaces a planar and continuous Si layer due to higher
ratio of lateral to vertical growth which allows in case of the (111) oriented
surface to laterally overgrow residual oxide areas (Berger et al. 2001). A higher
temperature to remove the native oxide prior to epitaxy from the porous Si
surface is needed.
Comparing the growth of epitaxial Si layers on porous Si using APCVD and
LPE, see (Fave et al. 2004), reveals that first of all for LPE a thicker porous Si is
needed, i.e., 5 m instead of 2 m. The annealing time of the porous Si is 2 h at
1,050 C combined with the Si saturation step compared to 10 min at 1,070 C for
the APCVD approach both in hydrogen atmosphere. Chemical etching revealed an
etch pit density of 2 104 cm2 and 1 104 cm2 for APCVD and LPE,
respectively.
The Hall mobility determined on epitaxial layers on high resistivity Si wafers
without a porous layer lied for LPE at 260 V cm2 s1 for a p-type doping
concentration of 3 1016 cm3 (Fave et al. 2004). The Hall mobility of LPE
grown layers on porous Si substrates was 192 V cm2 s1 for a doping concentration of 7.1 1016 cm3 (Kraiem et al. 2005). From light beam-induced current
measurements on Schottky samples, the diffusion length of charge carrier was
determined to be 125 m for 4 1016 cm3 and 120 m for 9 1016 cm3 for
APCVD and LPE grown layers, respectively (Fave et al. 2004).
Nishida et al. developed a reactor for LPE for depositing epitaxial layers on a
5 in. Si wafer and subjected to it porous Si double layers for layer transfer
processes (Nishida et al. 2001). They presented the highest solar cell efficiency
published up to now of 9.5 % (VOC 0.52 V, JSC 27.5 mA/cm2, FF 66 %,
cell area 0.2 cm2).
574
B. Terheiden
Epitaxy on Non-Sintered Porous Si

Experiments of Homoepitaxy on Non-reorganized Porous Si
For the FIPOS (full isolation by porous oxidized silicon) technique, a porous layer
of high porosity for a later thermal oxidation is needed. The pores need to stay open
during epitaxy and subsequent oxidation. Therefore, processes were developed to
achieve high-quality epitaxial layers on non-reorganized porous Si layers. Si
epitaxy on such porous Si layers for the investigation of the growth mechanism
was carried out by molecular or electron beam epitaxy, e.g., (Ito et al. 1990; Lin
et al. 1986; Guoliang et al. 1991; Halimaoui et al. 1995), by rapid thermal CVD
(Oules et al. 1992) or by UHV-CVD (Halimaoui et al. 1995). Epitaxial growth of Si
layers was demonstrated in all cases.
The main finding was that a minimum surface density of nucleation sites needed
to be provided by the Si pore walls allowing a bridging over the open pores. A pore
size of 5 nm is suitable to provide enough nucleation sites (Zheng et al. 1998). To
achieve a small enough pore size and at the same time having large enough pores
for oxidation, a low-porosity layer on a higher porosity layer was used (Zheng
et al. 1998; Huang et al. 2001). For a high crystal quality, SiO2 has to be removed
from the porous Si surface while keeping the oxidized porous Si deeper in the
porous layers.
A high-temperature annealing can do this, but at the same time the porous
structure reorganizes. This was avoided by keeping the temperature low and
using a Si beam which reacted with the SiO2 on the surface on the top surface of
the pores and formed SiO which desorbs from the Si surface at temperatures as low
as 700 C (Ito et al. 1990; Lin et al. 1986). A Ge beam was also successfully applied
(Zheng et al. 1998).
The initial stage of epitaxy on porous Si with a porosity of 26 % using electron
beam evaporation at ultrahigh vacuum was investigated by Ito et al. (1990). X-ray
photoelectron spectroscopy (XPS) data showed the growth of an 1.5 nm thin SiO2
layer during the preoxidation step at 300 C to stabilize the porous structure. Before
the subsequent epitaxial deposition of the Si layer, nothing more than a heating step
at 800 C for 50 min was carried out. After this step, a diffraction pattern was taken
showing a diffuse (1 1) pattern originating from the Si bulk. Ito et al. explained it
by the presence of Si pores with a thin oxide layer that allow the 5 keV electron
beam to reach the Si bulk. By only depositing 1 nm Si, the SiO2 is removed from the
porous Si surface due to the production of volatile monohydrides as confirmed by
strong (1 1) pattern (Ito et al. 1990). Further Si deposition led to the evolution of
a (7 7) pattern which was first also diffuse but became sharper, the thicker
(68 nm) the Si grew. The clear and sharp (7 7) pattern indicated that the surface
of the specimen was totally covered with flat Si. At a thickness of only 8 nm the
pattern was almost identical to that of a (111) monocrystalline Si wafer. The pores
disappeared at the surface.
The epitaxial layer deposited by rapid thermal CVD at 830 C on highly doped
(0.01 cm) porous Si substrates was found to show a quality as high as epitaxial
575
layers that were grown on Si wafers without a porous Si layer for porosities up to
50 % (Oules et al. 1992). The wafers did neither get a preoxidation nor an explicit
heating step. On lowly doped Si substrates, the porosity was limited to values of
above 60 %, and thus the defect density was as high as 107108 cm2 (Oules
et al. 1992).
Simulations of Homoepitaxy on Non-reorganized Porous Si

The initial state of epitaxy on porous Si (111) (Novikov et al. 1999; Zverev
et al. 2001; Chemakin et al. 2002) and (001) (Chemakin et al. 2002) surfaces was
also simulated using different 3D Monte Carlo models. It was determined how
many Si bilayers, i.e., two neighboring monolayers, were necessary to achieve a
closed and smooth surface, i.e., a sealing of all open pores with Si in dependence of
the growth conditions and surface properties. Pore diameters between 2.7 and
20 nm at a pore depth of 30 nm were studied, the pore density lied between 1011
and 1012 cm2. The deposition rate was between 0 and 104 monolayer/s, and the
studied deposition temperature range was 4501,000 K (Chemakin et al. 2002).
Chemakin et al. demonstrated that the epitaxial growth on (111) porous Si surface
was different to that on (001) surfaces. The critical dose which is needed to seal all
pores is at the same deposition temperature and rate for the (001) surface one order
of magnitude higher than for (111) surfaces. While the (111) surface remains flat on
the (001) surface, pyramidal pits arise.
Homoepitaxy Applying Ion-Assisted Deposition

Brendel (1997) applied IAD (Oelting et al. 1994) for epitaxially growing Si layers
on a porous Si double layer on a Si wafer with regular inverted pyramids, (Brendel
et al. 1998) which allows for low temperature epitaxy in combination with high
growth rates (Oelting et al. 1992). In contrast to MBE and CVD, the surface
mobility of the Si atoms is generated by the ion bombardment by the Si ions
which they get while being accelerated toward the substrate. Therefore, a lower
substrate temperature can be used (Oelting et al. 1992).
Using IAD instead of CVD allows deposition of conformal epitaxial layers, i.e.,
the epitaxial layer follows the surface structure leading to so-called waffle solar
cells. The porous Si wafer was heated at 850 C for 10 min to remove the native
oxide but keep the porous structure. The deposition temperature with 700 C up to
850 C was much lower than that of the APCVD and LPE. Typical deposition rates
were 0.1 m/min, and the highest rate achieved with that set up was 0.3 m/min
(Brendel 2003). The epitaxial Si layer was Ga doped with 2 16 cm3 and showed
a Hall mobility measured by the van der Pauw geometry of 275 cm2V1 s1. But
also the boron doping with IAD was reported (Oberbeck et al. 2001).
The CuK X-ray diffraction spectrum verified that the crystalline Si layer on the
porous silicon has a (100) orientation (see handbook chapter X-Ray Diffraction
576
B. Terheiden
in Porous Silicon). The monocrystallinity was approved by Laue images of the

epitaxial film and the Si substrate and the preferential fracture of the epitaxial film
in two directions perpendicular to each other (Brendel et al. 1998). No defects were
visible in a transmission electron micrograph, but the etch pit density after chemical
etching was 103104 cm2 on (100) oriented flat porous Si substrates. The density
of stacking faults was investigated on the waffle structures (Krinke et al. 1999). The
main surface area shows (111) lattice planes. On those lattice planes, the density of
stacking faults decreases from 9 109 cm2 to 4 107 cm2 with increasing
growth temperatures between 600 C and 850 C, respectively.
The electronic quality of the layer was determined measuring the bulk minority
carrier lifetime on a free-standing Si epitaxial layer passivated with a corona charged
(Schofthaler et al. 1994) thermal oxide. From a measured Hall mobility of the holes
of 186 cm2/Vs, the bulk lifetime of (0.27 0.08) s, a diffusion length of 11 m for
the electrons in the p-type Si could be estimated. The diffusion length of 11 m was
about double the epitaxial layer thickness of 5.8 m. Therefore, the IAD method
seemed suitable for the production of epitaxial Si solar cells (Krinke et al. 1999).
Summary
The quality of epitaxially grown Si layer, using different deposition techniques and
various types of porous silicon, was assessed by etch pit density, minority carrier
lifetime, Hall mobility, microscopy, and device performance.
From this review, it can be concluded that APCVD is in combination with a
closed porous Si surface layer as a seed layer, the most promising approach to
produce high-quality epitaxial layers.
In particular for the industrial production of thin solar cells, a high-throughput
reactor needs to be developed. Recently two companies started to set up production
lines for producing solar cells from epitaxial layers grown on porous Si. Both
companies developed their own CVD reactor for a throughput between 300 and
440 wafer per hour in pilot production scale (Hering and Martinez 2012). Another
approach was realized by Reber et al. (2009, 2012) developing the ConCVD (continuous CVD) and subsequently the ProConCVD reactor a high-throughput prototype
CVD reactor capable of a throughput of more than 1,000 wafers/h. However, the
ProConCVD has not been applied for epitaxy on porous silicon up to now.
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10671074
Heteroepitaxy on Porous Silicon

Reza Sabet Dariani
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Material Epitaxy on Porous Silicon: A Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Merits and Uses of a Porous Silicon Substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon as a Compliant Substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
581
582
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585
585
Abstract
The literature on epitaxial growth of different materials on porous silicon

substrate has been surveyed. This field was stimulated by the theoretical prediction in 1986 of stress field and hence defect reduction in lattice-mismatched film
grown on a mesoporous substrate. Data now exists not only on Ge, SiC, and
diamond films but also on a range of both IIIV and IIVI semiconductors, as
well as other crystalline materials. Recently there has been most interest in GaN
growth on porous silicon for optoelectronic applications.
Introduction
There exists tremendous interest in the possibility of growing high-quality epitaxial
layers of foreign materials on lattice-mismatched semiconductor substrates. In
pursuing this direction, the objective is to enhance the range of useful devices
available with a given substrate. However, the difference in lattice constant (lattice
mismatch) between different semiconductors results in the existence of a critical
film thickness (hc). A heteroepitaxial film can be grown nearly free of misfit
R. Sabet Dariani (*)
Department of Physics, Alzahra University, Tehran, Iran
e-mail: dariani@alzahra.ac.ir
DOI 10.1007/978-3-319-05744-6_59
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R. Sabet Dariani
dislocations provided the thickness is kept below hc. Such an hc restriction greatly
limits the device application because its value can be very small. When utilization
of the hetero-interface is not required, one is willing to tolerate various intermediate
layers, so long as the top working layers are of desired device quality. Of the many
pitfalls in the path of this development, some, such as the possible chemical
incompatibility of the two materials, are not directly related to the lattice mismatch.
The latter however manifests itself adversely by generating misfit dislocations,
which thread the epitaxial layers, thus degrading their quality.
The start of heteroepitaxy on porous silicon was initiated by a Luryi and Suhir
paper in 1986 (Luryi and Suhir 1986). They theoretically predicted a possible
approach for growing dislocation-free lattice-mismatched heteroepitaxial layers
on small seed pads of lateral dimension L, having a uniform crystal orientation
over the entire substrate wafer. It was proposed that when L is smaller than a
specific length Lmin, which depends on the lattice misfit as well as the dislocation
energy, the entire elastic stress in the epitaxial films will be accommodated without
dislocations. Porous Si, studied at that time for dielectric isolation purposes (Imai
1981), was named as a suitable substrate.
Material Epitaxy on Porous Silicon: A Survey

Table 1 gives a comprehensive listing of the various materials grown on porous
silicon to date and the different growth techniques utilized. Most heteroepitaxy has
been conducted on mesoporous layers fabricated from anodization of (100) p-type
wafers, although (111) orientation and heavily doped n-type wafers have also been
used. Porosity values are typically in the range 1580 % and thicknesses 0.510 m.
The crystalline quality of the epitaxial deposit is typically assessed using X-ray
diffraction, electron microscopy, defect etching, or Raman analysis and compared
to that of growth on bulk Si substrates under similar conditions. Initially, the main
interest was in Ge and diamond growth, but in recent years direct bandgap semiconductors, such as GaN and ZnO, have received increasing attention.
Figure 1 illustrates some of the highly varied range of materials grown on porous
silicon.
Merits and Uses of a Porous Silicon Substrate

It is believed that the nanoscale surface morphology of PS has advantages for the
growth of nanostructures like nanowires by increasing the number of nuclei sites
and reducing strain (Hsu et al. 2005; Lee et al. 2003; Yang and Lieber 1997).
Separation of the PS layer from silicon substrate is also possible through layer
transfer techniques which provide the opportunity to reuse the Si substrate (Solanki
et al. 2004). This is discussed in more detail in the handbook chapters
Homoepitaxy on Porous Silicon and Porous Silicon and Solar Cells.
583
Table 1 Various materials grown epitaxially on porous silicon

Class of
epitaxial
material
Group IV
semiconductors
Epitaxial
material
SiGe alloys
SiC
Ge
IIIV
semiconductors
IIVI
semiconductors
Others
Epitaxy technique(s)
CVD, HFCVD
APCVD reactor,
SSMBE,
carbonization
SME
Diamond
CVD, HFCVD,
MPCVD
Carbon
nanotubes
GaAs
CVD
MOCVD, MOVPE
GaN
MOVPE, MOCVD,
CVD, RF-sputtering,
magnetron sputtering
InP
InN
MOCVD
Reactive magnetron
sputtering
MOVPE
CBD
AlN
CdS
ZnO
CVTC, solgel spin

coating, RF
magnetron sputtering
PbS, PbTe
ZnSe
Cobalt
silicide
BST
Epitaxial
CVD
MBE
Tin oxide
Protein
crystallization
Pulsed laser
deposition
Atomic layer epitaxy
Vapor diffusion
hanging drops
References
Halimaoui (1995), Novikov
(2003)
DArrigo (2006), Vasin (2007)
Wietler et al. (2012), Jawad

(2012), Aouassa et al. (2012)
Mirzakuchaki et al. (1995), Raiko
et al. (1996), Iyer and Srinivas
(1997), Khan et al. (1998),
Baranauskas et al. (2001)
Fan et al. (1999)
Lajnef et al. (2008), Wiesner
et al. (2009)
Chaaben et al. (2004), Boufaden
et al. (2004), Dong et al. (2006),
Cheng et al. (2007), Ishikawa
et al. (2008), Buzynin
et al. (2008), Bergaoui
et al. (2008), Matoussi
et al. (2010), Ishikawa
et al. (2010), Carvajal
et al. (2012), Zainal et al. (2012),
Liang et al. (2003)
Joshi and Goorasky (2010)
Chuah et al. (2009)
Chaaben et al. (2006)
Mahdi et al. (2012)
Rajabi et al. (2011), Cai
et al. (2009), Shabannia and Abu
Hassan (2013), Suhail
et al. (2012)
Belyakov et al. (1997)
Chang and Lee (2000)
Kao et al. (1987)
Liu et al. (2004)
Ducso et al. (1996)
Chayen et al. (2001)
584
R. Sabet Dariani
Fig. 1 SEM pictures of different materials grown on porous silicon: (a) GaAs layer (Wiesner
et al. 2009); (b) ZnO rods (Rajabi et al. 2011); (c) GeSi layer (Xie and Bean 1990a); (d) barium
strontium titanate (BST) film (Liu et al. 2004)
Some substrates like sapphire are electrically insulating material; it introduces

complexity to device fabrication processes when grown crystals are applied to
carrier injection-based light-emitting devices. Electrically conductive Si substrates
via porous silicon can relieve this problem. In addition, the crystal quality of the Si
substrate is expected to be markedly higher than that of the sapphire substrate (Kim
et al. 2011).
Growing high-quality ZnO on Si substrate has been pursued for its low cost and
the advantages of Si-based integration of optoelectronic devices (Suhail et al. 2012).
Porous silicon is used as an intermediate layer between silicon and ZnO films,
and it provides a large area composed of an array of voids (Chuah et al. 2010).
Due to their high density of small pores, PS layers are considered to be a flexible
material which may avoid the use of an intermediate epitaxial buffer layer. Hence,
PS substrate has been studied as a candidate for the growth of GaN films by metal
organic vapor phase epitaxy (MOVPE). It is expected a relaxation of stress and the
reduction of defect density of the GaN films, caused by the large misfit between
GaN layers and Si substrate, by straining small crystalline columns in PS layers
(Missaoui et al. 2000; Buzynin et al. 2008). The PS provides a large area composed
of an array of voids and interconnected silicon clusters or rods. This spongelike
structure could limit strain and crack development after the post-growth cooling
(Matoussi et al. 2001).
585
GaAs films have been grown on porous Si substrates by molecular beam epitaxy
(MBE) in anticipation that the total defect density of the films would be reduced.
Porous Si layers were considered to be a deformable material, so the stress due to
the large misfit could be relaxed by straining small crystalline columns in porous Si
layers, instead of by formation of misfit dislocations in GaAs films, resulting in
GaAs films with improved crystalline quality (Hasegawa et al. 1989).
The stress due to the thermal expansion coefficient difference between Si and
GaAs could also be accommodated via a porous Si layer (see handbook chapter
Thermal Properties of Porous Silicon). GaAs layers of higher quality were
achieved on PS in comparison with the GaAs layers on single Si (100) substrates.
To optimize thick epilayer quality, a two-step growth process was used, where the
first layer, which plays an important role in determining the epilayer quality,
is grown at a relatively low temperature, followed by high-temperature growth
(Kang et al. 1992).
Porous Silicon as a Compliant Substrate

Following the pioneering Luryi et al. study (Luryi and Suhir 1986), both the
validity of the theoretical model and the use of porous silicon were initially
queried. Xie et al. (Xie and Bean 1990a) studied the growth of GexSi1-x on both
regular Si and porous Si substrates. Their experimental results indicated
no reduction in dislocation density by using porous Si substrates, and an
alternative approach was proposed (Xie and Bean 1990b). Since then, however,
both theoretical and experimental studies have provided continuous support for
the Luryi and Suhir proposal (Novikov et al. 2003; Huangfu et al. 2013;
Christiansen et al. 1996; Zubia and Hersee 1999; He and Yu 2014), and recent
experimental data on Ge and SiGe epitaxy (Wietler et al. 2012; Aouassa
et al. 2012; Kim et al. 2007; Blanchard et al. 2011; Gouder et al. 2014) also
indicates that porous silicon is indeed a strong contender for specific pseudosubstrate applications. Often, the structure is intentionally partially oxidized
prior to epitaxy, in order to stabilize the mesoporosity and/or introduce controllable levels of strain into the epilayer. This approach was first developed for
homoepitaxy. Related handbook chapter of relevance is Homoepitaxy on
Porous Silicon.
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Oxidation of Macroporous Silicon

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Deformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microstructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
589
590
591
592
594
597
Abstract
Thermal oxidation is a common technique to manipulate macropore shape and

realize a variety of novel structures in silicon. The stress and deformation
induced by such oxidation, kinetics of oxide growth, and its anisotropy are
reviewed. Uniform arrays of both silicon and silica microstructures such as
needles and tubules have been realized via thermal oxidation.
Introduction
The thermal oxidation of macroporous silicon (see handbook chapter
Macroporous Silicon for detail on its prior fabrication) is the most frequently
employed posttreatment procedure. This procedure is commonly performed, as also
in the microelectronics technology, at a high temperature T 8001,200 C in
oxygen or water vapor (dry or wet oxidation, respectively) (Burger and Donovan
1967). The process of SiO2 formation is accompanied by an increase in volume. It
follows from the relationship between the gram-atomic weight of Si (28 g) and its
E.V. Astrova (*)
Ioffe Physical Technical Institute, St. Petersburg, Russia
e-mail: east@mail.ioffe.ru
DOI 10.1007/978-3-319-05744-6_60
589
590
E.V. Astrova
density (2.33 g/cm3) that one gram-atom of Si occupies a volume of 12 cm3. One
gram-molecule of SiO2 with a gram-molecular weight of 60 g and density of
2.2 g/cm3 occupies a volume of 2.27 times that of silicon from which this SiO2
was formed. The arising compressive stresses in a silicon dioxide film
and tensile stresses in silicon itself relax via viscous flow of the oxide at
T > 960 C. Thus, the main factor leading to the appearance of stresses in
oxidized silicon after cooling to room temperature is the difference between the
thermal expansion coefficients: (2.54.5) 106 K1 for Si and 5 107 K1
for SiO2 (Hu 1991).
Kinetics
On the planar surface of silicon, the increase in the volume of the oxide is
accommodated via free expansion of the film in the direction perpendicular to
the Si/SiO2 interface. Residual stresses due to the mismatch between the thermal
expansion coefficients are concentrated in the oxide and directed in parallel to the
plane (biaxial compressive stress). Their magnitude is estimated at 0.3 GPa for
a 1-m-thick film (Jaccodine and Schlegel 1966). In oxidation of a profiled
Si surface, there appear additional stresses directed perpendicular to the
silicon/oxide interface. These stresses strongly affect the oxidation kinetics of
2D structures (macropores, pillars, trenches, etc.) (Uematsu et al. 2002; Liu
et al. 1992). The results obtained in studies of oxidation of nonplanar surfaces
are also applicable to macroporous silicon. One fundamental feature of 2D
oxidation (Kao et al. 1987, 1988) is that the oxidation rate of convex and concave
silicon surfaces decreases. This retardation is more pronounced for concave
surfaces. The oxide thickness strongly depends on the radius of curvature of the
silicon surface: the smaller the radius, the thinner the oxide. Figure 1 shows an
oxidized Si pillar where the oxide thickness is strongly reduced in the area of
maximal curvature.
The effect also depends on other factors: the lower the oxidation temperature,
the stronger the retardation. The phenomenon is observed in both dry and wet
oxidation, being more pronounced in the case of oxidation in dry oxygen. Presence
of a phosphorussilicate glass film on the surface of heavily doped Si reduces the
retardation of oxidation. The main reason for the retardation is the nonuniform
deformation of the oxide film. Arising stresses reduce diffusivity of oxygen in the
oxide and change the kinetics of reaction on Si-SiO2 interface. The stresses normal
to the Si/SiO2 interface retard the oxidation reaction for curvilinear surfaces of both
signs. Additional compressive stresses in the bulk of the oxide on concave surfaces
enhance the retardation effect. According to some evidence, the oxidation process
of thin Si wires is self-limiting (Liu et al. 1993); according to other data, their
complete oxidation is possible (Kim et al. 2011). Anyway, the effect in which
oxidation of nonplanar Si surfaces is retarded is a generally recognized fact. For
small wires (<35 nm) oxidation rate is reduced by factor of two compared to bulk
silicon (B
uttner and Zacharias 2006).
591
Fig. 1 TEM micrograph of

an oxidized Si nanostructure
(dry oxidation at 850 C for
3 h) shows the diffraction
contrast between the
crystalline Si core and the
amorphous oxide skin scale
bar is 10 nm (Reprinted with
permission from (Liu
et al. 1992). Copyright 1992,
American Vacuum Society)
SiO2 on the surface of macropores or Si pillars is widely used as a sacrificial

layer for making larger the pore diameter (reduce the pillar diameter) or smoothen
the surface irregularities (Wehrspohn and Schilling 2005; Lehmann 2002; Trifonov
et al. 2008; Wehrspohn et al. 2004; Lau et al. 1996). The thickness tSi of the
silicon layer being removed is less than half the thickness tSiO2 of the oxide
grown (tSi 0:44tSiO2 ). It is recommended to use thin oxide layers (tSiO2 100 nm
(Langner et al. 2011)) to preclude appearance of stronger stresses in a sample.
In order to markedly change the geometric dimension of pores, multiple thermal
oxidation and removal of the oxide in an aqueous solution of HF is performed.
Anisotropy
At high temperatures, the oxidation process can be considered nearly isotropic,
whereas at low temperatures, the dependence of the oxidation rate on the crystallographic direction becomes noticeable. The (111) plane is oxidized at the highest
rate and the (100) plane at the lowest. Table 1 lists the wet-oxidation rate ratios for
planar (100) and (110) silicon surfaces in relation to temperature.
The anisotropy of the oxide formation rate was used to convert the crosssectional shape of macropores in (100)-oriented Si wafers from rounded square to
circular upon an increase in their diameter via removal of the sacrificial SiO2 layers
(Trifonov et al. 2007). Figure 2 presents the results for a sample subjected to
11 cycles of oxidation in dry oxygen at 1,100 C for 1 h. Note that the tendency
toward pore rounding due to the oxidation rate anisotropy is enhanced by the
oxidation retardation on the concave surface at square corners.
592
E.V. Astrova
Table 1 Conditions for wet planar oxidation (Kao et al. 1987)

Temperature
Time (min)
)
tox(100) (A
tox(110)/tox(100)
800 C
1,440
5,027
1.29
900 C
300
4,575
1.25
1,000 C
96
4,735
1.18
1,100 C
40
4,880
1.05
1,200 C
24
5,554
1.03
Fig. 2 Change of the macropore shape in oxidation/oxide-removal cycles (scale bar 4 m):
(ac) SEM micrographs (bottom views) of a macroporous silicon membrane after (a) 1st, (b) 6th,
and (c) 11th oxidation step; (d) pore shape extracted from SEM micrographs taken after selected
oxidation steps indicated by numbers (Trifonov et al. 2007)
Deformations
The increase in the diameter of straight macropores, to the point of disappearance of
walls between neighboring pores, enables fabrication of silicon pillars. Figure 3a
and b show a structure with through-oxidized walls, from which pillars with a
triangular cross-section are produced after the oxide is dissolved. The stresses due
to the presence of the oxide lead to distortion of the round pores, making these pores
593
Fig. 3 Macroporous Si with triangular pore arrangement: (a, b) front view images of oxidized
initially round pores under (a) optical and (b) electron microscopes, (c) front view of roundedsquare-shaped pores after removal of the oxide, scale bar is 10 m (Astrova et al. 2011) (With kind
permission from Springer Science+Business Media), (d) broadening of symmetrically modulated
pores upon their merging along the square corners, scale bar is 6 m (Trifonov et al. 2008) (With
permission from Elsevier, 2008)
hexagonal in accordance with the symmetry of the pore array. The pattern
symmetry and the cross-section of the pores predetermine the shape of the pillars
being formed. A structure with pillars having a butterfly cross-section, produced by
merging of pores with cross-sections in the form of rounded squares, is shown in
Fig. 3c. A structure formed from macropores with a diameter varying along their
length is presented in Fig. 3d.
The stresses and deformations appearing in macroporous silicon samples in
oxidation/oxide-removal cycles were studied by means of X-ray diffraction
analysis, topography (Astrova et al. 2002, 2003; Shulpina et al. 2001), and
micro-Raman spectroscopy (Perova et al. 2003). It was found that oxidation leads
to deformation of the crystal lattice, with a strain of 104. The lattice deformation is
mostly due to misorientation of the planes that are perpendicular to the wafer
surface. After the oxide is removed, the strain decreases by an order of magnitude
(Astrova et al. 2001). Being combined, the residual stress fields can lead, as also in
the case of oxidized mesoporous silicon (Barla et al. 1986), to a strong bending of
wafers. Figure 4 shows the shape of a sample with a diameter of 25 mm and a
porous region (20 mm in diameter) in the middle of the sample after six oxidation/
594
E.V. Astrova
Fig. 4 Shape of an oxidized

macroporous Si wafer: (a)
convex sample subjected to
six oxidation/oxide
dissolution cycles (wafer with
through channels and pits).
(b) Image of the sample
backside (Astrova et al. 2003)
oxide-removal cycles. The oxidation was performed in water vapor at T 1,200 C,

with an oxide thickness of 1.2 m and initial porosity of ~1 %.
In oxidized samples with dead-end pores, the most-strained regions are the
interface between the porous region and the substrate in the vertical direction and
between the porous region and the pore-free rim in the horizontal direction. These
regions are sources of the emerging dislocations. The significant bending of the
oxidized macroporous Si is due to the large inner surface area of the channels
subjected to oxidation. For samples with a triangular lattice of cylindrical pores, the
specific surface area per unit volume is Sv 3.6 d/a2, where d is the pore diameter
and a, lattice constant. Typical values Sv 2,0006,000 cm2/cm3. The sample
curvature is linear in the specific surface area of macroporous Si, and its sign is
determined by the manner in which porosity and the specific surface area varies
across the structure thickness. The stress introduced by oxidation is of mixed
elasticplastic nature. It grows with increasing number of oxidation cycles because
the channel diameter becomes larger (Fig. 5).
Microstructures
The thermal oxide on the surface of macropores is successfully used as a mask in
etching of silicon in alkaline solutions. The minimal thickness of SiO2 that protects
Si surface depends on KOH concentration and temperature (Kendall 1979). Figure 6
shows the standard scheme for substrate removal to obtain through macropores (the
initial wafer is oriented in (100) plane).
The pore opening process was precisely controlled in (Mathwig et al. 2011) by
means of bias-assisted KOH etching. If the dissolution of silicon is continued after
stage (c) in Fig. 6, silica arrays can be obtained (Schilling et al. 2004; Trifonov
et al. 2005; Astrova et al. 2005; Rodriguez et al. 2005; Zhao et al. 2007). An
example of these arrays is shown in Fig. 7. Careful removal of bottoms of these test
595
Fig. 5 Variation of the

curvature in the course of
three-step cyclic
oxidationdissolution
(sample with dead-end pores;
pits removed; initial porosity
5.6 %) (Astrova et al. 2003)
Fig. 6 Schematic of membrane fabrication: The etched macroporous silicon (a) is oxidized
(b) and subsequently etched in KOH (c). The angle between the (100) surface and the remaining
(111) pore wall is 54.7 . Silicon dioxide can be removed by dipping in an HF solution to
obtain a porous membrane (d) (Langner et al. 2011) (With kind permission from Springer
Science+Business Media)
tubes with HF immediately after the pore opening enables fabrication of

microneedles (Fig. 8). Oxidation of macroporous silicon in the presence of a
catalyst leads to crystallization of amorphous SiO2 to give, depending on temperature, quartz, tridymite, or cristobalite. The microtubes fabricated by lithiuminduced crystallization are shown in Fig. 9.
A through oxidation of Si walls has been used to obtain thick oxide layers
for thermal insulation purposes (Kan and Finstad 2005; Barillaro et al. 2003).
596
E.V. Astrova
Fig. 7 Silicon dioxide shells

formed upon the oxidation of
pore walls and removal of the
bottom bulk silicon substrate
(Reprinted with permission
from (Schilling et al. 2004).
Copyright 2004, AIP
Publishing LLC)
Fig. 8 SEM micrograph

(bottom view) of an array of
microneedles with a 70-nm
wall thickness and square
arrangement (Rodriguez
et al. 2005) (With permission
from Elsevier, 2005)
Fig. 9 Macroporous Si
annealed in the presence of
LiNbO3 at 1,200 C for
24 h. SiO2 (cristobalite)
appears as a bright contrast
(Zhao et al. 2007)
The thermal oxidation can be utilized to determine the inner surface area of
macropores by weighing (Nechitailov et al. 2007). It is assumed here that the
thickness of the oxide covering a 2D structure is the same everywhere. This
technique is applicable to macroporous silicon with both regular and random
pores and is compatible with gravimetric determination of porosity.
597
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a microchannel silicon studied by X-ray diffraction. Tech Phys Lett 27:4144
Astrova EV, Ratnikov VV, Remenyuk AD, Shulpina IL (2002) Strains and crystal lattice defects
arising in macroporous silicon under oxidation. Semiconductors 36:10331042
Astrova EV, Ratnikov VV, Remenyuk AD, Shulpina IL (2003) Strains in macroporous silicon
introduced by cyclic oxidation. Phys Stat Sol (a) 197:1621
Astrova EV, Borovinskaya TN, Zamoryanskaya MV, Perova TS (2005) Silica micro tubes formed
during the patterning of oxidized macroporous silicon. Phys Stat Sol (C) 2:32133217
Astrova EV, Fedulova GV, Smirnova IA, Remenyuk AD, Kulova TL, Skundin AM (2011) Porous
silicon based negative electrodes for lithium ion batteries. Tech Phys Lett 37:731734
Barillaro G, Diligenti A, Nannini A, Pennelli G (2003) A thick silicon dioxide fabrication process
based on electrochemical trenching of silicon. Sensors Actuators A 107:279284
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Burger RM, Donovan RP (1967) Fundamentals of silicon integrated device technology,
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Kan PYY, Finstad TG (2005) Oxidation of macroporous silicon for thick thermal insulation. Mater
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silicon. I. Experiments. IEEE Trans Electron Devices ED-34:10081017
Kao D-B, McVittie JP, Nix WD, Saraswat KC (1988) Two-dimensional thermal oxidation of
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Kim B-H, Pamungkas MA, Park M, Kim G, Lee K-R, Chung YC (2011) Stress evolution during
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(eds) Molecular- and nano-tubes. Springer, New York, p 431
Lau HW, Parker GJ, Greef R (1996) High-Aspect ratio silicon pillars fabricated by electrochemical etching and oxidation of macroporous silicon. Thin Solid Films 276:2931
Liu HI, Maluf NI, Pease RFW, Biegelsen DK, Johnson NM, Ponce FA (1992) Oxidation of
sub-50 nm Si columns for light emission study. J Vac Sci Technol B 10(6):28462848
Liu HI, Biegeisen DK, Johnson NM, Ponce FA, Pease RFW (1993) Self-limiting oxidation of Si
nanowires. J Vac Sci Technol B 11(6):25322537
Mathwig K, Geilhufe M, Muller F, Gosele U (2011) Bias-assisted, KOH etching of macroporous
silicon membranes. J Micromech Microeng 21:035015
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Perova TS, Astrova EV, Maurice R, Potapova D, Vasunkina TN, Moore RA (2003) Characterisation of macro-porous silicon for electronic applications. Proce SPIE 4876:396403
Rodriguez A, Molinero D, Valera E, Trifonov T, Marsal LF, Pallare`s J, Alcubilla R (2005)
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Schilling J, Scherer A, Gosele U, Kolbe M (2004) Macroporous silicon membranes as electron and
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Sintering of Porous Silicon

Izabela Kuzma-Filipek
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sintering Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sintering Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Sintering: Device Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
599
601
602
604
607
607
Abstract
High surface area mesoporous silicon is prone to sintering, which can be an issue
for some applications and be exploited for others. The mechanisms of silicon
sintering, conditions that promote it, methods of characterizing, effects on
properties, and potential uses are reviewed.
Introduction
Since the porous silicon surface is hydrogen terminated, its functionalization is easy
to tailor (Song and Sailor 1999; Stewart et al. 2000; Gao et al. 2002). Depending on
the pore size and porosity, bioactive, biodegradable, or bioinert Psi can be realized
(Canham et al. 1997). Although tailoring of the porous silicon can occur during the
anodization process itself, the size of the pores could be changed reliably only with
a certain degree of freedom and often on an expense of widening of the pore size
distribution (Herino et al. 1997; Labunov et al. 1986) or using chemically aggres-
I. Kuzma-Filipek (*)
IMEC, Heverlee, Belgium
e-mail: kuzma@imec.be
DOI 10.1007/978-3-319-05744-6_62
599
600
I. Kuzma-Filipek
sive electrolytes (Canham et al. 2000). However, enlargement of the pores with
uniform pore size distribution can occur by means of thermal annealing (Herino
et al. 1984; Ogata et al. 2001; Muller et al. 2003).
There are specific areas of application where controlled enlargement of pores is a
must, and this is, e.g., as a carrier for controlled release of large biomolecules
(Salonen et al. 2008). Salonen et al. has studied porous silicon annealing for this
particular application (Salonen et al. 2009). Layer transfer techniques and buried
Bragg reflectors are other examples where sintering of porous silicon is an essential
step to obtain specific function of porous structure (Brendel 2001). In principle the
porous silicon annealing phenomena can occur, wanted or unwanted in all applications which require surface conditioning at temperatures as low as 400 C as for
those temperatures the very first structural changes in porous silicon were already
observed (Ogata et al. 2001). Intentional temperature treatment of porous silicon is
typically applied for the following purposes: (i) surface passivation and reduction
of surface defects; (ii) gettering functionality; (iii) enhancement of optical properties; (iv) enhancement of electrical properties by conductivity enhancement;
(v) fabrication of separation layers, tailoring mechanical strength; and
(vi) enhancement of trapping and controlled release of large molecules. On the
other hand unintentional structural changes can lead to non-beneficial losses as
well, which are related to losses in surface area for sensing devices and nonbiodegradability for medical use.
Example of high-temperature treatment of mesoporous silicon into reorganized
macropore-size voids can be seen in Fig. 1 (Kim et al. 2006). In this case porous
silicon free-standing film serves as a template layer for epitaxial silicon growth,
where reorganization controls surface closure of pores and reduction of stacking
faults. Sintering controls also electrical properties of the porous layer and the actual
distribution of voids which is expected to play a role in the mechanical properties of
porous silicon (Martini et al. 2012).
Fig. 1 Reorganized porous

structure due to hightemperature treatment (1,130

C) in H2 and atmospheric
pressure chamber (Kim
et al. 2006)
601
Sintering Mechanism
Sintering is defined as the thermal treatment of porous or powder materials below
their melting point (for silicon it is 1,412 C) accompanied by structural changes.
Sintering can often occur during processing of porous silicon (see, e.g., handbook
chapter Homoepitaxy on Porous Silicon). Silicon itself is a model material
for studying the sintering of covalently bonded nonoxide ceramics; therefore,
significant amount of literature database exists, with good understanding of
physics and chemistry of the sintering of silicon (Greskovich and Rosolowksi
1976; Moller and Welsch 1985; Coblenz 1990). The microstructural changes in
porous silicon single layers during high-temperature annealing under various
conditions can be explained with the aid of the classical theory of sintering
(Geguzin et al. 1984). Sintering starts at temperatures higher than Tammans
temperature which for silicon is at 572 C. The main driving force of this
phenomenon is the minimization of the inner surface energy responsible for
morphological changes in Psi, as in this investigated case, during the annealing
(M
uller et al. 2000, 2003; Eaglesham et al. 1993). The temperature is a trigger to
activate both volume and surface transport mechanisms; the later one was experimentally proven to be the dominant mechanism during porous silicon sintering
(M
uller et al. 2003). All diffusion mechanisms can be seen by its graphic
representation in Fig. 2.
Non-morphological changes of p-type porous silicon were observed for the
temperatures as low as 350400 C using X-ray diffraction and were attributed to
desorption of hydrogen and changes in the density of dangling bonds (Ogata
et al. 2001). As it was shown by Ott et al. (2003, 2004) and earlier by Labunov
et al. (1986, 1987); at first stage bridges are being formed at the places of local
narrowing of the pore channels, leading to the closing of the pore capillaries and to
the formation of a chain of individual cavities (from the columnar nanometer-sized
spongy kind of pores, through elongated but closed pores, and to spherical and
Fig. 2 Graphical illustration of the basic diffusion mechanisms responsible for the
reconfiguration during sintering on monocrystalline solids (Wolf 2007; Muller et al. 2002)
602
I. Kuzma-Filipek
closed pores). The open dendritical structure closes to form isolated pores and the
adjacent pores merge into larger voids. The second stage defines the evolution of
the frequency, size, and shape of the closed pores (Muller et al. 2003). It was shown
by the group of Ott et al. (2004) that the pore size distribution reveals an increasing
median with the annealing temperature and annealing time. Annealing the samples
at a constant temperature for times from 30 min up to 120 min leads to a similar
evolution of the pore structure, as during increase of the annealing temperature
from 880 C to 1,050 C.
The surface energy of a spherical-shaped void with a constant volume can be
reduced further by faceting (Ott et al. 2004; Eaglesham et al. 1993). The surfaces
{111} and {100} are the ones with the lowest observed surface energy in silicon
(Eaglesham et al. 1993), with the angle of 54.73 between (100) and (111) oriented
facets. According to (Eaglesham et al. 1993), the pore with the facetted shape is the
equilibrium shape of pores in silicon (see Fig. 3f). Another observed phenomenon is
the formation of the void-free thin capping layer during sintering process first
reported by (Sato et al. 1995). This capping layer is formed as a result of the porous
macroscopic surface acting as a vacancy sink. Pores initially located close to the
surface dissolve into the gas phase, leaving behind a several 10 nm thick monocrystalline layer free of pores (Sato et al. 1995). The TEM images presented in
Fig. 3a, d (Kuzma-Filipek 2010) demonstrate such dense layer, in a multilayer
system where same effect is observed at the interfaces between adjacent layers
exposed to sintering in H2 at >1,100 C.
Sintering Conditions
Figure 3 shows TEM images of the multilayer structures consisting of 15 layers of
alternating porous silicon prepared in the same way. The layers were (A) as grown,
(B) exposed to argonoxygen mixture, (C) exposed to argon and subsequently to
hydrogen at low pressure, and (D, E, F) hydrogen at atmospheric pressure. They all
revealed completely different reorganization morphologies for the same multilayer
stack. After argonoxygen, as well as nitrogen anneal, no clear sintering of porous
material is seen (Kuzma-Filipek et al. 2007). It is known that for the reorganization
of Psi, the internal surface must be free of native oxide, since the presence of an
oxide suppresses the mobility of silicon atoms (Herino et al. 1984). It was found
that argon annealing was causing a 2030 nm oxide layer on a macroporous
structure, not present while annealing in hydrogen (Depauw et al. 2008, 2009).
Lack of oxide while annealing in hydrogen is due to the chemical affinity of
hydrogen to oxide, hydrogen being a strong reducing agent.
The mechanism of pore reorganization in argon is similar to the one in hydrogen
ambient but is slower and less effective due to the absence of H2 species which
accelerate formation and degassing of SiO (Claassen and Bloem 1980). Possible
scenario of reorganization of pores in Ar and H2 was given by Depauw et al. (2008,
2009), proposing that (i) at the initial stage a thin oxide layer is formed by aging on
the pore walls after anodization and (ii) in Ar at high temperature, the oxide is
603
Fig. 3 Different reorganized microstructures for the multilayer porous silicon reflector structure:
(a) as etched, (b) treated in argonoxygen (14slm Ar, 1,000 C), (c) after treatment in argon and in
hydrogen under low pressure (14slm Ar, 1,000 C + H2 reduced pressure 1,000 C), and (d, e, and
f) after treatment in hydrogen at atmospheric pressure (1,130 C, 25slm H2, atmospheric pressure)
(Kuzma-Filipek 2010)
604
I. Kuzma-Filipek
etched into gaseous SiO. Part of it is escaping the pores during the heat treatment
and part may stay inside the pores trapped during the progressive closure of the
pores due to surface energy minimization. During cooling down the inner SiO
converts back into SiO2. In hydrogen, this situation is different since the etch rate of
SiO2 is much faster than pore closure allowing most of the SiO to escape from the
pore. In case of mesoporous multilayer structure annealed in argon, the SiO etching
is most likely prevented due to confinement of the layers (See Fig. 3b).
Due to low-pressure conditions, like in Fig. 3c, reorganization is inhomogeneous
and does not start simultaneously for each layer until spherical closed voids are
formed, but rather the maturity of voids is reached much faster at the surface than in
the regions located away from the surface. This is the reason why the layers below
are not transforming homogeneously and reveal still the intermediate elongated
types of pores, while the top layer consist of overgrown voids which are merging
into large cavities. Figure 3df presents the fully reorganized complex multilayer
structure under condition of atmospheric pressure and hydrogen treatment which is
used as a preconditioning in silicon epitaxy to avoid oxide formation.
Table 1 gathers literature results about porous silicon sinter processes under
various conditions and the effect of sintering.
Porous Silicon Sintering: Device Applications

There are numerous device applications requiring using porous silicon processed at
high temperatures, as mentioned earlier. These can be divided into two categories:
sintered porous silicon used as a sacrificial layer in the layer transfer processes
(LTP) and heat-treated porous silicon embedded in the structure for other purposes
(light trapping, gettering). The layer transfer techniques using porous silicon as a
sacrificial and separation layer, or as an active and separation layer, are the sintered
porous silicon process (SPS) (Tayanaka et al. 1998) or (PSI) process (Kuchler
et al. 2000) or the quasimonocrystalline silicon process (QMS) (Rinke
et al. 1999). The first large-scale commercial product based on sintering processes
of porous silicon uses mesopores for producing silicon on insulator (SOI) wafers,
and it is known as the Epitaxial Layer TRANsfer (ELTRAN) process from CANON
(Yonehara et al. 1994).
Similar processes were investigated by other groups (Brendel et al. 2001; Reuter
et al. 2009). Active layer formed on top of sintered porous silicon has been
successfully integrated into device fabrications as the sintering reduces the amount
of stacking faults and improves crystalline of the porous silicon template layer
(Kuzma-Filipek 2010; Solanki 2004). This can be due to that fact that sintering of
porous silicon causes lattice contraction at above 350 C, meaning that lattice
spacing of the PSi layer decreases with increasing annealing temperature
(Sugiyama and Nittono 1989).
Both macroporous and mesoporous silicon are similarly exploited to achieve
various types of separation and/or seed layers by high-temperature anneal and
formation of active layer by epitaxial growth or epitaxial free processing
605
Table 1 Porous silicon reorganization conditions

Porous silicon system
Nano-mesoporous
monolayer
P+ (10 2 cm)
P (1015 cm)
Mesoporous and
macroporous mono-/
multilayer, low-level
porosities 20/40 %
Sintering process
100800 C,
vacuum furnace
(10 610 9 Torr)
8801,130 C H2
(100750 Torr)
Effect
Observed desorption
of hydrogen from
Psi layer at 400 C
or lower causes the
strain variation
Dangling bond
density starting to
increase at 350 C
up to 500 C and
plays a significant
role in the structural
changes
Lattice contraction
of Psi after thermal
treatment
(at 350 C)
Psi under tension
after annealing
Structural changes
start at temperatures
>450 C. Thin
oxide layer formed
on pore surfaces can
suppress the surface
migration of Si
atoms
H desorption
responsible for
strain variation in
Psi, ends at 550 C
Pore coarsening
observed at 600 C
Structural
reorganization until
facetted shape voids,
pore size
distribution reveals
an increasing
median with the
annealing
temperature
and time
880 C, 30 min
H2- isolated
elongated pores;
972 C, 30 min
H2- isolated
spherical
pores;1,070 1,130

C facetted pores
Authors
Ogata et al. (2001)
Buttard et al. (1999)
Sugiyama and
Nittono (1989)
Labunov
et al. (1987)
Ogata et al. (2001)
Ogata et al. (2001)
Herino et al. (1984)
Halimaoui
et al. (1995)
Gardelis
et al. (1995)
Kuzma-Filipek
(2010)
Depauw et al.
(2008)
Ott et al.
(2003, 2004)
Sugiyama and
Nittono (1989)
(continued)
606
I. Kuzma-Filipek
Table 1 (continued)
Porous silicon system
Sintering process
Effect
1,000 C,
atmospheric
pressure, ArO2,
N2, and forming gas
(100750 Torr)
Lattice spacing of
the Psi layer
decreases with
increasing annealing
temperature
No clear sintering
effect due to SiO,
SiOH, and SiN
bonds blocking the
surface diffusion
Macroporous
monolayer
1,0001,100 C,
atmospheric
pressure, Ar, H2
anneal (<100 Torr)
Mesoporous multi-/
monolayer,
low-level porosities
20/40 %
1,000 C reduced
pressure conditions
Mesoporous multi-/
monolayer, high-level
porosities > 40 %
>1,000 C
(100750 Torr), H2
and vacuum
Structural
reorganization
present with thin
oxide layer
Transformation of
pores into
completely empty
spheres resembling
SOI, called ESS
(empty space in
silicon)
Enhanced surface
diffusion, enhanced
structural changes
close to the top
surface in reduced
pressure conditions
and preconditioning
with H2
Dendritic
microstructure with
higher initial
porosity shows
slower restructuring
during heat
treatment
Authors
Depauw et al. (2008,

2009)
Kuzma-Filipek
et al. (2007)
Lehman
et al. (2002)
Depauw
et al. (2009)
Mizushima
et al. (2000)
Kuribayashi
et al. (2004)
Kuzma-Filipek
(2010)
Kuribayashi
et al. (2004)
Sato et al. (2000)
Ott et al. (2004)

Zheng et al. (1997)
(Depauw et al. 2008, 2009; Brendel et al. 2010). Similar studies of void shape
evolution and SON (silicon-on-nothing) structure formation from masked
anisotropic reactive ion etching resulting in square arrays of holes during H2 anneal
were shown in Sudoh et al. (2009). Other less costly techniques using purely
electrochemical macroporous silicon were also proposed (Lehmann et al. 1992;
Solanki et al. 2004).
Sintered porous silicon is also known to improve optical properties by scattering
light at the 10100 nm voids, which was investigated by numerous of authors
607
(Wolf et al. 2008; Ghannam et al. 2006). Additionally while constructing multilayer
porous designs, these promote constructive interference by multiple reflections at
the layer interfaces, which are preserved after high-temperature treatment. For
those reasons it is incorporated in thin film solar cells as optical boosters (Zettner
et al. 1998; Duerinckx et al. 2006; Kuzma-Filipek et al. 2008; Krichen et al. 2009).
Authors in Duerinckx et al. (2006) and Kuzma-Filipek et al. (2007) additionally
emphasize that the high-temperature driven reorganization of the nm-sized pores
into voids surrounded with silicon matrix preserves the conductivity of the majority
of carriers in the devices (Kuzma-Filipek et al. 2007, 2008; Duerinckx et al. 2006).
It was shown in Kuzma-Filipek et al. (2007) that the reorganization of porous
silicon by sintering at 1,130 C in pure H2 is assuring no resistive losses for the
current flow.
Conclusions
Numerous applications in, e.g., biomedical or microelectronics require application of sintered porous silicon, and this is for either controlled molecule release,
enhancement of mobility, conductivity, or optical properties of porous silicon. In
the layer transfer processes (LTP), sintering is a critical step to form a sacrificial
porous layer used for active layer detachment. Sintering process of porous silicon
is well described by classical theory of sintering and is driven by the minimization
of the surface energy, linked to the internal surface area. The annealing temperature and annealing ambient atmosphere are triggers to activate both volume and
surface transport mechanisms, with the emphasis to the later one. Elongated
annealing time can lead to similar evolution of the pore structure as increasing
temperature.
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Porous Silicon and Conductive Polymer

Nanostructures Via Templating
Farid A. Harraz
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Various Classes of Porous Silicon Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Filling Porous Silicon Templates with Various Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Selective Dissolution of Porous Silicon Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
612
613
614
618
619
620
Abstract
Conductive polymer nanostructures synthesized using porous silicon (PSi) templates are described, with an emphasis on PSi template advantages, pore-filling
phenomenon, mechanism of polymerization, and selective removal of PSi to
release the polymeric structures. The interaction of pyrrole monomers, as a case
study, on the entire surface of PSi under both galvanostatic and potentiostatic
deposition modes is presented with discussion on the processing issues associated with the electrochemical deposition process inside the pores. Additionally,
various materials infiltrated into PSi templates are briefly described. Examples
of free-standing conductive polymer structures formed by selective dissolution
of PSi are provided.
F.A. Harraz (*)

Nanostructured Materials and Nanotechnology Division, Central Metallurgical
Research and Development Institute (CMRDI), Cairo, Egypt
Promising Centre for Sensors and Electronic Devices (PCSED), Advanced Materials
and NanoResearch Centre, Najran University, Najran, Saudi Arabia
e-mail: fharraz@cmrdi.sci.eg
DOI 10.1007/978-3-319-05744-6_63
611
612
F.A. Harraz
Introduction
Template synthesis is a commonly used tool for the preparation of nanomaterials
and has been developed independently in various fields of nanotechnology.
Several studies and reviews on various template syntheses are well documented
(Hulteen and Martin 1997; Johnson et al. 1999; Whitney et al. 1993; Martin 1996;
Moller and Bein 1998; Tian et al. 2003; Raman et al. 1996; Bhushan 2004; Yang
et al. 1999). Compared to other sophisticated methods such as molecular beam
epitaxy and nanolithography, the template synthesis is an elegant, cost-effective
with a high-yield alternative technique (Martin 1994; Hu et al. 1999;
Aravamudhan et al. 2007; Chen et al. 2006). Prefabricated nanostructured materials with cylindrical nanopores are often used as shape-defining molds. For the
fabrication of one-dimensional polymer nanostructures, three main strategies
have been defined including self-assembly (Shimizu 2008), electrospinning
(Greiner and Wendorff 2008), and template synthesis. However, significant drawbacks are associated with the former two techniques as the number of materials
that could be self-assembled is limited, in addition to the difficulty to achieve
diameters below 100 nm with good degree of organization using electrospinning.
However, template synthesis is advantageous and has become one of the interesting and active synthetic approach in that field. It acts to direct the growth or
organization of nanostructures under conditions that preserve the original shape
or symmetry of template. The most common templates are track-etch polymeric
membranes (Chakarvarti and Vetter 1998) and porous alumina (Masuda and
Fukuda 1995). However, PSi (Lehmann 1993) template has significant advantages
over the traditional templates in fabrication of one-dimensional nanostructured
arrays with high aspect ratios and narrow diameter distributions. One of the unique
properties of PSi is the ability to precisely tune the pore diameter and surface
morphology via varying the Si dopant type and level and controlling the applied
current and time during the electrochemical etching. The compatibility of PSi with
conventional silicon processing technology adds another advantage. A variety of
materials including metals, conductive polymers, carbons, oxides, and semiconductors can be deposited within the cylindrical pores of PSi templates by different
methods such as electrochemical deposition, solgel, and chemical vapor deposition, leading to different morphologies including nanotubes, nanowires or
nanorods, nanorings, nanodots and heterogeneous nanostructures, etc. The dimensions of as-formed nanostructures can be easily controlled by regulating the
template pores and shapes and the deposition conditions. We focus on conducting
polymers; the process flow for fabrication of polymeric nanostructures using PSi
templates is depicted in Fig. 1.
Since the main objective of this handbook is dedicated to the fabrication,
characterization, processing, and applications of PSi, this chapter focuses on
utilizing PSi as a template-directing synthesis of polymeric nanostructures.
We begin with the preparation of various shapes and morphologies of PSi
templates. This is followed by a brief summary and tabulation of the main studies
Porous Silicon and Conductive Polymer Nanostructures Via Templating
613
Fig. 1 Process flow for

fabrication of polymeric
nanostructures using porous
silicon template
on polymer and other materials incorporation into PSi templates. We then focus on
the electrochemical polymerization of pyrrole into PSi templates as a case study
and discuss the processing issues associated with its deposition inside the nanoscale
pores under both potentiostatic and galvanostatic deposition modes. Selective
dissolution of PSi templates to release the deposited polymers is consequently
presented. Finally, a summary of the chapter is given.
Various Classes of Porous Silicon Templates

With PSi templates, pore diameters from <5 nm up to >1 m are accessible.
Typical examples of SEM micrographs of PSi templates, mainly ordered
macropores (5 m), medium-sized pores (120 nm), and mesopores (20 nm), are
presented in Fig. 2. The templates were prepared by electrochemical dissolution of
Si in HF-based solutions (see handbook chapter Porous Silicon Formation by
Anodization). For ordered macropores (Kobayashi et al. 2006), p-type Si(100),
1020 cm, was used. Ordered etch pits were initially created on Si surface by
photolithographic pre-patterning technique and subsequent alkaline etching
process. The dissolution was conducted, after removal of a SiO2 resist film, in a
solution 47 wt% HF/H2O/2-propanol at current density 13 mA cm 2 for 60 min. For
medium-sized pores (Ogata et al. 2007), 6 wt% HF + 8 mM KMnO4 + 3,000 ppm
NCW-1001(surfactant) was used as anodizing solution with n-type Si(100),
0.01000.0180 cm at 25 mA cm 2 for 125 s. For mesopores (Harraz 2006), a
p-type Si(100), 0.01-0.02 cm, was anodized in 28 wt% HF/H2O/ethanol solution
at 50 mA cm 2 for 30 s.
614
F.A. Harraz
Fig. 2 SEM top views (-1) and cross-sectional views (-2) of porous silicon templates with
different pore diameters. (a) Ordered macropores: 5 m. (b) Medium-sized pores: 120 nm. (c)
Mesopores: 20 nm (Fukami et al. 2008)
Filling Porous Silicon Templates with Various Materials

Porous silicon has been employed as a template for infiltrating various materials.
The variety of materials includes but is not limited to metals, oxides, magnetic
alloys, and conducing polymers. Table 1 lists the main studies on polymer impregnation into various PSi templates together with the deposition methods and work
objectives. The template nanostructures with specific physical properties are
expected to demonstrate a broad range of utility in spintronics, magnetic and
magneto-optic devices, and biochemical, acoustic, drug delivery, photovoltaic,
and sensing applications. Table 2 collects various materials that have been infiltrated into PSi templates. It is worthy to note that a common drawback for most
studies listed in Table 2 is related to the observation of pore mouth blockage due to
pore plugging effect. In case of polymer deposition and under optimized conditions,
such plugging effect could be avoided to a large extent. The use of PSi as a
template-directing synthesis of polymeric nanostructures is explored in this section.
Conducting polymers are usually synthesized from the appropriate monomers by
either chemical or electrochemical oxidative polymerization. Electrochemical
polymerization is preferred for better penetration inside the nanopores. Polypyrrole
(PPy) is one of the most important and extensively studied conducting polymers
(Moreno et al. 1999; Vrkoslav et al. 2006; Lewis et al. 1997; Akundy and Iroh
2001). The deposition of PPy into PSi templates could be achieved by the electrochemical oxidation of pyrrole monomers at constant current or potential in the
acetonitrile solution containing tetrabutylammonium perchlorate as supporting
electrolyte. Typical potential (Et) and current transients (it) recorded during
the deposition of PPy into mesoporous silicon templates are shown in Fig. 3.
Poly( pphenylenevinylene)
Polyaniline
Polypyrrole, polyaniline,
polythiophene
Poly-vinyl-carbazole
MEH-PPV
PMMA
Variety of organic and

biopolymers
PDMS
Mesopores
Mesopores
Mesopores, medium-sized
pores, ordered macropores
Medium-sized pores
Macropores
Macropores
Mesopores
Macropores
Mesopores
Deposited polymer
Poly(bithiophene), poly
(3-dodecylthiophene)
Polypyrrole
PSi template type

Mesopores
Solution cast
Wetting in
solutions or
melts
Solution cast
Electrochemical
Spin coating
Spin-on coating,
immersion
Electrochemical
Chemical
Electrochemical
Deposition
method
Electrochemical
Sensing and drug

delivery
Gecko for mimetic
devices
Improve rectifying
performance
Pore filling, tuning
surface morphology
Photovoltaic device
Improve
photoluminescence
Pore filling
Improve electrical
contact, gas sensing
Light-emitting device
Objectives
Pore filling
Table 1 List of the main studies on polymer impregnation into porous silicon templates
Guo et al. (2013)
Li et al. (2003)
Steinhart et al. (2002)
Harraz (2006, 2011), Harraz

et al. (2008a, b), Fukami et al. (2008)
Nahor et al. (2011)
Mishra et al. (2008)
Fan et al. (1998), Halliday et al. (1996)
References
Schultze and Jung (1995),
Errien et al. (2005)
Moreno et al. (1999), Vrkoslav
et al. (2006)
Nguyen et al. (2003)

615
616
F.A. Harraz
Table 2 List of various materials infiltrated into porous silicon templates

PSi
template
type
Macropores
Deposited
material
LiNbO3
Micropores
Macropores
NaNO2
SnSe, Sn,
SnO2
Macropores
Ni, Cu,
Mesomacropores
Mediumsized pores
Mediumsized pores
Au, NiCo
CoPt
alloy
Fe3O4
Deposition
method
Impregnation in
solution
Infiltration
Chemical
reduction or
oxidation
Electroless,
electrochemical,
immersion
plating
Electrochemical
Electrochemical
Infiltration
Objectives
Silicon photonics
References
Zhao et al. (2005a)
Template filling
Murzina et al. (2007)

Zhao et al. (2005b)
Pore filling, high

aspect ratio
metallic
structures
Pore filling,
ferromagnetic
Magnetic
structures
Ferromagnetic
characteristic
Zhang et al. (2006),

Kobayashi
et al. (2006), Harraz
et al. (2005)
Chourou et al. (2011),
Rumpf et al. (2011)
Harraz et al. (2013)
Harraz (2013)
Fig. 3 Potential transient

(galvanostatic deposition:
1 mA) and current transient
(potentiostatic deposition:
0.8 V) of PPy in mesoporous
silicon templates in 0.1 M
pyrrole monomers
The mechanism of polymer infiltration into the pores is of major importance in

order to obtain the desired structures and control the final morphology.
Different characteristic stages of PPy deposition could be observed. The sharp
potential rise through AB region is related to nucleation of PPy at the pore bottom
and partial oxidation of PSi. Constant potential recorded during BC period is
attributed to polymer growth inside the pores (pore filling). At point C, the pores are
completely filled with PPy. A potential shift accompanies the stage transition of
617
Fig. 4 SEM images of cross-sectional views of porous silicon templates after deposition of
polypyrrole into (a) macropores, (b) medium-sized pores, (c) mesopores, and deposition of
polyaniline into (d) macropores with inhomogeneous pore filling
CD. Further polymerization after step D results in a potential leveling. At this

stage the polymerization proceeds preferentially on the outer surface of template.
One can observe different characteristic stages of potentiostatic deposition
(it transient) resemble those obtained for (Et) transient. Two current minima
are observed at points B and D, of which the deposition proceeds inside the pores
and at the outer surface, respectively. The current decrease during CD stage in it
curve is corresponding to a potential increase in Et curve. It is worthy noted that,
the amount of charge consumed for complete pore filling with PPy (qAC) and during
the stage transition CD (qCD) in both galvanostatic and potentiostatic techniques is
equivalent each other. The shape of the above transients is essentially dependant on
the type of conducting polymer and pore size, depth, and morphology of PSi
templates. This means that the time of electrochemical polymerization is different
with each template. For the case of macropore filling, the potential shift was not
observed after 5 h electropolymerization. After pore filling, the as-formed polymer
arrays can be obtained by a selective dissolution and removal of PSi templates in
alkaline solution.
Cleaved cross-sectional samples shown in Fig. 4 revealed that the porous
templates are filled with polymer (bright areas corresponding to polypyrrole deposition). However, image (d) is related to the deposition of polyaniline in random
618
F.A. Harraz
macroporous silicon template, of which inhomogeneous pore filling can be

observed. This is actually related to the electrochemical polymerization of
polyaniline is not optimized with respect to deposition potential or current values
and solution chemistry.
Selective Dissolution of Porous Silicon Templates

Porous silicon template could be carefully removed via selective chemical etching
in tetramethyl ammonium hydroxide (TMAH) solution at 4090 C. Such dissolution process is crucial and not so easy to control. The etch rate is not the same
for different Si templates. It depends on the Si dopant type and level as well as on
the pore depth and diameter. The removal of template could be done using KOH
solution, but the etching behavior is completely different from the case of TMAH.
Ethylene diamine pyrocatechol is also reported as a chemical etch solution at
115 C to successfully remove the silicon (Tondare et al. 2008). Some technical
challenges exist during Si template removal, including control of gas evolution
during the dissolution, avoiding the corrosion of infiltrated material, and to
achieve a high purity of the remaining structures. The released polymeric
nanostructures are shown in Fig. 5. Well-ordered, linear micro rods and nanowires
of PPy are obtained. The polymers are true replicas of the original pores. Image
(f) is related to the released arrays of polyaniline. The formation of nanowires
actually is a proof that the deposition of polymer proceeds preferentially at the
Fig. 5 SEM images of polypyrrole nano- and microstructures after selective removal of porous
silicon templates. Images (ae) are related to polypyrrole, image (f) is for polyaniline. (d) is a
magnified image of (b). Image (e) corresponds to partially filled pores. Templates used are (a)
ordered macropores and (c) mesopores while (b, d, e, f) medium-sized pores
619
pore bottom and grows toward the outer surface. The different pore sizes of
templates do not appear to hinder the polymerization process. Furthermore, no
pore blockage with polymer was observed by applying such electrochemical
techniques. Some of the nanowires are oriented in different directions; this
observation was not a result of imperfections in either the PSi template or
polymerization behavior as the original pores were almost aligned in parallel
(Fig. 2). Instead, this bundling is most likely an artifact of mechanical forces on
the nanowires incurred during the dissolution and drying processes (see handbook
chapter Drying Techniques Applied to Porous Silicon).
It appears now that surface morphology of polymeric micro- and nanostructures
could be tuned via the tuning of PSi templates, which is considered a unique
property of PSi compared to other porous templates. Additionally, due to the
semiconducting behavior of PSi layer as well as the silicon pore walls, one expects
that the polymerization proceeds homogeneously from the pore bottom or preferentially at the pore walls, depending on the dopant type of the starting silicon
substrate and the mode of electropolymerization process. This facilitates the preparation of different shapes, like wires, rods, or tubes. However, this is not possible
in case of porous alumina, for instance. Furthermore, due to the insulating character
of porous alumina, one should create an electrical contact on the backside before
inserting the template in the electrolytic solution. However, this step is not needed
in case of PSi, particularly the case of porous layers prepared using heavily doped
substrates. Finally, such hybrid nanostructures of PSi and conducting polymers
could be beneficial to current and future technologies based on conducting polymers, including photovoltaic devices and sensing applications.
Conclusions
To summarize this chapter, a variety of porous silicon layers (mesoporous,
medium-sized pores and macroporous regimes) could offer a versatile approach
as a template-directing synthesis of polymeric micro- and nanostructures. The
pores are filled homogeneously with polymer using the electrochemical technique. Selective dissolution of the silicon template is possible using an alkaline
solution, thereby releasing well-ordered polymeric nanostructures having the
same architectures of that of host PSi templates. The current template synthesis
technique is advantageous compared to other conventional porous templates,
especially the frequently used porous alumina template, since the surface
morphology of deposited material could be carefully tuned. Such combined
approach (porous silicon template electrochemistry) is expected to demonstrate
a broad range of utility for fabricating various micro- and nanostructured materials. Finally, one further expected benefit of PSi template synthesis which is
challenging with other approaches is the ability to infiltrate dissimilar materials
into a single nanostructure. This actually would allow for coupling between
materials that have, for instance, complementary optical and magnetic properties
that can interact in a novel way.
620
F.A. Harraz
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Melt Intrusion in Porous Silicon

Armando Loni
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Calculation of Payload . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Loading of Freestanding Flakes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Loading of Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
623
624
625
626
627
627
Abstract
Loading porous silicon by bringing it into contact with a molten substance

facilitates complete pore filling through capillary action, or melt intrusion. If the
intrusion is carried out at elevated temperature, the molten active can return to a
solid form at room temperature, remaining in the pores. Reviewed herein are the
methodologies used for loading freestanding porous silicon flakes and powders.
Introduction
Many applications of porous silicon make use of the available void fraction,
whereby the pores are filled with some substance of interest, for example, a
beneficial active compound (see, e.g., the handbook chapters Drug Delivery
with Porous Silicon and Porous Silicon and Functional Foods). The loading
methodology depends, to some extent, on the properties of the active material to be
loaded. If the active can be dissolved in a suitable solvent, and assuming the solvent
does not interact with the porous silicon, then high payloads can be achieved by
A. Loni (*)
DOI 10.1007/978-3-319-05744-6_64
623
624
A. Loni
Table 1 Actives loaded into porous silicon by melt intrusion (authors data, except where
indicated)
D-Panthenol
Function
Humectant/moisturizer
Triclosan
Ciprofloxacin (Wang et al. 2012)
Ethyl butyrate
Camellia
Peppermint
Erythritol
Antibacterial
Antibiotic
Flavoring/fragrance
Fragrance
Flavoring
Sweetener
Lauric acid (Saffie and Canham L

Composite material comprising a
porous semiconductor
impregnated with an organic
substance. US Patent US 8, 088,
401 B2, 3 Jan 2012)
Vitamins E and K (Saffie and
Canham L Composite material
comprising a porous
semiconductor impregnated with
an organic substance. US Patent
US 8, 088, 401 B2, 3 Jan 2012)
Cosmetics additive
Thermal properties relevant to

loading
Viscous oil; thins at 75 C;
useable to 135 C
Melts at 55 C
Molten at 250 C
Thin oil at room temperature
Melts at 121 C; useable to
250 C
Melts at 44 C
Supplement
Viscous oils; thin at 70 C
Active
sequential dosing and drying. For an active with intrinsically low solubility, and
that possesses good thermal stability up to its melting point, an alternative loading
technique is melt intrusion. Used originally for impregnating porous glass with
metal oxide (Bartholomew and Garfinkel 1969) and semiconductor (Huber and
Huber 1988) materials and, more recently, to produce metal-porous silica
nanocomposite structures (Charnaya et al. 2011) and polymer composites from
porous silicon (Steinhart et al. 2002; Li et al. 2003), the melt intrusion technique
facilitates, in principle, complete pore filling in a single dose.
Melt intrusion can be used in situations where the active to be loaded is either in
a concentrated liquidus phase at room temperature or can be rendered molten from a
solid at elevated temperature. Some actives can be too viscous at room temperature
although the application of heat (while avoiding thermal decomposition) can
facilitate pore intrusion. Examples of active compounds that have been loaded
into mesoporous silicon by melt intrusion are listed in Table 1.
Calculation of Payload
The payload, as determined experimentally, is typically calculated in weight percent, following the formula:

Weight% WA = WA WpSi 100
625
(1)
where WA and WpSi refer to the weights of active (in the pores) and porous silicon,
respectively. The maximum theoretical payload corresponding to completely filled
pores can be calculated if the porosity of the porous silicon (pSi) and the density of
the active (A) are known; in terms of density (), Eq. 1 can be rewritten to give a
maximum predicted payload:
h
i
Weight% A = A pSi 100 P =P 100,
where P is the porosity (% void) and pSi 2.33 g/cm3. Porosity and pore volume
are, of course, related. Pore volume is usually defined in terms of unitary weight
of material (ml/g, cm3/g); for porous silicon, therefore, multiplying the measured
pore volume by the density of the active gives an upper limit for the weight of
active that will completely fill the pores, and the theoretical payload can be
written as
Weight% VA A =VA A 1 100,
where VA is the available pore volume (in ml/g) that can be completely filled with
active.
Loading of Freestanding Flakes

If a molten active is slowly added to the surface of a porous silicon film attached
to its parent wafer, it intrudes into the pore structure at a rate that depends
primarily on both the viscosity of the melt and the pore morphology. If the porous
silicon is in the form of detached, freestanding flakes, these can be immersed
completely in the melt; with two surfaces in contact with the melt, the loading is
quicker, the uniformity in both cross section and depth can be better, and payloads
can be higher than those achievable with wafers, especially so for very thick
layers.
As melt intrusion proceeds, air is displaced from the porous silicon flake
and air bubbles may be evident. Depending on viscosity and the layer thickness,
the pores can be completely filled within a couple of minutes. On removal from
the melt, any excess on the surface of the flake can be wiped off with filter paper or
a cotton swab slightly wetting these items, first, with a solvent that is known to
dissolve the active, minimizes any residual surface excess; this is particularly
useful when measuring payload, since it is the active that is in the pores, alone,
that contributes to the calculation. Flakes are therefore useful as model structures,
since information such as how payloads vary with porosity can readily be
obtained, Fig. 1.
626
A. Loni
Fig. 1 Payload dependency

on porosity for Triclosan,
loaded from melt (Authors
data; mesoporous silicon
prepared from 5 to 20 mcm
p-type wafers by anodization)
Loading of Powders
While knowledge of the available pore volume is useful to know, in practice it is not
strictly necessary. If the porous silicon is in powder form, the active can be slowly
added to the porous silicon and mixed the mixing action homogenizes the blend
and allows empty particles to make contact with residual molten active that has not
yet been adsorbed; with subsequent addition and mixing, all of the porous particles
eventually become filled by capillary action. Alternatively, the porous silicon
powder can be added to the molten active a slurry is formed, initially, which
gradually thickens and dries as more powder is added. The end of either process
is defined as the wet point, where the powder is on the verge of being freeflowing.
The wet point is an inherently variable state that depends on individual judgment. Without prior knowledge of the maximum permissible weight of active, and
depending on the skill of the formulator, the loading will usually be taken slightly
beyond the wet point, leaving residual surface active; in this situation, additional
porous silicon powder can be added to effectively adsorb the residue the downside
then is that there will be a small fraction of material that is not fully loaded,
although this will be homogenized within the overall blend.
Another method for loading powders is to blend and melt. If the active
compound is in a solid powder form, this can be blended with the porous silicon
powder the composite blend is then heated to beyond the melting point of the
active, where it starts to be adsorbed within the porous silicon. Careful manipulation of the ratios (together with uniform blending) can facilitate loading to just
before the wet point, such that residual active on the surface of the porous silicon
can be minimized. The blend and melt technique has been applied to the loading
of Ciprofloxacin (Wang et al. 2012), Triclosan (Wang et al. 2010), and Ketoconazole (Tang et al. 2013).
627
Discussion
As with solution loading, the surface passivation of the porous silicon is important
when loading by melt intrusion if the active is hydrophilic, for example, then the
payload is likely to be small for hydride-passivated porous silicon. Some actives
can, during loading, chemically oxidize or etch the porous silicon at elevated
temperature, while some actives can degrade when in contact with the internally
passivated silicon hydride surface. For the majority of applications, the highly
reactive hydride surface will be modified before loading, more often than not
by thermal oxidation (with, of course, subsequent reductions in pore volume
and payload).
Payloads achievable through melt intrusion are dependent on the viscosity of the
active as well as loading time. The loading time will also be dependent on pore
morphology and either layer thickness or particle sizes. Experimental values for
payload tend to be lower than theoretical estimates, Fig. 1; this is likely to be related
to both the pore morphology whereby it is more difficult for intrusion to occur
within smaller interconnecting pores or branches and pore depth, if pores become
blocked before being filled to the pore tip, for example, (Salonen et al. 2005); for
very high-porosity material, there may also be some degree of pore collapse on
air-drying, and this would also contribute to different experimental payloads.
If the active reverts to a solid while confined in the pores (e.g., after cooling), its
physical properties are likely to be determined by the nanostructure the freezing
and melting points of pore-confined solids, for example, have been shown to
be dependent on pore size and geometry (Charnaya et al. 2011; Jackson and
McKenna 1990), and, depending on pore size, the active may remain amorphous
or recrystallize.
Residual active on the surface of loaded powders is difficult to avoid if the pores
are to be completely filled and will depend on the particle size distribution smaller
particles will become fully loaded before larger ones, for example. Residual surface
active will not be in a nanostructured form and, if solid at room temperature,
will cool to a crystalline state rather than remain amorphous (as it could be in
small mesopores). This dual physical nature of the active can be characterized
(see X-ray Diffraction in Porous Silicon) and should be taken into consideration for any proposed application.
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Porous Silicon and Electrochemical

Deposition
Yukio H. Ogata and Kazuhiro Fukami
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Displacement Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Micro- and Nanostructure Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
630
630
631
632
632
636
Abstract
Porous silicon is a promising template for the preparation of metal

nanostructures by electrochemical deposition. Because porous silicon is a
semiconductive porous electrode, electrochemical deposition of metals occurs
not only at the bottom of pores but also on the pore wall and pore openings.
Thus, the control of electrochemical deposition within porous silicon has been a
challenging issue. Electrochemical deposition on porous silicon is influenced by
illumination conditions. Metal deposition on porous silicon is possible by displacement deposition. Many studies have reported on electrochemical deposition of metal for practical applications. In this chapter, electrodeposition under
polarization is firstly reviewed. Secondly, displacement deposition on porous
silicon is explained. Finally, the microscopic structure formation by electrodeposition on porous silicon is summarized.
Y.H. Ogata (*)

Institute of Advanced Energy, Kyoto University, Uji, Kyoto, Japan
e-mail: ogata.yukio.34m@st.kyoto-u.ac.jp
K. Fukami
Department of Materials Science and Engineering, Kyoto University, Kyoto, Japan
e-mail: fukami.kazuhiro.2u@kyoto-u.ac.jp
DOI 10.1007/978-3-319-05744-6_65
629
630
Y.H. Ogata and K. Fukami
Fig. 1 Schematic illustrations of typical morphologies obtained in electrodeposition on porous

silicon. Illustrations of (a), (b), and (c), respectively, show pores capped with a metal film, pores
modified with discrete metal islands, and pores completely filled with metal
Introduction
Metal deposition on porous silicon has been studied since the early period of porous
silicon research. The major target started from the improvement of the luminescent
properties (Canham 1997), the formation of an effective heterojunction between
semiconductor and metal for applying the junction to various types of electronic
devices at the time. Afterwards, the target spreads to versatile fields such as optical
diagnostics/plasmonics, fabrication of metalsilicon hybrid materials for catalyst,
microstructure formation of a metalsilicon hybrid material, and low-dimensional
structure formation. These applications utilize the characteristic structure of porous
silicon: (a) fine porous structure with high aspect ratio; (b) easily oxidizable nature;
and (c) neither conductive nor nonconductive, but semiconductive material. Basic
understanding on the deposition behavior on a porous silicon surface is indispensable for meeting a variety of requirements depending upon the application (Hyde
and Compton 2003; Oskam et al. 1998; Zhang 2001).
Since application of a wet process for copper wiring was demonstrated by the
IBM group in 1997 (Andrecacos et al. 1998), applicability of the electrochemical
deposition to fine structure formation has been widely recognized. Electrochemical
deposition enables to prepare various types of porous silicon modified with metal as
illustrated in Fig. 1. We confine the topic in this section to the wet processes here.
The processes consist of electrodeposition and displacement or electroless
deposition.
Electrodeposition
Silicon is a semiconductor and it causes specific characteristics which are not
expected in the deposition on a conductive substrate. Metal deposition or reduction
reaction requires the supply of electrons at the conductive band or the hole injection
to the valence band.
Men ne ! Me
or
631
Men ! Me nh
(1)
where Me stands for metal. The hole-injection process is only possible when the
redox potential or the Fermi level of metal/metal-ion system stays below the energy
level of the valence band. It happens in some noble metal systems. Otherwise
electrons at the conduction band are required for the progress of metal deposition
reaction. n-type silicon meets this requirement, whereas p-type silicon lacks this
condition. Illumination helps the progress of deposition on p-type porous silicon.
Deposition becomes possible even on p-type silicon when breakdown occurs under
very high polarization. Heavily doped silicon or degenerate silicon, n+ or p+ silicon,
behaves like conductor, where illumination is not the requirement even it is p-type
silicon. It must be noted that cathodic reaction proceeds on a semiconductor surface
following its kinetics at the beginning of deposition, but the surface covered with
deposited metal behaves as a metal electrode. The two kinetics are usually very
different from each other.
Displacement Deposition
Silicon is a less-noble material. The redox potential (2) is difficult to measure
directly in aqueous solution since silicon is easy to be oxidized and cannot stay as
silicon itself. The value estimated from thermodynamic data (Bard et al. 1985) is as
follows:
Si 2H2 O ! SiO2 4H 4e
Eo 0:85 V versus SHE
(2)
Porous silicon readily undergoes oxidation in aqueous solution. Electrons

formed by the oxidation reduce metal ions thermodynamically, if the equilibrium
potential stays positive compared with the potential of reaction (2).
When porous silicon is immersed in an aqueous solution containing noble
metal ions such as silver and copper, the metal is deposited on porous silicon.
Oxidation of the porous silicon surface is confirmed by IR spectroscopy (Hilliard
et al. 1994) and XPS spectroscopy (Jeske et al. 1995). In contrast, displacement
reaction does not take place in deposition of less-noble metals such as nickel and
iron (Tsuboi et al. 1998; Ronkel et al. 1996). Deposition behavior does not show a
significant difference between n-type and p-type silicon substrates (Tsuboi
et al. 1999). The potential is determined by a mixed potential of the cathodic
and anodic reactions. The rate of reaction (2) slows down in progression since the
reaction leaves insulative SiO2 resulting in the decrease of active silicon surface.
It leads to the decrease in metal deposition rate. In some cases, holes participate
in place of electrons. The deposition and oxidation do not necessarily take
place at the same site. Produced charge carriers can migrate in silicon or metal,
and they can be consumed at the different sites from the electron source
632
(Harraz et al. 2002). The deposition ceases after the silicon surface exposing to
electrolyte is completely oxidized.
There are competitive reactions to metal deposition. The most influential
reaction is hydrogen evolution reaction. The reaction competes with metal deposition reaction. As a result, noble metal is deposited, but less-noble metal is
difficult to be deposited. The potential of hydrogen evolution reaction shifts
toward negative with increasing solution pH. One can deposit less-noble metals
in solution of high pH (Takano et al. 2000; Harraz et al. 2003). Solution
containing fluorides is also used for the displacement solution. Presence of
fluorides reduces it to a binary system eliminating the oxides (Harraz
et al. 2003). The oxidized silicon dissolves or silicon directly dissolves away
into the solution.
Micro- and Nanostructure Formation

Metal deposition creates a hybrid material of metal and semiconductor
and the new material is expected to develop a new function, where
microstructuring is crucial. A variety of techniques have been utilized for producing the 2D and 3D structures. They are controlled physically, mechanically,
optically, and electrochemically. Some examples of the 2D or position-selective
local deposition are summarized in Table 1. The optical control is only
possible on p-type silicon and deposition of less-noble metal. Illumination
creates charge carriers and the illuminated spot undergoes deposition.
Otherwise, excess free electrons and displacement deposition hinder the selective
deposition.
The advantage or uniqueness arises from the micro- and nanostructures. It is
often preferred that deposition copies precisely the porous silicon structure. The
hybrid structure or the structure after removing the porous silicon substrate can be
utilized in a wide variety of applications. Metal deposition in these structures and
the successive silicon dissolution have been utilized to form the 3D structures.
Many interesting results have been obtained (Table 2).
Conclusions
Electrochemical deposition enables wide applications of porous silicon in many
fields such as optics, sensing, microfabrication, and catalysis. Fine tuning in
morphology of deposits, which is crucial for applications, has been desired. As
reviewed in this chapter, control of metal electrodeposition has greatly improved in
the recent decades. However, there still exist many open questions, such as nucleation and growth and mass transfer for 3D structure formation. They are doubtlessly
important and seem to be future issues.
633
Table 1 2D structure formation of deposits on porous silicon

Type
Optical
Physical
Deposit
Ni, Cu
Technique
DP, 532 nm laser
irradiation
Ni, Cu
ED, Ar+ laser,

scanning
Au
Laser heating
with its
interference
pattern, alloying
Au, Cu
ED, Si2+ ion

implantation
Ag, Cu
DP, porous
Al2O3 or
polystyrene
colloidal crystal
as mask
DP, inkjet
printing
Ag
Mechanical
Pd
Au, Ag
Co
Electrochemical
ED,
AFM-scratching
through the SiO2
layer
DP, nanoindentation
Cu
ED,
electrochemical
machining with
ultrashort
voltage pulses
Cu
ED,
electrochemical
scanning
capillary
microscope
DP displacement deposition, ED electrodeposition
Remarks
Smallest diam.
5 m with P ion
implantation
Metal patterning
without mask or
resist.
Suppression of
DP is necessary
for Cu. 20 m
Laser heating
after uniform Au
deposition. Etch
pattern
formation: pit,
ring, line
High deposition
rate at the
defected sites.
Patterning
Natural
lithography,
50100 nm size,
starting from flat
Si
Direct patterning
on porous silicon.
SERS
applications
Defects,
sub-100 nm
width
Defects,
3050 nm
resolution
Roughened
surface accept
the nucleation,
500 nm size.
Starting from flat
Si
Pure
electrochemical,
200 nm size,
using a flat Si
References
Kordas et al. (2001),
Scheck et al. (2004)
Sasano et al. (2003;
2004)
Koynov et al. (2006)
Schmuki and Erickson

(2000)
Ono et al. (2007)
Chiolerio et al. (2012)
Santinacci
et al. (2003)
Kubo et al. (2005)
Trimmer et al. (2005)
Staemmler
et al. (2004)
Mesoporous (normal:
550 nm in diameter)
Porous silicon
Mesoporous (fine: 35 nm in
diameter)
DP
ED
ED
ED
ED
ED
Fe
Fe
Ni-Fe/Au
Co-Fe
Ni, Co,
NiCo, Fe
ED, DP
Pt
Cu
DP
Au
DP
DP
Pt
Ag, Au
Technique
DP
Deposit
Pt
Table 2 3D structure formation and deposition control on porous silicon
p-Si, catalytic activity of Pt

nanoparticles on CO oxidation,
methanol as solvent for the deposition
bath
p-Si, micro and meso, plasmon
resonance studies, ethanol as solvent for
the deposition bath
p-Si, chemical modifications of the pore
wall, effect of the affinity of pore wall
with water
p-Si, dendrite growth, Si nanowire
formation
p-Si, n-Si. Deposition behavior at the
pore opening
p-Si. Chronoamperometry
n-Si. Characterization by XPS
p-Si, n-Si. 40 nm and 290 nm in
diameter
XANES investigation. Coverage of the
top surface by Fe, but penetration of Co
in pores
n-Si, shape varied between spheres,
ellipsoids, and wires, and their magnetic
properties
Remarks
n-Si, micro and meso, catalyst for fuel
cells
(continued)
Rumpf et al. (2010),

Granitzer et al. (2010)
Bandarenka
et al. (2012; 2013)
Renaux et al. (2000)
Ronkel et al. (1996)
Aravamudhan
et al. (2007)
Kashkarov
et al. (2009)
Peng and Zhu (2004)
Fukami et al. (2012)
Polisski et al. (2011)
References
Brito-Neto
et al. (2006), Hayase
et al. (2004)
Polisski et al. (2008)
634
ED
Cu
Au
Electroless deposition
ED
Cu
Cu, Ni-B
ED
Cu, Ni
DP, metal-catalyzed CVD
ED, single solution for porosification

and deposition
ED, dark for Cu, illumination for Ni
Ni
Au
Technique
DP, pore widening of with oxidation
and dissolution in HF
Deposit
Ni
DP displacement deposition, ED electrodeposition
Others
Porous silicon
Macroporous
Table 2 (continued)
p-Si, application of Cu deposited Si

nanowires to Li-ion batteries
n-Si, medium-sized pores (~100 nm in
diameter), surface plasmon resonance
study
p-Si (111), Si nanowire arrays,
vaporliquidsolid growth
p-Si, mesopores formed by metalassisted etching, adhesive metal films
n-Si, macropores formed by metalassisted etching
p-Si, n-Si, Cu micro-rods, Ni microtubes
Remarks
p-Si, complete replication of pores.
Freestanding arrays of high-aspect-ratio
Ni pillars
n-Si, microneedles with 10 m diam
Lee et al. (2009)
Yae et al. (2011)
Yasseri et al. (2006)
Munoz-Noval
et al. (2013)
Kobayashi
et al. (2006), Fang
et al. (2007)
Foell et al. (2010)
Sato et al. (2005)
References
Zhang et al. (2006)

635
636
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Gas and Liquid Doping of Porous Silicon

Riccardo Rurali
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Direct Charge Injection and Passive Impurity Reactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reduced Dielectric Mismatch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
639
640
641
642
643
Abstract
There is now both experimental and theoretical data relating to conductivity

changes in porous silicon and other silicon nanostructures arising from the
adsorption of specific molecules. The phenomenon is reviewed with emphasis
on the potential mechanisms involved and its exploitation with regard sensing
applications.
Introduction
Since the early years, porous Si (p-Si) attracted great interest for possible applications in the field of sensors, from the former IBM Patent including p-Si into a
C-MOS device (Burkhardt and Poponiak 1977) to the first studies on p-Si reactivity
to vapors and moistures (Anderson et al. 1990; Schechter et al. 1995; Motohashi
et al. 1996; OHalloran et al. 1999; Foucaran et al. 1997) to the evidence of p-Si
luminescence quenching in interaction with nitrogen dioxide (Harper and Sailor
1996). The high surface-to-bulk ratio and the porous structure itself seemed ideally
R. Rurali (*)
Institut de Cie`ncia de Materials de Barcelona (ICMAB-CSIC), Campus de Bellaterra,
Bellaterra, Spain
e-mail: rrurali@icmab.es
DOI 10.1007/978-3-319-05744-6_66
639
640
R. Rurali
suited for the efficient detection of molecules in the liquid or in the gas phase. More
recently, though, porous Si has emerged as an effective playground to test in a
simple and cost-effective way several ideas applied to the rising field of semiconducting nanowires (Bruno et al. 2007; Rurali 2010). Although chemical sensing is
an interesting field per se also for the nanowires community, the similarity between
these two materials naturally reoriented the research in porous Si toward applications that naturally lay in realm of (nano)electronics. Molecular doping, after all, is
nothing else that a special class of gas sensing, that is, the capability to tune the
electronic properties of the material, namely, its carrier density, in a controlled way.
This approach is in principle very appealing for nanowires, as the efficiency of
conventional impurity doping has been shown to decrease as a result of several
mechanisms, such as quantum confinement (Niquet et al. 2010), dielectric
mismatch (Bjork et al. 2009), and surface segregation (Fukata et al. 2011).
Direct Charge Injection and Passive Impurity Reactivation

The first and more convincing reports of reproducible n-type doping were related to
the adsorption of ammonia (Geobaldo et al. 2003; Chiesa et al. 2003; Garrone
et al. 2005). At first a short transient where the adsorption results in a decrease of
carrier density is observed. Samples are obtained from highly boron p-type doped Si
wafers; thus, the first electrons transferred are recombining with the holes present,
compensating the residual p-type character of the material. After that, a systematic
increase of the carrier concentration as the NH3 partial pressure is increased is
consistently observed (Garrone et al. 2005). Further, electron spin resonance (ESR)
measurements and first-principles calculations based on density-functional theory
(DFT) convincingly show that the injected charges are electrons and n-type doping
is achieved. The theoretical calculations show that the NH3 molecule can easily
bind a surface dangling bond via the nitrogen lone pair and then transferring one
electron to the Si skeleton (Miranda-Durn et al. 2010; Miranda et al. 2012); see
Fig. 1. Interestingly, Konstantinova et al. (2009) reported a dependence of the
ammonia doping effect on trace water presence, a mechanism that is not yet fully
clear and needs to be explored further.
Some of these and other experiments also related the adsorption of NO2 to an
increase of hole concentration, indicating the achievement of p-type doping
(Garrone et al. 2003, 2005; Boarino et al. 2001; Geobaldo et al. 2001, 2004;
Gaburro et al. 2004). Here, however, the situation is not as clear as with NH3.
The same DFT calculations that supported the n-type character of NH3 here suggest
that NO2 should not provide measurable effect of the conductivity of the porous Si
sample. Specifically, both the HOMO and the LUMO of the molecule fall well
inside the Si bands, thus failing in providing shallow levels similar to those
provided in conventional impurity doping (Miranda-Durn et al. 2010).
Nevertheless, it should not be forgotten that upon etching, most of the active
boron impurities end up at subsurface sites where they form an electrically inactive
complex with a surface dangling bond. It then turns out that what NO2 adsorption
641
Fig. 1 Adsorption of (a) NH3 and (b) NO2 at a Si dangling bond. NH3 adsorption results in n-type
doping, pinning the Fermi level close to the conduction band (c), while the NO2 adsorbed system
remains intrinsic, with no half-filled level next to any of the bands (d). The projected DOS of the
side panels illustrates the contribution of the atomic species. N and O are shown in blue and red
spheres, respectively, while yellow and white spheres represent Si and H atoms (Reprinted with
permission from . Miranda-Durn et al. (2010) Nano Lett. 10 (9), 3590. Copyright 2010
American Chemical Society)
does is not providing itself a hole, but rather reactivating the passive subsurface
boron atoms. It can be said that NO2 is electronegative enough to take the electron
of the dangling bond, but not enough to create a hole in the valence band.
Clearly, this looks like a less reliable doping mechanism, as it ultimately relies
on the concentration of the preexisting doping impurities and on how many of them
were passivated at subsurface locations, then amenable to reactivation.
Reduced Dielectric Mismatch

Other experiments presented results that, at first sight, are even more puzzling than
those related to the adsorption of NO2. Ethanol, acetone, and water are expected to
be virtually inert when brought in contact with a Si surface (Chiesa et al. 2005;
Timoshenko et al. 2001; Cultrera et al. 2013). No strong chemical interaction is
observed and DFT calculations yield fully occupied, mid-gap molecular levels,
which are too deep for their electrons to be thermally activated to the host
conduction band.
Interestingly, here the mechanism is fundamentally different to the cases
discussed above, although it shares with NO2 adsorption the fact that the carriers
642
R. Rurali
responsible for the increase in the conductivity were already present in the material,
but deactivated. Let us see how.
Before quantum confinement effects can be observed, there is a regime often
referred to as dielectric confinement or dielectric mismatch. There, the average
thickness of the Si instances that make up the spider web that results from the
electrochemical etching process is around 512 nm. At these sizes quantum confinement cannot effectively deactivate dopants by making their electronic levels
deep, but dielectric confinement can. In a nutshell, when the host material tries to
screen an ionized impurity, image charges accumulate at the nanostructured Si
surface and change the dielectric problem (Diarra et al. 2007). This new situation is
easily shown to lead to deeper, thus electrically inactive, impurity levels. This is
going to be the situation of those boron atoms that have not ended up at passive
subsurface locations discussed above.
Upon pore condensation with, say, ethanol, the effective dielectric constant of
the medium surrounding the nanostructured Si changes and increases from 1 (vacuum) to 25 (ethanol). A simple model based on dielectric mismatch is discussed by
Timoshenko et al. (2001) shows that in such conditions the activation energy of a B
acceptor decreases from 105 to 30 eV. It should be kept in mind that B impurities
are present in large concentrations in porous Si samples.
Again, like in the case of NO2 adsorption, this is not a genuine doping mechanism where the molecule injects a charge in the host material. Here the concentration and the doping type (n- or p-type) depend on the chemical nature of the
impurities that are reactivated.
Liquid doping can feature considerably subtler effects and is more difficult to
capture with simple model as the adsorption of a few gas molecules (Canham 1986;
Beale et al. 1992; Gelloz et al. 1996, 2000). For instance, Canham (1986) observed
that the near-infrared PL of bulk n-type silicon was reversibly lowered upon
exposure to oxygen and reversibly increased upon exposure to water, but in
p-type silicon water had the opposite effect, lowering the PL efficiency. This was
interpreted within the Stevenson-Keyes theory as surface potential changes due to
adsorbed surface states. Water vapor can be effective in pushing the surface Fermi
level toward the conduction band edge, while oxygen is known to induce negative
charging on etched Si surfaces. Non-radiative surface recombination velocity was
thereby affected and hence PL efficiency. Although these observations were made
on bulk and not nanostructured Si, they give a hint of the possible intertwined new
effects that can come into play. In the same line, cross-sectional imaging of EL
suggested that the conductivity of wet porous silicon could be dramatically higher
than that of the same structure dried (Beale et al. 1992).
Conclusions
Gas and liquid doping has been reported in porous Si, including porous Si-related
systems such as nanowires that hold great promises for the next generation of
(nano)electronic devices. In this chapter we have given an overview of the most
pyridine
643
ethanol
e-
e-
h+
h+
h+
h+
e-
Fig. 2 Cartoon illustrating the two doping mechanisms: charge transfer from the adsorbates (left)
and dopant reactivation upon adsorption (right).
noticeable success cases in this field. It must be kept in mind, nonetheless,

that doping is the controlled modification of the conductivity of a semiconducting
material and in this sense conventional impurity doping is intended and
works. Unfortunately, in many of the cases discussed, the level of control of
the increase of free carrier is poor or absent and relies on the characteristic of
the undoped material. NO2 adsorption, ethanol pore condensation, and similar
mechanisms effectively reactivate latent dopants, but it is the concentration
of the latter that will determine the conductivity of the material. It is only through
the chemisorption of ammonia and pyridine, among the cases discussed
here, that molecular adsorption influences directly the variation of free carriers
(Fig. 2).
When it comes to sensing, on the other hand, many of these limitations disappear, and we envisage this to be the field where porous Si might be most useful. At a
large extent, in a gas sensor, what matters is detecting gas concentration above a
certain threshold, and any change in the conductivity giving this information will
serve this purpose. It does not really matter now if the carrier concentration
increases because of preexistent dopant reactivation or genuine charge injection,
as long as a measurable jump in the current shows up.
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Functional Coatings of Porous Silicon

Frederique Cunin
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Functional Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Characterization Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Functionalities and Application Areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
647
648
648
649
649
656
Abstract
This chapter reports on the variety of functional coatings for porous silicon
structures, and reviews the methods developed for their respective deposition,
the spectroscopic and analytical techniques used for their characterization, and
the functionalities imparted to porous silicon related with their specific domains
of application.
Introduction
Functional coating refers to thin layer or covering of functional material that is
applied to a substrate in order to create additional function on the substrate and
specifically design its surface properties for a practical application. Functional
coatings are developed for applications in various areas: soft functional biocoatings
F. Cunin (*)
Institut Charles Gerhardt Montpellier, Montpellier, France
e-mail: frederique.cunin@enscm.fr
DOI 10.1007/978-3-319-05744-6_67
647
648
F. Cunin
are designed for medical and biosensing uses (chapters Drug Delivery with
Porous Silicon, Porous Silicon Immunoaffinity Microarrays, and
Porous Silicon in Brachytherapy), carbon coatings for stable battery anodes
(chapter Porous Silicon and Li-Ion Batteries), and metals for electrical contact
(chapter Ohmic and Rectifying Contacts to Porous Silicon) or gas detection
(chapter Porous Silicon Gas Sensing). They play a key role in improving/
controlling the mechanical and chemical stability of the substrate, which is
crucial for sensing applications (chapters Porous Silicon Diffraction Gratings,
Porous Silicon Photonic Crystals, and Porous Silicon Optical Biosensors),
for the development of micro-optic devices (chapters Porous Silicon
Functionalities for BioMEMS, Porous Silicon for Microdevices and
Microsystems, and Porous Silicon Photonic Crystals) or for tuning the
biodegradability of a medical nano-tool (chapter Chemical Reactivity and
Surface Chemistry of Porous Silicon). Functional coating appears as continuous
or discontinuous film of variable thickness depending on its chemical nature and
way of deposition, which covers the outer and/or the inner surface of the porous
substrate. Coatings variety with the different deposition techniques attempted are
first summarized. Classical and specific characterization techniques for coating
layers and composites are reported. Finally, selected useful functionalities and
their domain of application are presented.
Figure 1 illustrates the variety of functional coatings on structures of porous
silicon including films, membranes, and micro- and nanoparticles. The outer and/or
the inner surface of the pores can be layered or fully embedded.
Functional Coatings
Table 1 lists various coatings on porous silicon structures (chip based, microand nanoparticles), and the methods are developed for their respective deposition.
Characterization Techniques
Commonly used spectroscopic or analytical techniques for characterizing surfaces
and coating layers on porous silicon are Fourier transform infrared spectroscopy
(FTIR), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy,
energy dispersive X-ray spectrometry, fluorescence spectroscopy, UVVis absorption/reflectance spectroscopy, thin film optical interference spectroscopy, impedance spectroscopy, optical microscopy, scanning electron microscopy, transmission
electron microscopy, atomic force microscopy, ellipsometry, nitrogen adsorption/
desorption analysis, and water contact angle.
Spectroscopic and analytical techniques specifically used to characterize coatings on porous silicon are secondary ion mass spectrometry (SIMS) (polymer
coatings), cyclic voltammetry and electrochemical measurements (conductive
649
Fig. 1 Various functional coatings onto porous silicon surfaces: (a) thermally responsive polymer/porous silicon hybrid for biosensing (Perelman et al. 2010), (b) porous silicon/polymer
nanocomposite for biosensing (Li et al. 2005), (c) BSA protein-adsorbed porous silicon surface
(Tay et al. 2004), (d) diamond-capped porous silicon film for optical devices (Fernandes
et al. 1999), (e) biocompatible polymer/porous silicon composite fiber (Kashanian et al. 2010),
(f) block copolymer-coated surface for templating (Qiao et al. 2007), (g) ZnO-deposited porous
silicon (Kayahan 2010), (h) SERS active silver-coated porous silicon (Virga et al. 2012)
(Reproduced, with permission, from Perelman et al. (2010), Li et al. (2005), Tay et al. (2004),
Fernandes et al. (1999), Kashanian et al. (2010), Qiao et al. (2007), Kayahan (2010),
Virga et al. (2012))
polymer, metals and metal oxides coatings), magnetic measurements (metals and
metal oxides coatings), Raman spectroscopy (carbon coatings), surface plasmon
resonance (SPR), and nuclear magnetic resonance (NMR) (lipid coatings and
organic layers).
Functionalities and Application Areas

Table 2 lists the various functionalities imparted to porous silicon, with relevant
coating types and domains of application.
Conclusion
Surface coating/capping is an essential step when designing porous silicon-based
systems. Initially developed for surface passivation purposes in the early 1990s for
stabilizing photoluminescence or refractive index, for example (Loni 1997), surface
coating has greatly evolved from passive to much more active duty. Nowadays
functional coatings not only passivate the surface but also impart specific
Coating nature
Polymers
Organization of the
composite (thickness
when relevant)
Coating in and
outside pores
Coating outside pores
(m to hundreds of
m)
(tens of m)
(tens of nm)
Coating in and
outside pores
Coating in and
outside pores

Coating inside pores
Deposition technique
Impregnation/drop
coating/contact
lamination
Spin coating/dip
coating/spray coating
Chemical vapor
deposition
Electropolymerization
Surface-initiated
polymerization
Microemulsion
Self-assembly
Covalent grafting of
polymers and oligomers
onto porous silicon
Table 1 Functional coatings and deposition techniques
Responsive polymers
and copolymers
Biocompatible or
biodegradable
Biodegradable
copolymers
Copolymers
Responsive and
biocompatible
Polymers
Conducting polymers
Study examples
Responsive polymers
and hydrogels
Biocompatible or
biodegradable
polymers
Copolymers
Industrial synthetic
polymers
Copolymers
Copolymers
Qiao et al. (2007)a

Schwartz et al. (2005), Kilian et al. (2007a), Britcher
et al. (2008), Segal et al. (2009), Godin et al. (2010)a,
Sciacca et al. (2011)
Fan et al. (2012)a, MP
Abalyaeva and Efimov (2000), Batra et al. (2006),

Urbach et al. (2007)a, Chiboub et al. (2010a, b)a,
Belhousse et al. (2010)a
McInnes et al. (2009)a, Bonanno and DeLouise
(2010)a, Wang et al. (2012)a, Vasani et al. (2011), Pace
et al. (2012a)a, Yoon et al. (2003)
McInnes et al. (2012)a
Li et al. (2005)MP, Tighilt et al. (2007), Zhang

et al. (2011)a

Bakker et al. (2003)a, DeLouise et al. (2005)a, Segal
et al. (2007)a, Wu and Sailor (2009)a, Alvarez
et al. (2009)a, Pastor et al. (2011)MP, Low et al. (2006),
Park et al. (2009)NP, Fan et al. (2009)MP, Kashanian
et al. (2010)a, MP, Gongalsky et al. (2012)a, MP,
Perelman et al. (2010)a
650
F. Cunin
Biomolecules
Carbonb
Metals and metal

oxides
In situ polymerization
of precursors and
thermal
decomposition
Deposition/
adsorption/selfassembly
Thermal
decomposition of
acetylene
Chemical vapor
deposition
Atomic layer epitaxy
Impregnation of
precursors and thermal
decomposition/
annealing
Sputtering/magnetron
sputtering
Immersion plating
Carbon
Proteins, peptides,
antibodies, DNA, lipid
layers, etc.
Coating in and
outside pores
Carbon
Diamond, diamondlike carbon
Carbon
Functionalized carbon
SnO, CoSi2, Si(1-x)Gex
Cu, ZnO, WO3, Al,

Ag, ZnO
Ag, Metal oxides (Sn,

Fe, Ni) Au
Ag, Au, Pd, Pt, Se, Cu,

Bi, W, Mo, Ni, Fe, Al,
Ti, Mg, Fe2O3

Coating in and
outside pores
Coating in and
outside pores
(tens of nm)
Coating in and
outside pores

(m)
(continued)
Tay et al. (2004)a, Steinem et al. (2004)a, Schwartz

et al. (2007), Perelman et al. (2008)a, Alvarez
et al. (2009)a, Wu et al. (2009)a, Flavel et al. (2011)a,
Salonen et al. (2004), Bjorkqvist et al. (2004, 2009),

Kaukonen et al. (2007)MP, Torres-Costa et al. (2008,
(2009), Bimbo et al. (2010)NP, Fang et al. (2010),
Sciacca et al. (2011), Makila et al. (2012), Jalkanen
et al. (2012), Rytkonen et al. (2012)NP
Cho (2010)MP, Kelly et al. (2011)a
Mattei et al. (2007), Fernandes et al. (1999)a,

Baranauskas et al. (2000), Makara et al. (2003),
Aroutiounian et al. (2007)
Ducso et al. (1996), Loni (1997)
Ghosh et al. (2002), Kumar et al. (2012), Sun

et al. (2010), Giaddui et al. (1998), Kim and Lee
(2008), Kayahan (2010)
Chan et al. (2003)a, Cobianu et al. (1997)a, Moshnikov

et al. (2012)a, Behzad et al. (2012)
Lin et al. (2004), Giorgis et al. (2009), Virga

et al. (2012), Canham (2006), Dhar and Chakrabarti
(1996), Park et al. (2006)a

651
Organic and
inorganic
monolayers
Coating nature
Table 1 (continued)
Lipid bilayers
Functional alkanes and

alkenes, silane,
organics

(nm)
Coating in and/or
outside pores
Fusion of lipid
vesicles (SUV, MLV,
giant, etc.)
Covalent grafting
(electro, UV, thermo,
catalyst, microwave
assisted)
Proteins, gelatin
Proteins, antibodies,
DNA, etc.

Coating in and
outside pores
Study examples
Spin coating
Covalent grafting
Deposition technique
Organization of the
composite (thickness
when relevant)
Choi and Buriak (2000), Buriak (2002), Schmeltzer

et al. (2002), Stewart and Buriak (2002), Boukherroub
et al. (2003), Vrkoslav et al. (2007), Lagrost
et al. (2007), Kilian et al. (2008), Pace et al. (2009,
2010), Velleman et al. (2010)a, Guan et al. (2011), Xue
et al. (2011)a, Sweetman et al. (2011b), Sweetman and
Voelcker (2012)
Bimbo et al. (2011)a, MP, Sweetman et al. (2012)a,

Sarparanta et al. (2012)a, NP, Bimbo et al. (2012)a, MP,
Kilian et al. (2007b), Mey et al. (2012)a
Orosco et al. (2006)a, Gao et al. (2008)
Dancil et al. (1999)a, Tinsley-Bown et al. (2000)a,
Voicu et al. (2004)a, Kilian et al. (2007c), Bocking
et al. (2008), Sam et al. (2010, 2011), Sweetman
et al. (2011a)a
Worsfold et al. (2006)a, Cunin et al. (2007)a, Pace
et al. (2012b)a
652
F. Cunin
Spin coating
Impregnation of
precursors and thermal
treatment
Electrochemical
anodization
Coating on top of
porous silicon
Coating in and
outside pores

Coating in and
outside pores
Porous silica
Silica gel
Dense silica
Porous silica
Functional alkanes and

alkenes
Nitrides
Lharch et al. (2003)
Posada et al. (2006)

Akusawa and Hara (2007)
Corban et al. (2003), Amato et al. (2005)
Frascella et al. (2009)
Buriak (1999)
The surface of porous silicon was oxidized or chemically modified prior to the coating step
Si-C (silicon carbide) coatings on porous silicon are not reviewed in this chapter
c
Silicon dioxide functional coatings are obtained by deposition of additional SiO2 material on the porous silicon substrates. Silicon dioxide layers obtainable
by direct controlled oxidation of the porous silicon films (by chemical, thermal, ozone, or aging treatments) are not reviewed in this chapter. Thermal oxidation
is reviewed elsewhere in handbook (chapters Oxidation of Macroporous Silicon)
MP
functional coating is realized on porous silicon microparticles
NP
functional coating is realized on porous silicon nanoparticles
Silicon dioxidec
Chemical vapor
deposition
Chemical vapor
deposition
Ultrahigh vacuum

653
654
F. Cunin
Table 2 Functionalities of coatings and utilization

Functionality
Surface chemical/
mechanical
stabilization; surface
passivation; surface
protective coating
Coating nature
Silicon dioxide
Carbon/diamond
Polymers
Biomolecules/
organic monolayers
Metals
Application area
Optical devices
Gas sensors
Surface hydrophilicity/
hydrophobicity
Biomolecules/
polymers/organic
layers
Carbon
Gas sensors,
biosensors,
controlled drug
delivery
Biomimetic surface/
artificial membrane
Lipid bilayers
Biosensors, drug
characterization,
diagnosis
Biocompatible surface;
bioactive surface, cell
adhesion promoting
surface; cell targeting;
biofouling surface;
furtivity
Polymers (natural,
biocompatible,
conductive, etc.)
Cell culture/
bioassays
Bioimaging/
biosensing/drug
delivery
Tissue
engineering/
implants
Biomolecules
(antibodies,
proteins, etc.)
Organic layers
Controlled drug
delivery
Membrane/
separation
Study examples
Posada et al. (2006),
Fernandes et al. (1999),
Fang et al. (2010),
Bimbo et al. (2012), Tay
et al. (2004), Salonen
et al. (2004), Bjorkqvist
et al. (2003, 2004, 2009),
Torres-Costa
et al. (2008, 2009),
Buriak (2002)
Buriak (2002), Pace
et al. (2009, 2010),
Sweetman and Voelcker
(2012), Salonen
et al. (2004), TorresCosta et al. (2008,
2009), Bimbo
et al. (2011, 2012),
Kovalainen et al. (2013),
Liu et al. (2012)
Worsfold et al. (2006),
Kilian et al. (2007b),
Cunin et al. (2007), Pace
et al. (2012b), Mey
et al. (2012)
DeLouise et al. (2005),
Schwartz et al. (2005),
Low et al. (2006),
Whitehead et al. (2008),
Park et al. (2009),
Alvarez et al. (2009),
McInnes et al. (2009),
Wu et al. (2009), Godin
et al. (2010), Sweetman
et al. (2011a, b, 2012,
Secret et al. (2012),
Flavel et al. (2011),
Guan et al. (2011),
Sarparanta et al. (2012)
(continued)
655
Table 2 (continued)
Functionality
Sensing active surface
(enhanced sensitivity,
specificity)
Stimuli responsive
surface
Coating nature
Silicon dioxide
Polymers
(responsive,
natural,
biocompatible,
conductive, etc.)
Application area
Optical devices
Sensors,
biosensors
Controlled drug
delivery
Biomolecules
(DNA, antibodies,
bacteria, peptides,
etc.)
Metal/metal oxides
Carbon/diamond/
functionalized
carbon
Surfaceenhanced Raman
spectroscopy
(SERS)
Polymers
(responsive,
biocompatible,
conductive, etc.)
Biomolecules
(antibodies, etc.)
Silicon dioxide
Smart responsive
surfaces and
scaffolds
Controlled drug
delivery/
nanovalves
Study examples
Corban et al. (2003),
Urbach et al. (2007),
Belhousse et al. (2010),
Bonanno and
DeLouise (2010),
Sciacca et al. (2011),
Gongalsky et al. (2012)
Dancil et al. (1999),
Tinsley-Bown et al.
(2000), Steinem et al.
(2004),
Voicu et al. (2004),
Kilian et al. (2007c),
Wu et al. (2009),
Jane et al. (2009),
Sam et al. (2010, 2011),
Chan et al. (2003),
Lin et al. (2004),
Gabouze et al. (2007),
Giorgis et al. (2009),
Jiao et al. (2010),
Virga et al. (2012),
Moshnikov et al. (2012),
Fernandes et al. (1999),
Kaukonen et al. (2007),
Kelly et al. (2011),
Makila et al. (2012)
Batra et al. (2006),
Wu and Sailor (2009),
Fan et al. (2009),
Segal et al. (2009),
Kashanian et al. (2010),
Perelman et al. (2010),
Vasani et al. (2011),
Pastor et al. (2011),
De Rosa et al. (2011),
McInnes et al. (2012),
Pace et al. (2012a),
Xue et al. (2011),
Anglin et al. (2008)
(continued)
656
F. Cunin
Table 2 (continued)
Functionality
Conductive/magnetic/
superconductive
surface
Coating nature
Carbon
Iron oxide, mixed
oxide, niobium
Polyaniline
Application area
Li batteries
Optoelectronic
Sensors
Low reflective surface
Porous silicon itself

Diamond-like
carbon
Optical and
optoelectrical
devices
Solar cells
Luminescence
enhancement/
modification/
stabilization
Silicon dioxide,
metals/metal
oxides, diamond,
polymers
(conductive,
bioresorbable)
Optical devices
Sensors,
bioimaging
Study examples
Kim et al. (2008),
Cho (2010), Mattei et al.
(2007), Park et al.
(2006), Chiboub et al.
(2010a, b), Abalyaeva
and Efimov (2000),
Thakur et al. (2012),
Trezza et al. (2008),
Dai et al. (2007)
Schirone et al. (1997),
Lipinski et al. (2003),
Panek (2004),
Aroutiounian
et al. (2007)
Kim et al. (2009),
Kim et al. (2012),
Wang et al. (2000),
Gongalsky et al. (2012),
Chen et al. (2013),
Halliday et al. (1996)
functionality and activity, e.g., increasing/changing photoluminescence properties,

enhancing sensitivity, providing superconductivity, etc. Remarkable accomplishments in functional coatings were also achieved in particular interfacing with
biological environments, opening great promises for nanomedicine.
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Electroencapsulation of Porous Silicon

Matti Murtomaa and Jarno Salonen
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrospraying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electroencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
Electroencapsulation is an application of electrospraying in which liquid is

atomized into micro- or even nanosized droplets using electrostatic forces
alone. The method allows better controllability of the capsulation process than,
e.g., the most commonly used spray drying. Due to the applied electrostatic
forces, it also enables production of complex capsule structures, like solid shell
covered liquid core particles. In this review, we will focus on electroencapsulation processes used to improve the handling, processing, and administration
of porous silicon-based drug delivery systems.
M. Murtomaa (*)
Department of Physics and Astronomy, University of Turku, Turku, Finland
e-mail: matti.murtomaa@utu.fi
J. Salonen
Turku, Finland
DOI 10.1007/978-3-319-05744-6_68
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Introduction
Recently, mesoporous silicon (PSi) has proven to be an appealing candidate as
a drug carrier (Salonen et al. 2008 and Handbook Chapter Drug
Delivery with Porous Silicon). However, there are some issues which hinder
its use in oral delivery. Firstly, nanoparticles have a strong tendency to
form aggregates because of forces such as van der Waals attractive force
(Parsegian 2006; Peng et al. 2010). This makes the handling, processing, and
dosing very challenging. Secondly, certain combinations of the loaded drug, PSi
porosity, and surface chemistry may encourage premature dissolution of the
drug in stomach (Salonen et al. 2001). For optimal drug absorption in the
body, it is often best that the dissolution of the drug takes place as the drug
carriers arrive to the small intestine (Kimura and Higaki 2002; Masaoka
et al. 2006). To avoid unwanted metabolism and degradation, and to increase
bioavailability, drug carriers need to be protected with a shell which dissolves
at the optimal delivery site. One possible method for achieving both
improved mechanical properties and targeted delivery is electroencapsulation,
which allows better controllability of the capsulation process than, e.g., spray
drying.
Electrospraying
Electroencapsulation is an application of electrospraying (electrohydrodynamic
spraying). In electrospraying, liquid is atomized into micro- or even nanosized
droplets using electrostatic forces alone (Bailey 1989). As high electric field is
applied to the tip of a capillary containing the liquid, high charge density is
induced on the liquid surface. The highly charged surface of the droplet experiences strong coulombic force due to applied external electric field and also due to
high unipolar charge density within the liquid. These forces cause elongation of
the meniscus. As electric field is increased, the diameter of droplets decreases and
the dropping frequency increases. This regime is called micro-dripping, and the
size of the droplets can be precisely controlled. When the electric field is high
enough, the liquid in the tip of capillary forms a so-called Taylor cone and the
surface disrupts into small droplets emitting from the tip. The formed droplets
have very narrow size and charge distribution. This mode of electrospray is called
cone-jet mode (Cloupeau and Prunetfoch 1994; Grace and Marijnissen 1994;
Jaworek 2007; Jaworek and Sobczyk 2008). The narrow size distribution is
enhanced by coulombic forces which tend to keep the uniformly charged droplets
apart (Brandenberger et al. 1999). Also, monodispersity can be enhanced using
pulsed or ac voltage superimposed in excitation (dc) voltage (Sample and Bollini
1972; Sato 1984).
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Electroencapsulation
In electroencapsulation, two immiscible liquids are atomized simultaneously using two
nozzles maintained at opposite polarities (Langer and Yamate 1969). Thus, emitted
droplets have opposite polarities and will be attracted by coulombic forces. As droplets
collide, they form a capsule where liquid with higher surface tension is covered with
liquid having lower surface tension. Simultaneously, the opposite charges cancel each
other resulting in electrically neutral structure which can be further processed. Another
method for electroencapsulation involves only one nozzle but there are two concentric
capillaries carrying immiscible liquids (Loscertales et al. 2002; Lopez-Herrera
et al. 2003). If this geometry, electro-coextrusion, is used, the resulting droplets remain
highly charged. The core capillary may contain PSi particles in a drug solution and the
surrounding capillary polymer solution, for example. In general, the core liquid
contains a drug solution or a suspension to be shielded. If a solid capsule is desired,
the solution used as shell liquid is chosen so that it can be solidified by, for example,
evaporation of solvent or by using anti-solvent method.
Electroencapsulation of PSi has been recently reported for the first time by Roine
et al. In their work, two oppositely charged sprays were used (Roine et al. 2012). Core
liquid contained drug-loaded PSi micro- or nanoparticles immersed in glycerol
(particles size <25 m and <1 m, respectively). Shell liquid consisted of Eudragit
E 100 in chloroform. Schematic diagram of two nozzle electroencapsulation system
is presented in Fig. 1a. The simplified diagram shows the collision of oppositely
charged droplets. More realistically, droplets are emitted as a conical spray and the
velocity of the droplets is quickly reduced below the grounded plate. Because the
droplets are small and carry high electric charge, they tend to quickly follow electric
field lines onto nearby grounded objects and spraying chamber walls. But as oppositely charged clouds mix, some droplets drift to close proximity and coulombic force
merges the droplets. Simultaneously, opposite charges cancel out, collisions come to
an end, and the neutral droplets fall due to gravity. As the formed capsule falls down,
solvent evaporates and a hard shell is formed. Evaporation can be further enhanced
by heating or by reducing the air pressure (Nystrom et al. 2010). Figure 1b shows a
photograph taken during the spraying. Fine mist of droplets is emitted from both
capillaries. As oppositely charged droplets merge, larger capsules are formed and
these can be seen at the lower end of the picture. Produced capsules have been studied
with different methods. X-ray microtomography pictures proved that the capsules
were spherical and the shell had relatively uniform thickness (Fig. 1c).
Process Development
It has been presented that it is possible to prepare free flowing powder of electroencapsulated PSi particles with uniform and narrow size distribution. However, the
technique suffers from several issues which need to be addressed before the method
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M. Murtomaa and J. Salonen
Fig. 1 From left to right: (a) Schematic diagram of a two-nozzle electroencapsulation setup; (b)
Photograph showing oppositely charged sprays mixing and the formation of larger droplets
(capsules); (c) X-ray microtomography image of a spherical 25 m capsule containing PSi
nanoparticles (<1 m). Thickness of Eudragit shell was 4 m
can be applied in larger scale. Firstly, yield of the process is strongly dependent on
the concentration of the dissolution, but usually lower than in spray drying. It is not
possible to increase the yield by increasing the liquid flow rate, since stable
electrospraying can be achieved at flow rates of approx. < 10 ml/h only. On the
other hand, electroencapsulation is an efficient method which provides much more
accurate possibilities to adjust the composition of the final particles than spray
drying.
Several methods have been presented to increase throughput of electrohydrodynamic spraying and these involve, for example, using multiple nozzles slits,
wires, or plates instead of a single capillary (Rulison and Flagan 1993; Bocanegra
et al. 2005; Deng et al. 2006). Some of these methods might not be applicable to
electroencapsulation. Secondly, the choice of used solutions can be challenging,
especially if pharmaceutical applications are considered. Core and shell liquids
need to be immiscible but mutually wettable and they must have different surface
tensions. Also, the conductivity of the solution should be in the range of 104 to
108 S/m in order to obtain a steady cone-jet mode (Jaworek 2007).
References
Bailey AG (1989) Electrostatic spraying of liquids. Physik in unserer Zeit 20:160
Bocanegra R, Galan D, Marquez M, Loscertales IG, Barrero A (2005) Multiple electrosprays
emitted from an array of holes. J Aerosol Sci 36:13871399
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Brandenberger H, Nussli D, Piech V, Widmer F (1999) Monodisperse particle production: a

method to prevent drop coalescence using electrostatic forces. J Electrostat 45:227238
Cloupeau M, Prunetfoch B (1994) Electrohydrodynamic spraying functioning modes a criticalreview. J Aerosol Sci 25:10211036
Deng WW, Klemic JF, Li XH, Reed MA, Gomez A (2006) Increase of electrospray throughput
using multiplexed microfabricated sources for the scalable generation of monodisperse droplets. J Aerosol Sci 37:696714
Grace JM, Marijnissen JCM (1994) A review of liquid atomization by electrical means. J Aerosol
Sci 25:10051019
Jaworek A (2007) Micro- and nanoparticle production by electrospraying. Powder Technol
176:1835
Jaworek A, Sobczyk AT (2008) Electrospraying route to nanotechnology: an overview.
J Electrostat 66:197219
Kimura T, Higaki K (2002) Gastrointestinal transit and drug absorption. Biol Pharm Bull
25:149164
Langer G, Yamate G (1969) Encapsulation of liquid and solid aerosol particles to form dry
powders. J Colloid Interface Sci 29:450
Lopez-Herrera JM, Barrero A, Lopez A, Loscertales IG, Marquez M (2003) Coaxial jets generated
from electrified Taylor cones. Scaling laws. J Aerosol Sci 34:535552
Loscertales IG, Barrero A, Guerrero I, Cortijo R, Marquez M, Ganan-Calvo AM (2002) Micro/
nano encapsutation via electrified coaxial liquid jets. Science 295:16951698
Masaoka Y, Tanaka Y, Kataoka M, Sakuma S, Yamashita S (2006) Site of drug absorption after
oral administration: assessment of membrane permeability and luminal concentration of drugs
in each segment of gastrointestinal tract. Eur J Pharm Sci 29:240250
Nystrom M, Murtomaa M, Salonen J (2010) Fabrication and characterization of drug particles
produced by electrospraying into reduced pressure. J Electrostat 68:4248
Parsegian VA (2006) Van der Waals forces: a handbook for biologists, chemists, engineers and
physicists. Cambridge University Press, New York
Peng ZB, Doroodchi E, Evans G (2010) DEM simulation of aggregation of suspended
nanoparticles. Powder Technol 204:91102
Roine J, Murtomaa M, Myllys M, Salonen J (2012) Dual-capillary electroencapsulation of
mesoporous silicon drug carrier particles for controlled oral drug delivery. J Electrostat
70:428437
Rulison AJ, Flagan RC (1993) Scale-up of electrospray atomization using linear arrays of Taylor
Cones. Rev Sci Instrum 64:683686
Salonen J, Lehto V, Bjorkqvist M, Laine E, Niinisto L (2001) Chemical stability of thermallycarbonized porous silicon. Mat Res Soc Symp Proc 638:F14.9.1F14.9.6
Sample SB, Bollini R (1972) Production of liquid aerosols by harmonic electrical spraying.
J Colloid Interface Sci 41:185
Sato M (1984) The production of essentially uniform-sized liquid droplets in gaseous or immiscible liquid-media under applied AC potential. J Electrostat 15:237247
Photoluminescent Nanoparticle
Derivatization Via Porous Silicon
Benjamin R. Horrocks
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Free-Standing Silicon Nanocrystals from Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Derivatization of Silicon Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silicon Nanoparticle Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
Photoluminescent porous silicon nanoparticles have many potential medical

uses if their properties can be optimized. The techniques for both fabricating
such particles and their surface chemistry manipulation are reviewed, including
recent approaches whereby such nanoparticles are embedded in other biomaterial matrices.
Introduction
Room temperature photoluminescence of porous silicon was observed in 1990 and
interpreted in terms of quantum confinement within the nanoscale structures in the
material (Canham 1990). Shortly afterwards, sonication was used to break up the
porous silicon layer and produce free-standing silicon nanocrystals with bright
orange luminescence (Heinrich et al. 1992). The nature and origin of the photoluminescence from these structures has been debated with interpretations based on
quantum confinement (Wilson et al. 1993) and on siloxene species being proposed
B.R. Horrocks (*)

School of Chemistry, Newcastle University, Newcastle upon Tyne, UK
e-mail: ben.horrocks@newcastle.ac.uk
DOI 10.1007/978-3-319-05744-6_69
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(McCord et al. 1992). Size-dependent photoluminescence has been observed

(Berhane et al. 1993; Lockwood et al. 1992; Takasuka and Kamei 1994; Kang
et al. 2008), and this provides strong evidence for quantum confinement; however,
there is clearly also an effect of the surface capping layer. Porous silicon prepared
under anaerobic conditions shows size-dependent photoluminescence, but the blueemitting material shows a large red-shift (1 eV) upon exposure to oxygen and this
effect was interpreted in terms of surface states related to Si-O species (Wolkin
et al. 1999). Computational studies (DFT and TDDFT) of hydrogen-terminated and
oxygen-terminated Si nanocrystals (SiNCs) suggest that the transition associated
with the energy gap is dipole allowed for hydrogen-terminated particles (diameter
2 nm) but red-shifted and forbidden for completely oxygen-terminated particles
(Zhou et al. 2003a, b; Walker et al. 2008). Because Si nanocrystals prepared by
sonication of porous silicon are rather easily oxidized under ambient conditions,
substantial efforts to cap these particles and stabilize them have been made
(Shirahata 2011). Further, the understanding that differences in the electronegativity of the capping layer and the nanocrystal can produce a red-shift of the luminescence (Zhou et al. 2003b) has motivated the use of chemistries based on Si-C
bonded alkyl monolayers (see Silicon-Carbon Bond Formation on Porous
Silicon by L. A. Huck and J. M. Buriak; chapter Drug Delivery with Porous
Silicon). The precise role of oxygen in silicon nanocrystals has been revealed to be
quite complex, because, as well as red-shifts of the HOMO-LUMO gap due to the
presence of O-atoms at the NC/cap interface, there have been reports of blue-shifts
due to reduction in core size upon oxidation of SiNCs in SiO2 matrices as well as
the appearance of new, blue photoluminescence peaks appearing on oxidation of
alkyl-terminated SiNCs (Chao et al. 2006; Hua et al. 2006). A computational
investigation of the progressive oxidation of SiNCs also shows that oxidetermination and hydroxyl termination of the particles have qualitatively different
effects on the optical gap (Eyre et al. 2008). Simple steady-state or time-dependent
photoluminescence measurements are not really able to distinguish emission from
localized states or quasi-direct transitions produced by quantum confinement
effects (Kovalev et al. 1998). Researchers have therefore turned to X-ray-based
techniques such as XEOL (Hessel et al. 2008; Siller et al. 2009), femtosecond
studies of the excited state dynamics (Zdek et al. 2010, 2011), the sensitivity or
otherwise of the photoluminescence to high magnetic fields (Godefroo et al. 2008),
and the pressure-dependence of the photoluminescence (Hannah et al. 2012) in
order to provide evidence for nature of the emitting state. It remains difficult to
prove that the observed photoluminescence in any particular preparation arises
from states that have evolved from bulk Si electronic structure due to quantum
confinement or from localized states related to defects or oxygen species and even
harder to make any general conclusions. Recently, a report has suggested much of
the blue PL from SiNCs is associated with nitrogen impurities (Dasog et al. 2013).
Nevertheless, SiNCs from porous silicon or other synthetic routes remain actively
investigated because of their potential in bioimaging (Shirahata 2011; OFarrell
et al. 2006), catalysis (Kang et al. 2011), and optoelectronics applications
(Ossicini et al. 2003).
Photoluminescent Nanoparticle Derivatization Via Porous Silicon
673
Free-Standing Silicon Nanocrystals from Porous Silicon

Free-standing SiNCs can be prepared from porous silicon by breaking up the porous
material using sonication (Heinrich et al. 1992; Bley et al. 1996), by high-current
pulses (Lie et al. 2002), or by boiling the chips in a solvent (Chao et al. 2007).
Rod-shaped particles of diameter 100200 nm and 200400 nm length were
prepared by a silver-assisted electroless etch (Xue et al. 2011). Mechanical techniques to pulverize the porous silicon can also be applied (Valenta et al. 2005). An
efficient process is to etch thick fully porous membranes and then to jet mill or
sonicate these (see Milling of Porous Silicon Microparticles by A Loni;
provisional chapter number Biodegradability of Porous Silicon). The size
distribution of particles produced by the disruption of porous silicon has been
measured using AFM, STM, TEM, and X-ray and neutron scattering techniques
(Chao et al. 2007; Choi et al. 2008). Disruption of porous silicon in a boiling solvent
leads to particle diameters of about 2.5 nm (Chao et al. 2007), whereas particles
produced by sonication have been reported with a median diameter of 3 0.2 nm
(and a log-normal distribution) using small-angle neutron scattering (Choi
et al. 2008). Favored discrete particle sizes have also been reported (Belomoin
et al. 2002). The color of the PL varies from red to yellow under ambient conditions,
and the measured PL energies, for particles in the 23 nm diameter range, generally
match the predictions of quantum confinement (Choi et al. 2008). The SiNCs
formed by sonication of porous silicon are typically H-terminated with varying
amounts of oxide/suboxide depending on the reaction conditions. Although disruption of porous silicon generally makes small amounts of SiNCs, the quantum
efficiency of the photoluminescence of individual particles may be close to
1 (Credo et al. 1999). Nanocrystals have also been prepared directly with the
addition of polyoxometalates to the electrochemical etch (Kang et al. 2007). Characterization of the nanocrystals by high-resolution electron microscopy and X-ray
diffraction shows that SiNCs from porous silicon approximately retain the
diamond-lattice of bulk Si (Chao et al. 2007); however, recent advances in electron
microscopy techniques have demonstrated the presence of lattice distortion in other
samples (Panthani et al. 2012), and similar results may be expected if the technique
is applied to samples derived from porous Si.
Derivatization of Silicon Nanocrystals

The development of SiNC capping chemistries has been motivated by applications
in bioimaging (OFarrell et al. 2006). SiNCs have several advantages over current
CdSe/ZnS core-shell quantum dots: (i) there is no possibility for leaching of toxic
heavy metal ions and therefore no acute cytotoxicity of SiNCs (Alsharif
et al. 2009), and indeed it has been shown that porous silicon nanoparticles are
biodegradable in vivo and excreted as silicic acid species without toxicity (Park
et al. 2009); (ii) the organic monolayers used to cap SiNCs are both stable and
compatible with a range of fictionalization chemistries; (iii) SiNCs will emit red
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light even at rather small particle sizes; and (iv) the overall size of an SiNC quantum
dot label is typically much smaller than the corresponding CdSe/ZnS label. Set
against these advantages are the following considerations: (i) the absorption and
emission spectra of SiNCs are not usually as sharp or well-defined as for CdSe;
(ii) the size control of synthetic methods for SiNCs is not yet as good as for CdSe/
ZnS quantum dots (Mastronardi et al. 2011); and (iii) the chemistry for preparation
of porous Si requires harsh conditions (aqueous HF, high currents/powerful
oxidants).
Although silicon nanocrystals are now more commonly prepared by a variety of
means which are easier to scale up, e.g., pyrolysis of silanes (Xuegeng et al. 2004),
thermal treatment of silsesquioxanes (Hessel et al. 2006, 2010), and from reactions
of molecular silicon compounds (Wilcoxon et al. 1999; Bley and Kauzlarich 1996),
this review will concentrate on routes which proceed via the formation of porous
silicon. More general reviews of silicon nanocrystals from physics and chemistry
perspectives are available (Shirahata 2011; Kang et al. 2011; Heitmann et al. 2005).
Derivatization of porous silicon and SiNCs usually relies on the chemistry of the
hydrogen-terminated silicon surface, which shares some of the organic reactivity of
hydrosilanes (Buriak 2002). Reaction with alcohols results in Si-O-C bonded
monolayers (Sweryda-Krawiec et al. 1999), but these are susceptible to hydrolysis
under ambient conditions. Alternately, addition of surface Si-H across a C C
double bond produces Si-C bonded monolayers, which are very stable, and the
resulting SiNCs are much less susceptible to oxidation or corrosion in air or water
(Shirahata 2011). The hydrosilation of 1-alkenes at the SiNC surface can be driven
photochemically (Kusov et al. 2010), thermally (Lie et al. 2002; Rytkonen
et al. 2012; Rogozhina et al. 2006), or using catalysts such as chloroplatinic acid
(Ahire et al. 2012). Bromination of the SiNCs and reaction with butyllithium to
produce butyl-capped SiNCs has also been demonstrated (Carter et al. 2005). A
common technical issue with derivatization of nanoparticles prepared from porous
silicon is the difficulty in carrying out organic reactions on small amounts of
material and purifying the derivatized nanoparticles from underivatized
nanoparticles and excess reagents (Fig. 1). This makes multistep derivatization
reactions hard to accomplish and limits the types of functional groups which are
accessible, e.g., 1, -functionalized alkenes with strongly polar groups may not be
compatible with the hydrocarbon solvents employed. The preparation of waterdispersible SiNCs is of particular interest for bioimaging and cellular uptake
studies; it was first achieved by grafting of polyacrylic acid onto SiNCs prepared
in a different way (Li and Ruckenstein 2004). SiNCs prepared from porous silicon
have also been dispersed in aqueous media by grafting polyacrylic acid (Wang
et al. 2011, 2012), by hydrosilation of an alkene bearing a terminal amine group
(Ahire et al. 2012) or undecylenic acid (Rytkonen et al. 2012), or by hydrosilation
of methyl pentenoate followed by base hydrolysis to form carboxyl-terminated
SiNCs (Rogozhina et al. 2006). Alternately, simple alkyl capping layers from
1-alkenes can be used to produce very hydrophobic SiNCs which are soluble in
organic solvents, e.g., tetrahydrofuran, and which can be rapidly mixed with excess
water to produce a metastable lyophobic sol (Dickinson et al. 2008).
675
Fig. 1 Schematic illustrations of two classes of method for the derivatization of porous silicon
nanoparticle surfaces. (i) Porous silicon prepared by a high-current density electrochemical etch is
broken up into free-standing nanoparticles by sonication or other means, and the hydrogenterminated silicon surface is reacted with 1, -functionalized alkenes to form an Si-C bonded
capping layer on the particles. The SiNCs must typically be separated from the excess alkene.
(ii) The hydrosilation chemistry is carried out on the porous silicon layer first, which is then
disrupted to form monolayer-capped free-standing nanoparticles. Excess alkene is easily removed
before the disruption of the porous silicon, but surfaces that are only exposed in the last step will
not be capped
Purification can be particularly difficult because the amount of material produced by breaking up porous silicon chips prepared on the laboratory scale is
typically small (<1 mg) and chemical separation techniques such as chromatography may not work as well with NPs as for molecular species. Although multiwafer
anodizing kits have allowed some scaling-up, with the order of kgs of porous silicon
powder being produced (Porous Silicon Formation by Anodization by Author,
and Porous Silicon and Electrochemical Deposition), the technology is not
readily available to many chemistry-oriented laboratories. It is however possible
to solve this problem by carrying out the derivatization on the porous silicon
before breaking up the layer. Excess reagents can be easily washed away from
high-surface area porous silicon. In fact, porous silicon is a satisfactory substrate
for solid-phase synthesis and complex chemical procedures can be carried
out ( Silicon-Carbon Bond Formation on Porous Silicon by L. A. Huck and
J. M. Buriak, and Drug Delivery with Porous Silicon). DNA oligosynthesis
of 24 base-pair sequences, involving a total of 168 chemical steps, is possible
(Lie et al. 2004). One of the major constraints of the method is that phosphoramidite
reagents must be selected with protecting groups that can be removed under mild,
nonaqueous conditions to avoid corroding the porous Si in the final deprotection step.
UltramildTM reagents and deprotection with methylamine vapor are a convenient
choice. Nevertheless, there are some disadvantages to functionalization prior to
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B.R. Horrocks
breaking up the porous Si: (i) bare (uncapped) surfaces are exposed during the
disintegration step and the final NPs may not be as stable as those with a more
complete capping layer; (ii) in the case of oligosynthesis, there is an oxidation step to
convert the P(III) phosphorus reagents to P(V) phosphate, and this leads to some
oxide formation on the SiNCs; and (iii) the choice of current density to prepare the
porous silicon is constrained by the requirement for the porous layer to remain intact
during the functionalization chemistry (Coxon et al. 2012). SiNCs have also been
conjugated to DNA after the NPs were formed. This procedure avoids the issues
related to the mechanical stability of porous silicon, but it did require high-energy
carbene species to functionalize the alkyl capping layer and, depending on the
application, one may have to separate the free DNA molecules from the SiNCDNA conjugates (Wang et al. 2004).
Silicon Nanoparticle Encapsulation

Recently efforts to derivatize SiNCs have employed a very different strategy:
instead of direct chemical derivatization of the SiNC capping layer, the SiNCs
are encapsulated in a larger organic structure such as a micelle or polymer particle
(Erogbogbo et al. 2008, 2010, 2011, 2012; Henderson et al. 2011; Harun et al. 2011;
Gongalsky et al. 2012). This has the advantage that the synthetic challenge of
preparing SiNCs and of derivatization are uncoupled, and there is a substantial
existing literature on organic polymer chemistry that can be exploited to produce a
wide variety of functional groups and additional useful molecules without having to
worry about the impact of these chemistries on Si. Block copolymer micelles have
been used in which a fraction of the polymer molecules bear a useful functional
group which self-assembles on the external surface of the micelle and which
allows conjugation of antibodies (Erogbogbo et al. 2008, 2011) or incorporation
of inorganic ions useful in imaging such as gadolinium (Erogbogbo et al. 2012).
The SiNCs need only have the correct hydrophilicity/hydrophobicity to favor the
micellar core (Gongalsky et al. 2012). Deoxycholate has been used to coat watersoluble undecenoic acid-capped SiNCs and to stabilize them for biological applications (Froner et al. 2011). Deoxycholate was found to be superior to synthetic
surfactants for this purpose because of reduced toxicity. Alternately, miniemulsion
polymerization techniques can be used to encapsulate SiNCs in polymer particles of
dimension 100200 nm diameter by dissolving simple alkyl-capped SiNCs in the
droplets of monomer (Harun et al. 2011). Again, functionalization is achieved by a
suitable choice of monomer (Fig. 2).
Micelles have advantages in that they form reversibly and spontaneously under
conditions of thermodynamic control. Control of micelle size can also be obtained
by control of the block copolymer molecular weight. This greatly facilitates the
preparation of complex NPs containing multiple individual SiNCs and other species, such as drug molecules, magnetic particles, or antibodies, which combines
multiple functions (Erogbogbo et al. 2011). In other applications, the reversibility
of micelle formation may be a disadvantage, because the micelle can disassemble
677
Fig. 2 Schematic illustrations of encapsulation of porous silicon nanoparticles in block copolymer

micelles or by miniemulsion polymerization. Instead of attempting to functionalize the nanoparticle
surface directly, a functional group X is incorporated into a suitable block copolymer (top) or in
the monomer droplet of a miniemulsion polymerization technique (bottom). These techniques
expand the range of functionalities that can be incorporated into SiNC-based systems and facilitate
greater synthetic control. The main disadvantage of such systems is the increased size of the final
object which may obviate particular applications, e.g., some intracellular imaging applications
depending on interactions with surfaces or changes in the solution chemistry.

Miniemulsion polymerization is a useful alternative encapsulation technique
because it produces robust latex particles under kinetic control: formation of
these structures is not reversible and they are chemically rather robust. For this
reason, they may be less useful in drug delivery but well suited to staining and
labeling applications. Miniemulsion polymerization is related to microemulsion
polymerization, but the reaction conditions are chosen to ensure that the polymer is
formed by polymerization of the monomer droplets in the emulsion and not by
dissolution of monomer molecules and initiation of polymerization in the bulk
phase. If the latter happens, the encapsulation will probably fail. Instead, n-alkylcapped SiNCs are dissolved in the monomer and remain in the monomer droplets in
a stable aqueous emulsion; the droplets are polymerized and a useful check on the
process is to characterize the droplet size before and after polymerization by light
scattering techniques. Little change in particle size is an indication that the droplets
themselves are polymerized. Since SiNCs can be difficult to observe in TEM
images of polymer particles, fluorescence microscopy was used to confirm that
each polymer particle contains SiNCs (Harun et al. 2011).
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Silicon-Carbon Bond Formation on Porous

Silicon
Lawrence A. Huck and Jillian M. Buriak
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
683
684
691
691
Abstract
Porous silicon has enormous potential for a variety of applications as a high

surface area variant of single crystalline silicon. Its high surface area is its
defining feature, which can dominate the properties of the material. The native
surface produced after an electrochemical etch is typically a hydride-terminated
surface that is only metastable in ambient air; this surface will oxidize over time.
Surface chemical functionalization can enable stabilization of the porous silicon
with respect to demanding chemical and biologically relevant environments and
can enable precise tailoring of properties to endow the material with particular
characteristics on demand. This chapter examines the surface chemistry of
porous silicon that produces direct silicon-carbon bonds, to enable the covalent
binding of just about any organic molecule of interest to the surface.
Introduction
Since the first report on the properties of porous silicon (porSi) by Canham (1990),
this morphologically complex form of hydrogen-terminated silicon has been extensively studied because of its photoluminescence, high surface area, and
L.A. Huck (*) J.M. Buriak
Department of Chemistry, University of Alberta, Edmonton, AB, Canada
e-mail: jburiak@ualberta.ca
DOI 10.1007/978-3-319-05744-6_70
683
684
L.A. Huck and J.M. Buriak
biocompatibility (Sailor 2012). Applications that have been explored with the goal
of taking advantage of this nanoscale architecture include drug delivery (Anglin
et al. (2008) and chapter Drug Delivery with Porous Silicon), chemical/biological sensors (Kilian et al. (2009) and chapter Porous Silicon Optical Biosensors), solar cells (Singh et al. (2010) and chapter Porous Silicon and Solar
Cells), and mass spectrometry (chapter Porous Silicon-Based Mass
Spectrometry).
One useful characteristic of freshly etched porSi is the metastable siliconhydrogen bond termination of its surface. While the SiH bonds render the surface
susceptible to hydrolysis and oxidation, these groups can act as chemical handles
through which a variety of organic molecules can be attached. Organic molecules
covalently grafted onto the surface not only impart additional functionality to the
porSi, but they can also inhibit hydrolysis and oxidation (Buriak et al. 1999;
Canham et al. 1999), thus extending the useful lifetime of the material. Typically
these molecules are linked to the surface through a SiC bond, or with a silyl ether
bridge (e.g., SiOC). While the bond strength of SiO is greater than SiC (Cotton
et al. 1999), the larger difference in electronegativity () between Si and O is
problematic with respect to hydrolysis because it increases the susceptibility of
nucleophilic attack at the silicon surface [ C,Si 0.65; O,Si 1.54 (CRC
Handbook of Chemistry and Physics 2013)], leading to oxidation and etching
(Linford and Chidsey 1993).
Using a SiC bond forming approach, it is possible to attach a wide variety of
organic functional groups to the porSi surface. Porous silicon can be rapidly
analyzed by transmission infrared spectroscopy (see Fig. 1 and chapter Characterization of Porous Silicon by Infrared Spectroscopy), thus making it possible
to easily track the progress of surface reactions. As will be shown below, reactions
often consume the surface Si-H bonds, so monitoring the decrease in area of (SiHx)
is a convenient method that permits the yield of the reaction to be calculated. Often
this is referred to as the efficiency (E) of the reaction (Buriak et al. 1999) and can be
calculated according to Eq. 1:
%E

ASiH, 0 ASiH, t
ASiH 100
ASiH, 0
ASiH, 0
(1)
Methods
As shown in the tables below, the value of %E varies considerably between the
different techniques used to functional porSi, but for absolute quantification, the
numbers require careful consideration due to potential competing oxidation reactions. It has been experimentally established that for hydrogen-terminated flat Si
(111) surfaces, the maximum coverage that can be obtained is ~5055 % of all
surface silicon atoms due the steric hindrance between alkyl chains bonded to the
surface (Scheres et al. 2010). Space-filling calculations substantiate the experimental evidence by showing that higher packing densities (>55 % of surface silicon
685
Fig. 1 Transmission FTIR spectrum of (a) freshly prepared porSi and (b) the same porSi sample
with a dodecyl chain grafted to the surface. Note the loss in (SiHx) intensity
atoms with an alkyl chain) are energetically unacceptable because the required
atomic positions are smaller than the van der Waals radii of the atoms in the chain
(Scheres et al. 2011). While porous silicon differs from Si(111), steric hindrance is
also expected to limit the packing density of the alkyl chains, and so 100 %
substitution is highly unlikely. In addition, depending upon the specific etching
conditions, the resulting morphology of the porous silicon may have inaccessible
crevices and regions that cannot be reached for hydrosilylation, and so these Si-H
bonds remain intact, further lowering the percent substitution. The size of the
reagent is also a consideration because larger molecules are less able to effectively
migrate within the porous framework.
Because some internal SiH bonds can only be accessed by very small molecules (Pietrass et al. 1995; Knagge et al. 2006), air and water should always be
excluded regardless of the chosen functionalization method (Ogata et al. 1995).
Whenever possible, procedures should be performed with dry and deoxygenated
reagents under an inert atmosphere. Working in a glove box is typically easiest
because it provides for more rapid throughput of samples; however, if a glove box is
not available, Schlenk techniques or other methods that exclude air are acceptable.
Thermal functionalization methods make up the majority of methods reported in
the literature for SiC bond formation on porSi (Tables 1, 2, 3, 4, 5, and 6). The
procedures are quite straightforward: samples can be placed in small flask or vial
(Fig. 2a), immersed in or coated with the reactant, and heated (if required). If a vial
is used, the cap should be lined with material that is inert to the vapors from the
liquid. For electrochemical functionalization methods (Table 7), use of the same
etching cell setup used originally to prepare the porSi works well (Fig. 2b). The
electrolyte/reactant and electrode (usually Pt) are placed within the well above the
porSi wafer. The wafer sits on a rectangular aluminum electrode, which in Fig. 2b
was cut from a weighing dish.
686
Table 1 Thermal heat only

Reaction
Reactant
R (CH2)nCH3
R (CH2)nCHCH2
R (CH2)nCO2Et
R (CH2)nCO2H
R (CH2)nCO2Et*
R (CH2)nCO2H*
R C6H5
R ferrocene
R (CH2)nCH3
Reference
Bateman
et al. (1998,
2000),
Boukherroub
et al. (2000,
2001)
Boukherroub
et al. (2000)
Boukherroub
et al. (2000)
Boukherroub
et al. (2002)
Boukherroub
et al. (2003),
Petit
et al. (2008)
Smet
et al. (2005)
Bateman
et al. (1998)
Bateman
et al. (1998)
Comments
E 3070 %
T 80180 C
t 1620 h
Alkene/alkyne often
used neat, although
high-boiling aromatic
solvents such as
mesitylene or toluene
can be used to dilute
the reactant
* microwaves used
to heat the system
(170 C, 30 min)
Table 2 Thermal radical initiators

Reaction
Reactant
n 2, 10
Reference
Guo
et al. (2005)
R (CH2)nCH3
Wang and
Buriak
(2006)
R (CH2)6CHCH2
R C6H5
R (CH2)nCO2H
cyclohexene
R (CH2)nCH3
R (CH2)nOH
R C6H5
R (CH2)4CCH
Comments
Initiator: benzoyl
peroxide
microwave heating
~10 min
Initiator:
diazonium salt
T room temp
t 3060 min
E 60 %
With photochemical functionalization methods (Table 8), a typical setup is

shown in Fig. 3. The custom-made lamp housing contains a halogen lamp from a
video projector as the visible light source and a CPU cooling fan. The biconvex lens
was obtained from a magnifying glass, while the infrared filters (Schott) were
687
Table 3 Thermal Lewis acid catalysis

Reaction
Reactant
R (CH2)nCH3
R Ph
Reference
Buriak et al. (1999),
Buriak and Allen (1998),
Allen and Buriak (1999)
2-Me-2-butene
2,3-Me2-2-butene
-pinene
R (CH2)nCH3
R (CH2)nCO2Me
R (CH2)nOH
R (CH2)nCN
R C6H4R0
Comments
E 30 %,
T room
temp
t < 12 h
(alkenes)
t<2h
(alkynes)
R0 H,
Me, Cl
Table 4 Thermal transition metal catalysis

Reaction
Reactant
R (CH2)nCH3
R C6H5
2-Me-2-butene
-pinene
R (CH2)nCH3
R (CH2)nCO2Me
R (CH2)nOH
R
R
R
R
R
R
(CH2)nCN
C(CH3)3
C6H4R0
(CH2)nCH3
C6H5
C6H4F
R OEt
R NHR0
Reference
Holland
et al. (1999)
Comments
RhCl(PPh3)3
Wilkinsons catalyst
E 15 %
T room temp
t 24 h
Residual Rh results in
photoluminescence
quenching
Li and
Buriak
(2006)
Saghatelian
et al. (2001)
R0 Me, Cl
Zr(Cp)2Cl2 + BuLi
E 19 %
(R C6H5), less for
aliphatic substituents
T room temp
t4h
Rh2(OAc)4; difficult
to remove Rh from
surface
R0 benzyl, butyl,
morpholine, dodecyl.
Reaction heated until
N2 evolution ceases
(<10 min)
688
Table 5 Thermal Grignard and organolithium reagents

Reaction
Reactant
R (CH2)nCH3
R C6H4F
Reference
Kim and
Laibinis
(1998)
R C6H5
R CCC6H5
Song and
Sailor
(1998)
Comments
SiSi bond cleavage; no
consumption of SiH
bonds
T room temp
t2h
SiSi bond cleavage; no
consumption of SiH
bonds
T room temp
t<3h
Table 6 Thermal hydride abstraction

Reaction
Reactant
R (CH2)nCH3
R
R
R
R
R
R
(CF2)nCF3
(CH2)4CHCH2
C6H5
(CH2)nCH3
(CH2)4CCH
(CH2)3Cl
Reference
Schmeltzer
et al. (2002)
Comments
Reagent:
CPh3BF4
E < 30 %
E < 20 %
T room
temp
t3h
Fig. 2 (a) A sealed vial used for the thermal functionalization of porSi. (b) A cell used for the
electrochemical functionalization of porSi
689
Table 7 Electrochemical
Reaction
Reactant
R (CH2)nCH3
R (CH2)6CHCH2
R (CH2)5CN
R (CH2)5CO2R0
R C6H4R00
R (CH2)nCH3
R (CH2)4CCH
R C6H4R0
(R0 H, Br)
R C6H4CCH
Reference
Gurtner
et al. (1999),
Lees
et al. (2003)
Robins
et al. (1999)
R C6H4PPh2
R (CH2)nCH3
R C6H5
Wang and
Buriak
(2005)
Comments
X Br, I. porSi is
cathode
T room temp,
t < 5 min
R0 Et, tBu
R00 H, CN
Cathodic
electrografting
(CEG). Only SiHconsuming reaction
able to preserve
triple bond. Anodic
electrografting
reduces triple bond
T room temp,
t < 2 min
E < 17 %
T room temp,
t < 5 min
Table 8 Photochemical
Reaction
Reactant
R (CH2)nCH3
R (CF2)nCF3
R (CH2)4CH CH2
Reference
Stewart and
Buriak
(2001)
Comments
E < 20 %; can be
increased to >60 %
in the presence of
electron acceptors
(Huck and Buriak
2012)
T room temp
t minutes (varies
with intensity)
Guan
et al. (2012)
Because UV light
does not penetrate
porSi, this is an
effective method for
functionalization of
the outer surface,
leaving the inner
surface unaltered
R C6H5
1,5-cyclooctadiene
R (CH2)nCH3
R (CH2)4CH CH2
R (CH2)8CO2H
690
Fig. 3 Photochemical
reaction apparatus for visible
light-initiated hydrosilylation
Fig. 4 Air-free chamber

used to enclose porSi for
photolyses in air
691
purchased from Edmund Optics. If a glove box is not practicable for photolyses, the
sample can be enclosed in an air-free chamber (Fig. 4) and irradiated using the same
apparatus.
The following tables provide a brief summary of the methods that lead to
formation of a SiC bond on the porSi surface. The reported functional group
tolerance of each method is given, along with some of the key references that
should be consulted for more details on the scope of the reaction and experimental
procedures. For a more general overview of the functionalization of porSi and other
forms of silicon, several reviews are available [e.g., references Bent (2002), Buriak
(2002), Hamers (2008), Ciampi et al. (2010)].
Concluding Comments
The reactions shown in the tables above are often just the first step in the functionalization of porSi. Subsequent modification using simple organic chemistry permits
limitless options for the covalent attachment of more complex molecules to the
surface. Examples of larger molecules grafted to porSi include DNA (Pike
et al. 2002), proteins (Li et al. 2010), fullerenes (Dattilo et al. 2006), poly(ethylene
glycol) (Schwartz et al. 2005), and anthracyclines (Hartmann et al. 2013).
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Bateman JE, Eagling RD, Worrall DR, Horrocks BR, Houlton A (1998) Alkylation of porous
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Bateman JE, Eagling RD, Horrocks BR, Houlton A (2000) A deuterium labeling, FTIR, and Ab
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Boukherroub R, Morin S, Wayner DDM, Lockwood DJ (2000) Thermal route for chemical
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Boukherroub R, Morin S, Wayner DDM, Bensebaa F, Sproule GI, Baribeau J-M, Lockwood DJ
(2001) Ideal passivation of luminescent porous silicon by thermal, noncatalytic reaction with
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Boukherroub R, Wojtyk JTC, Wayner DDM, Lockwood DJ (2002) Thermal hydrosilylation of
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Boukherroub R, Petit A, Loupy A, Chazalviel J-N, Ozanam F (2003) Microwave-assisted chemical functionalization of hydrogen-terminated porous silicon surfaces. J Phys Chem B
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Buriak JM (2002) Organometallic chemistry of silicon and germanium surfaces. Chem Rev
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Cotton FA, Wilkinson G, Murillo CA, Bochmann M (1999) Advanced inorganic chemistry, 6th
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Dattilo D, Armelao L, Maggini M, Fois G, Mistura G (2006) Wetting behavior of porous silicon
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de Smet LCPM, Zuilhof H, Sudholter EJR, Lie LH, Houlton A, Horrocks BR (2005) Mechanism
of the hydrosilylation reaction of alkenes at porous silicon: experimental and computational
deuterium labeling studies. J Phys Chem B 109:1202012031
Guan B, Ciampi S, Luais E, James M, Reece PJ, Gooding JJ (2012) Depth-resolved chemical
modification of porous silicon by wavelength-tuned irradiation. Langmuir 28:1544415449
Guo D-J, Xiao S-J, Xia B, Wei S, Pei J, Pan Y, You X-Z, Gu Z-Z, Lu Z (2005) Reaction of porous
silicon with both end-functionalized organic compounds bearing -bromo and -carboxy
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Gurtner C, Wun AW, Sailor MJ (1999) Surface modification of porous silicon by electrochemical
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Hartmann KI, Nieto A, Wu EC, Freeman WR, Kim JS, Chhablani J, Sailor MJ, Cheng L (2013)
Hydrosilylated porous silicon particles function as an intravitreal drug delivery system for
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Milling of Porous Silicon Microparticles

Armando Loni
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hand-Milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rotor-Milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ball-Milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Jet-Milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
695
696
696
698
701
702
704
Abstract
The production of microparticles from anodized silicon wafers requires a topdown approach in that, after anodization, the porous silicon is in the form of a
layer that is detached from the silicon wafer as whole intact membranes or large
flakes. Such macroscale layers can then be milled into powder using either of four
main comminution techniques hand-milling, rotor-milling, ball-milling, and
jet-milling each described in detail herein. The choice of technique governs the
particle size distribution achievable. It is shown that the physical properties and
purity of porous silicon powders are significantly influenced by the milling technique and conditions used an important consideration for practical applications.
Introduction
Many of the current and foreseen practical applications of porous silicon require the
material to be in a powdered form, with a well-defined particle size distribution and
comprised of either nanoparticles or, more suitably, microparticles. A key
A. Loni (*)
DOI 10.1007/978-3-319-05744-6_71
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characteristic used to describe milled powders is particle size distribution this is

defined by the values D10, D50, and D90, where D refers to particle size (e.g., in
microns) and the lower case numbers refer to the percentage of material with a size
below the associated value. Size distributions are conveniently measured by optical
scattering (using, e.g., the Malvern Instruments Mastersizer 2000). Of use in
determining the outcome of the milling process itself on the properties of the
powder, an often neglected factor, is nitrogen gas adsorption, whereby the surface
area, pore volume, and average pore size of the particles can be determined (using,
e.g., the Micromeritics TriStar 3000).
Hand-Milling
The most basic way of creating powder is to manually grind the membranes using a
mortar and pestle (e.g., of the agate or quartz type). Hand-milling relies upon forced
contact between the two grinding surfaces with the particulates momentarily held
between the two. Generally applicable for small batch sizes of around 1 g in weight
(possibly more, depending on vessel size), effective size reduction to beyond a
course powder can only really be achieved with very much smaller amounts of
material. The degree of size reduction is generally limited, and the nature of the
method itself can lead to irreproducibility; for example, the variables include
weight of starting material, the degree of force used to grind, the grinding time,
and the grinding technique (which differs from person to person), and these make it
difficult to obtain a reproducible size distribution on a batch-to-batch basis. Given
the relatively mild physical nature of the procedure, the effects on the properties of
the resultant powder are hardly noticeable (with the exception, perhaps, of very
high porosity material).
Rotor-Milling
Milling of much larger batches requires equipment with high throughput. A rotor
mill is a convenient tool for achieving particle size reduction with throughput up to
20 g/min and typical D90s of tens of microns (possibly lower, depending on the
nature of the material). A typical laboratory-scale unit is the Fritsch Pulverisette
P14 (Fig. 1). Material fed into the mill drops onto a stainless steel rotor that is preset
to spin at very high speed (typically a maximum of 20,000 rpm). The very high
angular momentum of the rotor acts in combination with the centrifugal forces that
throw the flakes against the fingers of the rotor, thereby breaking them down into
powder. Once the powder reaches the outside perimeter of the rotor, it passes
through a sieve ring a stainless steel cylindrical foil mesh with, typically,
80 m holes (trapezoidal in shape and therefore directional) into a stainless
steel circular collection plate. The nature of the process is such that feed rate has
little effect on the degree of size reduction, as the process is essentially
instantaneous.
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Fig. 1 Fritsch Pulverisette

P14 rotor mill
Pre-milling preparation of the porous silicon involves reducing the membranes

to fragmented flakes, typically around 10 mm2 (shape is not important), that can
conveniently pass through the hopper en masse this can be achieved by manually
shaking the flakes in a sealed plastic pot, for example. The prepared flakes are fed
into the mill via the hopper at a predetermined rate (this can be done manually or by
using a vibratory feeder), the whole process being completed in around 2 min (for a
30 g batch and 20,000 rpm rotor speed). If too much material is fed into the mill,
blowback of powder out of the hopper and past the various internal seals can
occur (caused by the buildup of size-reduced particles at the sieve ring), which
lowers the process yield.
The resulting particle size distribution depends primarily on the rotor speed used
and also, to some extent, on the porosity and pore morphology of the starting
material: lower porosity, for example, equates to a physically harder material that
would require additional energy to achieve the same size distribution as a higher
porosity material, while particles with a columnar pore structure will break differently to those with a more spongelike pore structure under identical conditions. A
typical size distribution, for porous silicon with porosities in the range 6575 %,
prepared from p+ wafers (520 mcm), and a rotor speed of 20,000 rpm, has the
typical D10/D50/D90 values listed in Table 1.
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Table 1 Typical 30 g batch processing of 6575 % mesoporous silicon (values for single-pass
milling, only based on authors sample database)
Technique
Rotor-milling
Ball-milling
Jet-milling (of rotor-/
ball-milled pSi)
Typical
conditions
20,000 rpm
300 rpm, 3 min
3 Bar grind, 2 Bar
injector
D10
(m)
26
34
<1
D50
(m)
1520
1825
35
D90
(m)
3850
5090
911
Pore volume
reduction
58 %
10 %
1118 %
Rotor-milling is a more aggressive process than hand-milling and, as such, does

have some effect on the resulting pore volume (porosity) of the powdered
porous silicon. As the fragments are continuously broken up, the pore volume is
continuously being reduced. After milling at 20,000 rpm, for example, the pore
volume is reduced by an amount between 5 % and 8 % for this type of porous silicon
(Table 1) there could be larger reduction for higher porosity material. A lower
rotor speed will have less effect upon pore volume, but, of course, the particle
size distribution will be towards the higher end. Further size reduction, albeit not
significant, can be achieved by re-milling.
The physical contact between the porous silicon and the various stainless steel
components, in particular the rotor fingers, does present a route to contamination.
While the porous silicon is relatively soft, trace metallic elements such as Fe, Cr, and
Ni can be transferred from the stainless steel; the levels can be low (e.g., <10s ppm)
but may be sufficient to cause concern depending on the ultimate application.
Titanium- and tungsten-coated rotors are available that can minimize contamination.
Ball-Milling
Ball-milling is an alternative to rotor-milling and can facilitate much smaller
particle sizes. Being more energetic in nature compared with rotor-milling, ballmilling can have a significant effect on the properties of the resulting powder (e.g.,
loss of pore volume).
A typical laboratory-scale planetary ball mill, the Fritsch Pulverisette P6, is
shown in Fig. 2. The two key components are the grinding bowl and grinding balls,
commonly manufactured from stainless steel. The grinding bowl is first charged
with the balls and then a known volume of flakes added a general recommendation is that the quantity of flakes should occupy around half of the working volume
of the bowl (excluding balls). The lid is clamped onto the bowl (with a PTFE gasket
between the mating surfaces) and the assembly held in place on a rotating platform.
As the platform rotates, the bowl rotates in the same direction about the central
platform axis and simultaneously contra-rotates about the vertical axis through the
center of the bowl a pseudo planetary motion, hence the name. Centrifugal forces
act in such a way that the flakes are ground to a fine powder between the internal
surfaces of the bowl and the grinding balls.
699
Fig. 2 Fritsch Pulverisette

P6 ball mill
The main process variables are platform rotation speed (typically up to 600 rpm)
and time. Other parameters include the volume of material to be milled, the
grinding bowl volume, and the number and size of grinding balls used. As the
process relies on the transfer of kinetic energy, the density of the grinding ball
material is also important and can have some effect on the size distribution. Typical
D10/D50/D90 values, for single-pass mild conditions, are listed in Table 1, with
typical parameter dependencies being shown in Figs. 3ac and 4 all for porous
silicon with porosities in the range 6575 %, prepared from p+ wafers (520
mcm).
The atmosphere within the bowl has an effect on the resulting powder ambient
air will oxidize the porous silicon to some extent, for example. Special bowls can be
designed that facilitate the use of inert gas and internal temperature measurement.
Ball-milling can also be carried out in a wet environment by the inclusion of a
suitable solvent (e.g., isopropyl alcohol or water), although, as will be discussed
further on, the solvent can affect the resultant passivation.
The use of all stainless steel grinding media presents the very likely possibility of
metal contamination of the powder, more so than rotor-milling. Metal
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Fig. 3 (a) Size dependency

on time (ball-milling). (b)
Size dependency on speed
(ball-milling). (c) Size
dependency on weight
(ball-milling)
contamination can be avoided by using either zirconia or agate grinding media. The
density of zirconia is lower than stainless steel similar diameter balls will
therefore yield totally different size distributions, under fixed conditions, since
the kinetic energy transfer will be different.
701
Fig. 4 Pore volume

dependency on milling time
(ball-milling)
Depending on requirements, ball-milling does offer a good degree of process

flexibility due to the number of parameters that can be changed. Re-milling can be
used to obtain consecutive size reduction, albeit at the expense of pore volume
(Fig. 4). If much smaller particles are required, a different approach must be
adopted.
Jet-Milling
A process that facilitates size reduction beyond that achieved with either rotormilling or ball-milling is jet-milling. A typical laboratory-scale spiral jet mill, the
Hosokawa Alpine Aeroplex 50AS, is shown in Fig. 5. The process uses a highpressure jet of gas to draw the particles into the main body of the mill, via the
hopper. The particles are then injected into the grinding chamber, through nozzles,
where they are accelerated by a grinding gas jet. Comminution results when the
particles impact against each other. The milled product is discharged into a filter
element, where it can be collected.
Jet-milling is done with powder, rather than flakes, and the size distribution of
the feedstock powder is one factor that can affect the final size distribution
obtained. Additional factors include the gas pressures used and the pressure difference between the injector gas and grind gas. The process is essentially instantaneous, although the volume of the grinding chamber and the size of the injector and
accelerating nozzles limit the feed rate to around 3 g/min for the 50AS mill
anything higher can result in clogging of the mill and blowback. Frequent
emptying of the filter bag is required to avoid loss of fines and blowback.
Jet-milling can be carried out using compressed air as the grinding gas, although
the use of an inert gas such as nitrogen is recommended, primarily to avoid potential
combustion of the highly reactive porous silicon.
The size distribution achieved after jet-milling either rotor-milled or ball-milled
feedstock is shifted towards the finer end (Fig. 6) with typical D90s less than 15 m
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Fig. 5 Hosokawa Alpine

Aeroplex 50AS jet mill
Fig. 6 Particle size distribution overlay for rotor-milled porous silicon (R998-R1015-D/W/RM)
and the same feedstock after jet-milling (R998-R1015-D/W/RM/JM) (Prepared from p+ wafers;
size in micron)
after a single pass (Table 1). Further size reductions are possible by multi-pass
jet-milling this comes at the expense of subsequent pore volume reduction as well
as further reducing the process yield.
Discussion
The yield associated with each milling technique can vary somewhat, but is
typically around 7090 %, and depends on how carefully the powder is collected
from the mill and how much wastage occurs as discharge of fines. The overall size
703
distribution achieved after milling need not necessarily be single population in type
(Fig. 6) and ultimately depends on the initial feedstock and the milling conditions
used. It is possible to cut or tighten the distribution to a specific size range by
incorporating a classifier or by the use of graded sieves after milling.
When using the optical scattering method (Mastersizer instrument), how the
sizing is carried out can affect the size distribution achieved. For example, a broad
size distribution or peaks at larger sizes can be associated with agglomeration the
use of an appropriate dispersant with added surfactant will minimize agglomeration. While sonication during measurement can break up the agglomerates, under
certain conditions it can also break up individual particles this will also affect the
measured size distribution.
Milling, in essence, breaks up and fractures the porous silicon to reveal fresh
surfaces that instantaneously passivate according to the environment under which it
has been carried out, more often than not ambient air. Even if milled under inert
conditions, once exposed to ambient air, the material will begin to oxidize. The
passivation of milled porous silicon powder will therefore be comprised of a
combination of hydride and oxide, the extent of each being dependent on the nature
and conditions of the process used. More importantly, perhaps, the loss of pore
volume due to mechanical breakup and potential sintering of the structure, as well
as through milling-induced oxidation, is an effect that should be taken into consideration when developing processes for applications that rely on this particular
characteristic. Example application areas are covered in the chapters Drug
Delivery with Porous Silicon, Porous Silicon and Functional Foods, and
Porous Silicon for Oral Hygiene and Cosmetics, elsewhere in this handbook.
In addition to porosity, the pore morphology is likely also to play some part in
how the material is fractured by milling (Bevilacqua and Ferrara 1996). Lower
porosity, for example, equates to a physically harder material that would require
additional energy to achieve the same size distribution as a higher porosity material,
while particles with a columnar pore structure will fracture differently to those with
a more spongelike pore structure under identical conditions. While changes in
shape have been reported for porous silica particles after ball-milling, transforming
from either modular or acicular to spherical (depending on the size range), milled
porous silicon microparticles retain the acicular shape to some degree; being more
brittle and mechanically softer, less aggressive milling conditions are required to
achieve comparable sizes (Heikkila et al. 2009); the use of prolonged, more severe
milling could, however, yield non-acicular shapes.
Rotor-milling and ball-milling are energy-intensive processes. Ball-milling, in
particular, can induce changes in the crystalline structure of a material, rendering
even bulk silicon amorphous (Stevulova et al. 1997). Mechanochemical processes
based on ball-milling have been used to produce functionalized powders from bulk
silicon (Stevulova et al. 1997; Heintz et al. 2010; Verdoni et al. 2011; Stephen and
Riley 1989) and porous silicon (Russo et al. 2011). When such methods are applied
to highly reactive, high surface area porous silicon feedstock, great care must be
taken to minimize pressure (and temperature) buildup within the sealed bowl
particularly important during aqueous wet-milling, where gaseous hydrogen can
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evolve (Stephen and Riley 1989) as well as subsequent sintering and agglomeration of the powder.
One final noteworthy point relates to health and safety. Appropriate risk mitigation should always be in place before any type of milling and powder handling is
carried out, with personal protective equipment and properly extracted work areas
being imperative such precautions are particularly important in the case of
jet-milling and for jet-milled powders, where the size distribution contains a
significant quantity of fines.
References
Bevilacqua P, Ferrara G (1996) Comminution of porous materials. Int J Min Proc 4445:117131
Heikkila T, Makila E, Ojanen S, Qu H, Louhi-Kultanen M, Riikonen J, Salonen J, Kumar N,
Yu Murzin D, Santos HA, Laaksonen T, Peltonen L, Hirvonen J, Lehto V-P (2009) Effect
of comminution on microparticle properties of mesoporous silicon and silica materials.
In: Proceedings of the 12th European symposium on comminution and classification, Espoo,
pp 117
Heintz AS, Fink MJ, Mitchell BS (2010) Silicon nanoparticles with chemically tailored surfaces.
Appl Organometal Chem 24:236240
Russo L, Colangelo F, Cioffi R, Rea I, De Stefano L (2011) A mechano-chemical approach to
porous silicon nanoparticles fabrication. Materials 4:10231033
Stephen RG, Riley FL (1989) Oxidation of silicon by water. J Eur Ceram Soc 5:219222
Stevulova N, Suzuki T, Senna M, Balintova M, Sepelak V, Tkacova K (1997) Mechanochemical
oxidation of silicon and selectivity of oxide superficial layer dissolution in aqueous solutions of
HF and KOH. Solid State Ion 101103(2):681686
Verdoni LP, Fink MJ, Mitchell BS (2011) A fractionation process of mechanochemically synthesized blue-green luminescent alkyl-passivated silicon nanoparticles. Chem Eng J 172:591600
Further Reading
Salman AD, Ghadiri M, Hounslow MH (eds) (2007) Handbook of powder technology: particle
breakage, vol 12. Elsevier, Amsterdam, pp 11227. ISBN 978-0-444-53080-6
Wang Y, Forssberg E (2003) International overview and outlook on comminution technology.
Downloadable working paper published by the Swedish Mineral Processing Research Association, Stockholm
Ohmic and Rectifying Contacts to

Porous Silicon
Jayita Kanungo and Sukumar Basu
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrical Contacts to PS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Surface Stabilization and Stable Metal Contacts to PS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
705
706
707
711
712
Abstract
Porous silicon (PS) is a promising material for photonic, optoelectronic, and sensor
devices. However, achieving stable metallic contacts to porous silicon has been a
challenge. Oxidation of the Si-Hx bond on porous silicon surface on exposure to
aerial atmosphere is the main reason of the instability. This review highlights the
attempts made to modify the PS surface and make stable ohmic and rectifying
contacts. Data on different metals, alloys, and conducting polymers utilized to treat
the surface of porous silicon prior to the formation of ohmic and rectifying contacts
are provided in tabular form. The methods deployed to deposit the contact materials
on porous silicon are also summarized. The performance of noble metal treatment
of porous silicon surface by electroless deposition is highlighted.
Introduction
Porous silicon (PS) has gained an important platform as a potential material for
scientific and technological applications for sensors, solar cells, and photonic devices
(Canham 1997; Sze 1985; Dimitrov 1995; Neamen 2003; Archer and Fauchet 2003;
J. Kanungo (*) S. Basu
IC Design & Fabrication Center, Department of Electronics &
e-mail: jayita_kanungo@yahoo.co.in
DOI 10.1007/978-3-319-05744-6_72
705
706
J. Kanungo and S. Basu
Barillaro et al. 2003). The appreciably large surface to volume ratio, the ease of
formation, the tailored surface morphology, and compatibility to silicon IC technology make use of PS for the development of smart systems-on-chip sensors.
However, a major problem of PS is the instability because of its native interface
with a metastable SiHx termination (Tsai et al. 1991). The degradation of PS
surface structure is mainly due to spontaneous oxidation of the metastable hydrogenated silicon in ambient atmosphere. This creates a genuine problem for PS to
obtain a stable ohmic and rectifying contacts (Deresmes et al. 1995; Stievenard and
Deresmes 1995) that are essential for the applications of PS-based electronic and
optoelectronic devices. To achieve the low-resistance stable ohmic contact or to
obtain a good rectifying contact with low leakage current, the passivation of
porous silicon surface is necessary. The passivation of PS surface by different
methods has been reported in the literature. Some of the successful attempts are
surface oxidation both thermally and anodically, plasma treatment, and modification by noble metal ions reported recently.
Electrical Contacts to PS
Different metals, like Al, Ag, Au, Ni, Cu, and Pd, metal alloys, and conducting
polymers are reported to have been used as the contact materials to porous silicon.
But only a very few reports are available on Al (Zimin et al. 1995; Zimin and
Komarov 1998; Simons et al. 1995; Kanungo et al. 2009a; Maji et al. 2010; Dhar
and Chakrabarti 1996), Ag (Vinod 2005, 2009, 2013), Ni (Dhar and Chakrabarti
1996; Kanungo et al. 2006; Andersson et al. 2008), and porous alloyed PtSi
(Ichinohe et al. 1996) as ohmic contact to PS. Most of the reports available on
gold (Simons et al. 1995; Ichinohe et al. 1996; Angelescu and Kleps 1998;
Matsumoto et al. 1998; Lue et al. 1999; Bhattacharya et al. 2000; Rabinal and
Mulimani 2007; Han et al. 1994; Gallach et al. 2012; Jeske et al. 1995; Diligenti
et al. 1996), copper (Jeske et al. 1995; Ghosh et al. 2002), palladium (Slobodchikov
et al. 1998; Vikulov et al. 2000; Slobodchikov et al. 1999), indium (Angelescu and
Kleps 1998; Diligenti et al. 1996), and titanium (Skryshevsky et al. 1998) as contact
metals were found rectifying to PS. The other reports on metallic contacts to porous
silicon using Al (Deresmes et al. 1995; Stievenard and Deresmes 1995; Zimin
et al. 1995; Angelescu and Kleps 1998; Rabinal and Mulimani 2007; Diligenti
et al. 1996; Skryshevsky et al. 1998; Martin-Palma et al. 1999; Anderson
et al. 1991; Zimin and Bragin 1999; Cherif et al. 2013), Ag (Lin et al. 2006), Ni
(Dhar and Chakrabarti 1996; Andersson et al. 2008; Jeske et al. 1995), AuIn
(Angelescu and Kleps 1998), In-Sn (Angelescu and Kleps 1998), etc., showed
rectifying behavior. Banihashemian et al. (2010) showed a nonlinear relation for
carrier transport by IV curve measured with PtSi/PS/PtSi structure. Conducting
polymers like polyaniline (PANI) (Li et al. 1994; Halliday et al. 1996; Fan
et al. 1998) and polypyrrole (Arenas et al. 2006; Shen and Wan 1998) were also
reported for rectifying contact to PS. However, Giebel and Pavesi worked with
different metals for contact to PS and reported the rectifying nature of p-PS/Si
Ohmic and Rectifying Contacts to Porous Silicon
707
interface independent of the metal/PS contact and dependent on the thickness of PS

layer (Giebel and Pavesi 1995). Table 1 gives the summary of contact to PS with
different metals and conducting polymers.
A common way to find out the nature of ohmic contact to semiconductor is to
measure the value of the specific contact resistance, c ( cm2). Zimin et al. (1995),
Zimin and Komarov (1998) measured the transition resistivity of the PS surfaces
prepared from both p-type and n-type silicon wafers with Al contact. Specific contact
resistance of Al and Ni to p-type PS (55 % porosity) was reported by Kanungo and
co-workers (Kanungo et al. 2009a; Kanungo et al. 2006). Maji et al. reported the same
for Al contact to macroporous silicon (2010). P. Vinod (2005, 2009, 2013) studied
silver ohmic contact to p-type porous silicon by quantitative measurements of
the specific contact resistance. Table 2 gives the summary of the reported work on
specific contact resistance/transition-specific resistivity measurements. A separate
chapter in this handbook Electrical Transport in Porous Silicon reviews the
various factors that influence the resistivity of the porous silicon layer itself.
Surface Stabilization and Stable Metal Contacts to PS

A low-resistance ohmic contact to porous silicon is an existing challenge for the last
two decades for its applications in electronic, optoelectronic, and sensor devices.
The PS layer contains a very high density of surface and interface states, of the
order of 1015 cm3 eV1 (Matsumoto et al. 1998), situated at the quasi-Fermi level
that arises mainly due to its nanostructure. These defect states can act as the
recombination centers, responsible for the uncontrolled surface oxidation
(Beckmann 1965; Astrova et al. 2002; Karacali et al. 2003; Petrova et al. 2000)
of PS and Fermi-level pinning (Deresmes et al. 1995; Kanungo et al. 2009a). Thus,
the stability of the material is affected, and it may cause an unreliable rectifying
metal contact to porous silicon.
The passivation of the surface and interface states may produce a stable and
reliable electrical contact to porous silicon. But the available reports on the
passivation of PS surface are mostly for optical measurements (Rossi et al. 2001;
Bsiesy et al. 1991; Petrova-Koch et al. 1992; Lees et al. 2003; Mandal et al. 2006;
Anderson et al. 1993; Lauerhaas and Sailor 1993; Andsager et al. 1994; Steiner
et al. 1994). Only few reports are available on the surface passivation of PS
for stable electrical contact formation. Jeske et al. (1995) reported on the
passivation of PS surface by oxidation during metallization. Bhattacharya
et al. (Bhattacharya et al. 2000) studied on the improvement of the junction
properties of PS by exposing it to hydrogen plasma before depositing Au metal.
Electronic charge transport of Al and Au contacts to surface passivated PS by
covalent attachment of 1-dodecyne molecules was reported by Rabinal and
Mulimani (2007). They observed that the chemical passivation reduces the
density of surface states on PS and so the interface between PS and metal becomes
sensitive to the work function of the contacting metal. Martin-Palma et al. (1999)
found a rectifying behavior of Al/PS/Si structures even after prolonged exposure
708
Table 1 Ohmic and rectifying contacts to porous silicon by different metals, metal alloys, and
polymer materials
Metal on
PS
Al
Type of
crystalline
Si for PS
formation
p
Type of
contact
Rectifying
Sputtering
Ohmic
Evaporation
Rectifying
Evaporation
Au
Metallization
technique
Evaporation
Sputtering
Ohmic
Evaporation
Rectifying
Evaporation
Sputtering
Rectifying
Electroless
Evaporation
Ag
Ni
Rectifying
Ohmic
Rectifying
Co2 SCF
Screen printing
Electroless
Ohmic
Electroless
Ohmic
Rectifying
Electroless
Electroless
Sputtering
Cu
n
p
References
Deresmes et al. 1995;
Stievenard and Deresmes
1995; Zimin et al. 1995;
Angelescu and Kleps 1998;
Rabinal and Mulimani 2007;
Skryshevsky et al. 1998;
Martin-Palma et al. 1999;
Cherif et al. 2013
Anderson et al. 1991;
Zimin and Bragin 1999
Zimin and Komarov 1998;
Kanungo et al. 2009a;
Maji et al. 2010; Dhar and
Chakrabarti 1996
Zimin et al. 1995;
Diligenti et al. 1996
Anderson et al. 1991;
Zimin and Bragin 1999
Zimin et al. 1995; Zimin and
Komarov 1998;
Simons et al. 1995
Angelescu and Kleps 1998;
Matsumoto et al. 1998; Lue
et al. 1999; Bhattacharya
et al. 2000; Rabinal and
Mulimani 2007
Ichinohe et al. 1996;
Han et al. 1994; Gallach
et al. 2012
Jeske et al. 1995
Simons et al. 1995;
Lin et al. 2006
Vinod 2005, 2009, 2013
Dhar and Chakrabarti 1996;
Andersson et al. 2008;
Jeske et al. 1995
Kanungo et al. 2006;
Andersson et al. 2008
Dhar and Chakrabarti 1996
Jeske et al. 1995
Ghosh et al. 2002
(continued)
709
Table 1 (continued)
Metal on
PS
Pd
In
Ti
Porous PtSi
Type of
crystalline
Si for PS
formation
p
n
p
n
p
p
p
Type of
contact
Rectifying
Metallization
technique
Evaporation
Rectifying
Rectifying
Rectifying
Rectifying
Rectifying
Ohmic
Rectifying
Electroless
Evaporation
Evaporation
Evaporation
Evaporation
Sputtering
Evaporation
References
Slobodchikov et al. 1998;
Vikulov et al. 2000
Slobodchikov et al. 1999
Angelescu and Kleps 1998
Skryshevsky et al. 1998
Banihashemian et al. 2010
Ichinohe et al. 1996
Angelescu and Kleps 1998
Au-In,
In-Sn
Au/
polyaniline
(PANI)
p/n
junction
n
Rectifying
spun cast
Li et al. 1994
Rectifying
Halliday et al. 1996
Au/
polypyrrole
p
n
Rectifying
Rectifying
Immersion under
ultrasonication
Spin coating
Electrodeposition
Spin coating
Fan et al. 1998

Arenas et al. 2006
Shen and Wan 1998
(~1,400 h) to the atmosphere, although the current decayed with time. They also
showed that the surface of PS layer, chemically etched with HNO3, gives more
stable current reading compared to the untreated samples. Maji et al. (2010)
reported that controlled pre-annealing treatment before metallization induces
growth and coalescence of the shallow nanocrystallites, thereby removing the
nanopores on macroporous silicon surface and yields ohmic contact. Table 3
presents the reported results of the surface modification of porous silicon to
improve the electrical contact.
Kanungo et al. (2009a) modified porous silicon surface by electroless dispersion
of the noble metals like palladium (Pd), ruthenium (Ru), and platinum (Pt) using the
corresponding chlorides in acidic aqueous solutions at room temperature (Kanungo
et al. 2009b). Metal ions formed are reduced to metal islands by a chemical
reduction process (Jeske et al. 1995; Porter et al. 2002), and h+ is released, which
oxidizes PS surface to an ultrathin layer of SiO2.
Figure 1a demonstrates that Fermi-level pinning of unmodified PS due to large
density of surface states creates a barrier against the current flow and so a
rectifying behavior is shown with Al (inset) that should have given ohmic junction
with PS following the work function concept. But after modifications, the PS
surface states are largely reduced by surface oxidation and Al contact shows
ohmic for the lateral structure (Fig. 1a). On the other hand, the sandwich structure
(Fig. 1b) exhibits a rectifying behavior with the same metal due to the presence of
710
Table 2 Specific contact resistance/transition-specific resistivity of the metal contacts to porous

silicon made by different methods
Type
of PS
n
Metallization
technique
Evaporation
Metal
used
Al
Type
of contact
Ohmic
n and
p
Evaporation
Al
Ohmic
Evaporation
Al
Ohmic
Evaporation
Al
Ohmic
Screen printing
Ag
Ohmic
Screen printing !
firing at 800 C in air
! annealing at
450 C in N2 ! Ag
electroplating
Screen printing !
baking at 240 C in
inert ambient !
firing at 725 C in air
! annealing at
450 C in N2 ! Ag
electroless
Ag
Ohmic
Ag
Ohmic
Electroless
deposition
Ni
Ohmic
Specific contact
resistance/transitionspecific resistivity
( cm2)
Transition specific
resistivity 8
1031.2 102
Transition resistivity
0.618 (PS on n-Si)
0.61.3 k (PS on p-Si)
Specific contact
resistance 1.51 101
Specific contact
resistance 0.57
(unannealed sample)
0.1 (annealed sample)
Specific contact
resistance 0.0736
Specific contact
resistance 1.01 106
Specific contact
resistance 1.025
104 (before
electroless Ag
deposition) 3.25
105 (After
electroless Ag
deposition)
Specific contact
resistance 1.76 102
References
Zimin
et al. 1995
Zimin and
Komarov
1998
Kanungo
et al. 2009a
Maji
et al. 2010
Vinod 2005
Vinod 2009
Vinod 2013
Kanungo
et al. 2006
PS/Si heterojunction, and after modification, the rectification becomes much better
due to the effective passivation of the recombination states. Therefore, the surface
passivation improves both the ohmic and rectifying contacts.
In order to verify the stability of Al contact to modified porous silicon, the IV
measurements were repeated at different intervals of time for a period of 28 days.
Pd-modified samples showed much better consistency and stability compared to
Ru- and Pt-modified samples. In Fig. 2 the IV curves practically overlap signifying
a stable Al contact to PS when the surface was modified with PdCl2 solution
(Kanungo et al. 2009a, 2010). Specific contact resistance of Al- to Pd-modified
PS, determined by TLM method, was 1.51 101 cm2.
711
Table 3 Different ways of porous silicon surface modifications before metal contact formation
Type of Si
for PS
formation
p
Modification
procedure
Simultaneous
oxidation during
metallization
Hydrogen plasma
modification
Surface modification
using 1-dodecyne
organic molecule
HNO3 treatment
Electroless dispersion
of Pd
Heat treatment
Metal
on PS
Au,
Cu, Ni
Metallization
technique
Electroless
deposition
Type of
contact
Rectifying
Au
Evaporation
Rectifying
Au,
Al
Evaporation
Rectifying
Al
Evaporation
Rectifying
Al
Evaporation
Ohmic
Al
Evaporation
Ohmic
b
200
100
Current (A)
500
150
1000
0
50
sandwich structure
Al contact
Temp 27C
Unmodified
250 PS
200
50
1.0 0.5
Bhattacharya
et al. 2000
Rabinal and
Mulimani
2007
MartinPalma
et al. 1999
Kanungo
et al. 2009a
Maji
et al. 2010
1500
300
0.0
0.5
1.0
Pd modified PS
Ru modified PS
Pt modified PS
500
1000
Current (A)
1000
Lateral structure
Al contact
Temp 27C
Unmodified
150 PS
References
Jeske
et al. 1995
100
50
0
50
1.0
0.5
0.0
0.5
1.0
500
Pd modified PS
Ru modified PS
Pt modified PS
0
1.0
0.5
0.0
Voltage (V)
0.5
1.0
1.0
0.5
0.0
0.5
1.0
Voltage (V)
Fig. 1 IV characteristics of unmodified (inset) and Pd-, Ru-, and Pt-modified PS for (a) lateral
and (b) sandwich structure using Al contact. (Unit is same for both the graphs.) (Taken from Basu
and Kanungo 2011)
Conclusion
Ohmic and rectifying contacts to porous silicon are important and challenging for the
commercial applications of PS-based electronic, optoelectronic, and sensor devices.
The choice of contact materials and the nature of PS surface (including porosity) are
the prime factors for the successful achievement in the contact formation with the
712
1500
Lateral structure
Pd modification
0.01M for 5 sec
Sandwich structure
Pd modification
0.01M for 5 sec
1000
500
Current (A)
Current (A)
1000
0
day-7
500
day-7
day-14
500
day-21
day-14
day-28
day-21
1000
day-28
1.0
0.5
0.0
Voltage(V)
0.5
1.0
1.0
0.5
0.0
0.5
1.0
Voltage(V)
Fig. 2 IV characteristics of Pd-modified PS surface with Al contacts for (a) lateral and (b)
sandwich structures, measured for 28 days at different intervals of time
desired specific contact resistance. Surface modification of porous silicon by Pd

improves both ohmic and rectifying contacts along with the stability as it was verified
by intermittent IV studies. Verification of specific contact resistance at regular
intervals can be an alternative method to study the junction stability.
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Processing of Macroporous Silicon

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Global Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Local Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
715
716
721
726
Abstract
Macroporous silicon layers, with micron diameter pores, can be subjected to

many standard processes developed by the microelectronics industry for silicon
wafers, but these processes require tuning and optimization. A variety of
processing techniques to manipulate macropore morphology, chemical composition, and patterning are reviewed.
Introduction
Methods for electrochemical, catalytic (metal assisted), and deep reactive ion
etching (DRIE) of silicon have been developed, which enable fabrication of arrays
of deep cylindrical or modulated pores, walls, tubes, combinations of these, and
other forms with vertical walls (Wu et al. 2010). As a rule, the regular arrays
produced by electrochemical etching are characterized by constant porosity and
pore depths (up to 500 m) and form a planar front propagating into the substrate.
Various devices and functional elements for micromechanics, photonics, chemical
power sources, microfluidics, photovoltaics, etc. (see Porous Silicon Application Survey chapter), are commonly fabricated on the basis of these arrays by
E.V. Astrova (*)
Ioffe Physical Technical Institute, St. Petersburg, Russia
e-mail: east@mail.ioffe.ru
DOI 10.1007/978-3-319-05744-6_73
715
716
E.V. Astrova
post-anodization treatment intended to modify the structure and properties of

macroporous silicon: to raise or reduce its porosity, change the shape of pores,
transform the pore array into a column array, change the properties of the inner
surface of pores, coat it with the film of a metal or insulator, open up pores, fill pores
with various fillers, dope the silicon walls, etc. Some procedures can be performed
locally, which requires formation of a pattern and subsequent structuring.
Compared with micro- and mesoporous silicon, macroporous silicon is the
closest in its properties to the starting single-crystal material, and, therefore, it
can be subjected to standard technological procedures of microelectronics: thermal
oxidation, high-temperature annealing, introduction of impurities by diffusion,
thin-film deposition, photolithography, etc. However, the processing of
macroporous silicon has its own specific features. For example, ordinary thermal
oxidation gives rise to mechanical stresses, which may lead to deformation of a
sample and can cause destruction or appearance of dislocations. Treatment in liquid
reagents requires that the solution should penetrate into pores, for which a good
surface wettability and prolonged keeping in solution (or forced pumping of the
solution via through pores) are necessary. To perform photolithography, it is
necessary to preliminarily planarize the surface by pore cupping or filling or to
form a pattern on the backside of the substrate. Samples of macroporous silicon
have a reduced mechanical strength and, because of the developed surface, possess
a higher reactivity, compared with ordinary silicon wafers. However, the problems
with drying and storage-induced aging characteristic for mesoporous silicon are
much less severe.
Global Processing
Let us consider in more detail various processes for posttreatment of macroporous
silicon, listed in Table 1.
1. The simplest way to open up pores is by mechanical removal of the substrate by
grinding and polishing. A disadvantage of this method is that a sample is
contaminated with wax used to glue a sample (its removal is no difficulty),
and abrasive particles and silicon fines are introduced (can hardly be removed).
A widely used way to fabricate membranes is by chemical dissolution of the
substrate in hot alkaline etchants. For this purpose, the inner surface of
macropores is preliminarily protected by thermal silicon oxide or by silicon
nitride, which is stable in alkalis and prevents dissolution of porous silicon. The
rate of SiO2 etching is approximately three orders of magnitude lower than that
of silicon (Kendall 1979). Also, the porous layer is frequently separated from the
substrate in the final stage of anodization, which is, strictly speaking, not related
to posttreatment. However, a combined variant is possible, in which rather thin
silicon walls are obtained at the end of the electrochemical etching due to the
increase in the pore diameter in the lower part of the porous layer. These walls
are oxidized across their entire thickness in the course of the subsequent thermal
717
Table 1 Post-anodization treatment of macroporous silicon (global)

N
1
Purpose of
posttreatment
Through pores
(membrane)
Pore
coalescence and
closing
Porosity
increase,
formation of
pillars and
wires, change of
pore shape
Conformal
treatment
Basis of technique
Substrate removal
Surface diffusion
of Si
Isotropic treatment
Technique
Mechanical grinding
Thermal
oxidation + substrate
etching (alkaline or
reactive ion)
Annealing in H2
Sacrificial thermal
oxidation
Chemical etching
Anisotropic
treatment
Chemical etching in
alkaline solutions
Smoothing
Anisotropic sacrificial
thermal oxidation
Sacrificial SiO2
p-n or
heterojunction
formation
Coating
Wet etching
Shallow diffusion
doping
Thin film spraying

Galvanic or chemical
deposition
CVD, ALD
Altering of surface
functionality
Chemical liquid or
vapor treatment
References
Astrova et al. (2003)
Langner et al. (2011)
Sato et al. (2000),

Mizushima
et al. (2000)
Lauet al. (1996),
Matthias et al. (2004,
2005a), Trifonov
et al. (2008), Muller
et al. (2000)
Ossei-Wusu
et al. (2011)
Lehmann (2007),
Matthias
et al. (2005b),
Chernienko
et al. (2013), Zharova
et al. (2011)
Trifonov et al. (2007)
Langner et al. (2011),
Kalem et al. (2009)
Astrova et al. (2011b)
Grigoras et al. (2000),
Badel et al. (2005),
Sun et al. (2005),
Xianyu Ao
et al. (2012),
Kui-Qing Peng
et al. (2010)
Cachet et al. (1997)
Fang et al. (2007),
Zacharatos and
Nassiopoulou (2008),
Gutman et al. (2008),
Steinhauer
et al. (2005)
Lehmann
et al. (1996), Langner
et al. (2008)
Gunko et al. (2003),
Kalem and
Yavuzcetin (2000),
Hayden et al. (2009)
(continued)
718
E.V. Astrova
Table 1 (continued)
N
5
Purpose of
posttreatment
Thick modified
layer
Pore filling
Basis of technique
Through doping of
Si walls
Through oxidation
of Si walls
Fluidity of
filler + wettability
of Si
Technique
Gas phase diffusion
References
Astrova et al. (2000)
High-temperature
heat treatment in
oxidizing atmosphere
Liquid or melt
infiltration
Kan and Finstad

(2005), Barillaro
et al. (2003)
Kitzerow
et al. (2007), Astrova
et al. (2010a, 2011a),
Lehmann and
Ronnebeck (2001),
Badel et al. (2004)
Fang et al. (2007),
Zacharatos and
Nassiopoulou (2008)
Matthias et al. (2002)
Electrical
conductivity
Galvanic deposition
Chemical deposition
Inverted
structures
Catalyst
pretreatment
Macroporous Si as
a template
Silicon
particulates
Fracture of
macroporous Si
Pore filling or
covering + removal
of Si mold
Sonication
Lehmann and
Ronnebeck (2001),
Matthias et al. (2002),
Palacios et al. (2008),
Chen et al. (2006),
Langner et al. (2008),
Trifonov et al. (2005),
Astrova et al. (2005a),
Schilling et al. (2004),
Rodriguez
et al. (2005), Zhao
et al. (2005),
Bharadwaja
et al. (2006)
Thakur et al. (2012)
oxidation, and the substrate is removed under dissolution of SiO2 in HF. For a
general review of both mesoporous and macroporous membranes, see Porous
Silicon Membranes chapter in this handbook.
2. The macroporous structure is radically transformed in high-temperature
annealing in hydrogen, when porous channels are converted to closed spherical
voids capable of merging under proper conditions to give, at a certain depth in
the sample, a plate-shaped empty space parallel to the surface, the so-called
silicon-on-nothing structures (Sato et al. 2000; Mizushima et al. 2000) (for
more detail, see Sintering of Porous Silicon chapter in this handbook).
3. The porosity can be made more pronounced, and a columnar structure can be
formed via repeated thermal oxidation, followed by dissolution of the oxide
in HF (Lau et al. 1996; Matthias et al. 2004, 2005a; Trifonov et al. 2008)
719
Fig. 1 Alkaline anisotropic posttreatment of cylindrical macropores organized in a square lattice

after subsequent etching in (a) 50 % KOH, 105 C for 10 sec, (b) 2 % KOH + 10 % propanol,
14 C for 10 h (Lehmann 2007)
Fig. 2 Shaping of macropores at room temperature (Chernienko et al. 2013) (With kind permission from Springer Science + Business Media B.V): (a) schematic of anisotropic transformation
of an initially round macropore when etch rate for <100> exceeds rate for <110> crystallographic direction. Structures obtained from macroporous Si organized in a triangular lattice upon
chemical shaping in 12 % aq. KOH + IPA (2:3): (b) squares when the initial pore rows are aligned
along <110> direction, (c) zigzag Si walls when the pore rows are aligned along <100> axis
(see Oxidation of Macroporous Silicon chapter in this handbook). The same

goal can be achieved through pore expansion under isotropic etching in
acid etchants (based on HF + HNO3) (Ossei-Wusu et al. 2011). Anisotropic
posttreatment in various alkaline solutions makes it possible to change the
cross-sectional shape of cylindrical macropores from circular to squared.
In alkaline solutions, the etching rate of the (111) plane is 2 orders of magnitude
lower than that of other planes. The ratio of the etching rates of the (100) and (110)
planes may be inverted, depending on the etchant composition and treatment
conditions (Zubel and Kramkowska 2002). This property was used to obtain
square pores oriented in a particular way relative to the crystallographic directions
(Fig. 1). Figure 2 shows macropores, produced by anisotropic posttreatment
at room temperature of the initially round pores in mixture of KOH and isopropyl
alcohol (IPA). Figure 3 presents a scaffold-like structure of a cubic threedimensional photonic crystal obtained by alkaline anisotropic etching.
720
E.V. Astrova
Fig. 3 Scaffold-like structure obtained by anisotropic etching of modulated macropores. SEM

pictures of (a) side view, (b) top view (Reprinted with permission from (Matthias et al. 2005b).
Copyright 2005, AIP Publishing LLC)
4. Conformal treatment presumes that surface characteristics (roughness, wettability, thin-film coating, etc.) are changed. Upon anodization, pore walls may be
covered with a mesoporous layer. This layer can be removed with a weak
alkaline solution. The hydrogen-terminated hydrophobic surface is converted
to hydrophilic via chemical oxidation or formation of hydroxy (OH) groups on
the surface. The surface of macropores can be coated with thin films of metals,
insulators, and semiconductors and be functionalized by various methods, such
as oxidation, electroplating, chemical vapor deposition (CVD), and atomic layer
deposition (ALD). These may be chemical processes, both involving silicon and
not. The coating of macropore inner surface can serve as a mask for subsequent
treatment or to prevent denaturation of protein-based probes on silicon
microarrays (Steinhauer et al. 2005). The main difficulty is in obtaining a
uniform coating of the 3D surface. The deposition of thin doped films and
formation of p-n junctions can be attributed to a separate group. These junctions
are formed as a result of high-temperature diffusion from the gas phase.
5. If the walls of a porous structure are subjected to a through diffusion saturation,
thick (tens and hundreds of micrometers) quasi-homogeneous diffusion layers
are obtained, and this method can replace epitaxy (Astrova et al. 2000). Similarly, full thermal oxidation of silicon walls makes it possible to obtain thick
oxide layers, which are used, e.g., for thermal insulation purposes (Kan and
Finstad 2005; Barillaro et al. 2003). The increasing volume of the oxide leads to
filling of pores, which enables, at a correct choice of the porosity (56 %),
formation of a thick monolithic SiO2 layer. For more details, see Thermal
Isolation with Porous Silicon chapter in this handbook.
6. The chemical inertness of silicon and its high thermal stability enable filling of
macropores with various fillers in the liquid state, including those in the form of
melts and gels. The rather high electrical conductivity of macroporous silicon
enables electroplating (see Porous Silicon and Electrochemical Deposition
721
chapter in this handbook). The infiltration of macropores with lead (Lehmann

and Ronnebeck 2001), cesium iodide (Badel et al. 2004), copper (Fang
et al. 2007; Zacharatos and Nassiopoulou 2008), gold (Matthias et al. 2002),
liquid crystals (Kitzerow et al. 2007; Astrova et al. 2010a, 2011a), conducting
polymers (Palacios et al. 2008), mesoporous silica (Chen et al. 2006), etc., has
been reported.
7. To the preceding processes of conformal coating and total infiltration of
macropores are closely related methods for fabrication of inverted structures,
in which the macroporous matrix is used as a sacrificial template and is removed
in the final stage. This can be done either by selective dissolution of Si (as a rule,
in alkaline solutions) or by pulling out the resulting structure (Chen et al. 2006).
In the former case, it is necessary that the filler should be resistant to a hot alkali.
Silica tubes and needles formed by thermal oxidation (Trifonov et al. 2005;
Astrova et al. 2005a; Schilling et al. 2004; Rodriguez et al. 2005), lithium
niobate (Zhao et al. 2005), ferroelectric (Bharadwaja et al. 2006) tubes, and
3D TiO2 microstructures (Langner et al. 2008) also belong to inverted structures.
8. Some applications require cheap electroconductive material based on small
silicon particulates of high surface area. Authors of paper (Thakur et al. 2012)
report on ultrasonically fractured macroporous membranes, mixing silicon particulates (size range 1050 m) with pyrolyzed polyacrylonitrile and application
of the mixture for producing long life anodes of lithium ion batteries.
Local Processing
In the procedures considered above, the structure is subjected to a global treatment.
A local transformation of the macroporous structure requires that a pattern should
be created in it. The simplest operation is local pore opening. For this purpose, a
mask is created on the backside of an oxidized (or Si3N4-coated) structure by
photolithography, the silicon substrate is anisotropically etched to a depth required
for reaching the pore tips, and the oxide protecting the macropore walls is removed
(Langner et al. 2011; Trifonov et al. 2005). A general review on Photolithography
on Porous Silicon is available elsewhere in this handbook. The thus opened-up
pores have been used to create anodes with a reinforcing skeleton for fuel cells
(Astrova et al. 2007) and to perform a local infiltration of macropores in fabrication
of heterojunctions and defects in a photonic crystal (Fig. 4).
Other methods for local infiltration of macropores have also been reported
(Intonti et al. 2006; Nolte et al. 2009), e.g., global closure of pores, followed by
their opening up by direct writing with a focused ion beam (FIB).
The flow of the latter of these is shown in Fig. 5: (a) macroporous silicon with
edges inclined in the process of etching, (b) global infiltration of the pores with wax
for their stabilization in the subsequent polishing step, (c) polishing of the samples,
(d) deposition of a seed layer of gold by sputtering, (e) removal of the previously
introduced wax and of the seed layer deposited over the pores, (f) selective removal
of the seed layer by FIB, (g) electrochemical extension of the gold layer by
722
E.V. Astrova
Fig. 4 Local opening and infiltration of pores: (a) example of a structure with locally opened
pores (back side view), (b) front view with a pore row infiltrated with a liquid crystal (LC) from the
back side (Zharova et al. 2011) (With kind permission from Springer Science + Business Media B.V);
(c) scheme of the infiltration
Fig. 5 Process steps during the local infiltration (Nolte et al. 2009) (Permission granted by SPIE)
electrochemical deposition from a KAu(CN)2 solution, (h) local infiltration with

either a solution or a melt, and (i) removal of the metal layer with a KI/I2 solution.
A local processing of the porous structure is used as well to fabricate structures
with vertical walls. The micromachining of structures with steplike high-aspect
features assumes that a long route is to be used, including various procedures for
posttreatment of macroporous silicon. This is done on the basis of a regular
macropore array. The macroporous matrix is used as a quasi-homogeneous substrate in which larger structures are created by photolithography and other technological processes (Ottow et al. 1996a, b). The photolithography in samples of
macroporous silicon meets severe difficulties because a positive photoresist flows
into pores, is not exposed there, and, accordingly, cannot be dissolved in the
development stage. A negative photoresist cannot solve the problem, either, and
therefore, a preliminary planarization of the surface via pore capping or filling is
necessary for performing photolithography. Figure 6 shows the Ottow process flow,
in which an aluminum layer was used for planarization purposes. First, the inner
surface of pores is covered by a protection layer. Then, aluminum is deposited by
723
Fig. 6 Scheme of the Ottow microstructuring process (Muller et al. 2002) (With kind permission
from Springer Science + Business Media B.V)
sputtering and patterned by the conventional photolithography. Subsequently, the

protection layer is removed by chemical etching. The following isotropic plasma
process removes porous silicon in the already unpassivated areas. To get complete,
compact microstructures, the pores can be filled with polysilicon (Fig. 7).
The Ottow technique was used to fabricate 2D photonic crystal bars of
macroporous Si with a precision of less than one pore lattice constant (Muller
et al. 2000; see Fig. 8a).
A variation of the method, which does not require any surface planarization and
plasma etching, is by photolithography on the substrate backside (Astrova
et al. 2004, 2005b; Chernienko et al. 2013; Zharova et al. 2011). Example of such
a structure is shown in Fig. 8b.
Another approach to fabrication of structures with vertical walls is by simultaneous electrochemical etching of pores and trenches first introduced by Geppert
et al. (2006). Forming a closed contour, the trenches define the sacrificial
parts of the structure, which fall out from a sample after the substrate is removed.
724
E.V. Astrova
Fig. 7 Microstructures
obtained after pore filling
with polysilicon (Ottow
et al. 1996b) (With kind
permission from Springer
Science + Business Media B.V)
Fig. 8 SEM images of macroporous silicon bars with vertical walls: (a) a bar of about 3.5 pore
layers or 5 m, obtained by Ottow process (Muller et al. 2000) (With kind permission from
Springer Science + Business Media B.V); (b) stripes fabricated by photolithography on the back
side of the substrate (Astrova et al. 2005b) (With permission from Elsevier, 2005)
Figure 9 shows a schematic of the method and a bar of a 2D photonic crystal,

produced by removal of sacrificial parts of the sample.
3D photonic crystals can be fabricated by means of focused-ion-beam drilling of
macroporous silicon. Yablonovite-like structure was formed by three sets of drilled
725
Fig. 9 Schematic for patterning of 2D structure: (1) removed square area, (2) bar of a 2D structure
constituted by six rows of macropores, (3) macropores, (4) trenches, (5) n+-layer, and (6) substrate
removed in opening of trenches and pores (Astrova et al. 2010b) (With kind permission from
Springer Science + Business Media B.V); (b) Scanning electron microscope (SEM) image of a
two-dimensional photonic crystal bar obtained by this technique (Reprinted figure with permission
from (Dyakov et al. 2012). Copyright 2012 by the American Physical Society)
Fig. 10 Scanning electron

microscope image of the
fabricated 3D Yablonovitelike crystal showing the
oblique interface obtained by
FIB milling (Reprinted with
permission from (Chelnokov
et al. 2000). Copyright 2000,
AIP Publishing LLC)
holes (Wang et al. 2000, 2003; Chelnokov et al. 2000; Fig. 10). Authors of paper
(Schilling et al. 2005) obtained 3D photonic crystal of orthorhombic structure with
large photonic band gap by utilization of only one orthogonal set of FIB-drilled
holes interpenetrating with photoelectrochemically etched macropores.
Methods suggested in Kleimann et al. (2001, 2005) and Bassu et al. (2012)
enable fabrication of high-aspect-ratio microstructures directly in the course of
electrochemical etching without any additional posttreatment. In the Kleimanns
method (Kleimann et al. 2001, 2005), n-Si is first etched through a mask in the
726
E.V. Astrova
isotropic mode, and then the etching is continued in the anisotropic mode. In
contrast, the Barillaros technique (Bassu et al. 2012) involves deep anisotropic
etching in the first phase and isotropic etching in the second, so that the diameter of
the pores grows in the lower part of the structure and they, being connected with the
neighboring pores, merge into a single void. In the isotropic-etching phase, freestanding and sacrificial parts of the wafer are detached from the substrate. Similar
approach was used in Bobo et al. (2012) for separating macroporous arrays from
p-type silicon substrate. Other micromachining methods have also been suggested.
For example, selective photoelectrochemical etching of macropores in highresistivity n-Si was performed in Tao and Esashi (2005), with a mask on the
electrolyte side and a mask on the side opposite to the illuminated surface. Then,
porous regions were dissolved in KOH to leave prescribed figures with vertical
walls. The walls are not very even because of the underetching and pore branching
at the mask edge.
Thus, various high-aspect-ratio structures can be fabricated by combination of
deep anodization with subsequent processing of macroporous silicon.
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Part V
Applications
Porous Silicon Application Survey

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Domains of Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Product or Function Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Application Survey by Reviews . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
734
734
735
736
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Abstract
All current applications of mesoporous and macroporous silicon under investigation are briefly surveyed, and more than 50 reviews over the period
19852014 are collated. Applications are grouped into twelve domains: electronics, optoelectronics, optics, diagnostics, energy conversion, catalysis, filtration, adsorbents, medical, food, cosmetics, and consumer care. Targeted
product/function examples are given for each domain, together with the current
level of industrial and academic activity. Comparisons are made with the major
industrial uses of silica, comparing high-value and low-value product areas.
Although porous silicon uses in electronics have the longest history of development, the most active R&D domains currently, as gauged by volume of literature, are energy conversion (lithium batteries), medical (drug delivery), and
diagnostics (chip-based biosensing and mass spectrometry).
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_74
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L. Canham
Introduction
This section of the handbook contains a series of reviews dedicated to specific
applications of porous silicon. Indeed, a wide variety of potential uses have been
explored since the 1980s. The objective of this survey is to provide the reader with a
broad overview of all applications considered to date and provide in one location a
published literature database on application reviews. There are some listed application domains which, while common for porous materials in general, have not
received sufficient study in the case of porous silicon to warrant a review in the
handbook. Many are however updates of previous reviews, and many others are
reviewed for the first time in this handbook.
Domains of Application
Twelve application domains are shown schematically in Fig. 1. Of these the four
porosified chip-based application areas on the right hand column are historically the
most developed. Those on the left-hand side utilize primarily porous silicon powders, and it is the medical domain that is currently receiving the most academic and
industrial attention. In the central column lie many of the traditional applications
for porous materials. Two of these domains, catalysis and adsorbents, have received
little attention with regard to porous silicon and so are not the subject of any
dedicated reviews in this handbook.
MEDICAL
ENERGY CONVERSION
ELECTRONICS
FOOD & NUTRITION
CATALYSIS
COSMETICS
FILTRATION
OPTICS
ADSORBENT
DIAGNOSTICS
CONSUMER
CARE
OPTOELECTRONICS
Fig. 1 Current broad application areas of porous silicon under evaluation. Applications are
arranged by the dominant physical form of porous silicon required. On the left-hand column,
applications require primarily powders, on the right-hand column primarily chip-based layers. The
central column applications utilize all three dominant forms: powders, membranes, and films
735
Product or Function Examples

Table 1 provides more detail for each application domain, providing examples of
porous silicon specific products or functions and a qualitative indication of the level
of industrial and research activity. It is arranged and color coded in accordance with
Fig. 1 where domains are grouped by the dominant physical form(s) of the material
required. Emerging domains and product areas given dedicated reviews for the first
time in this handbook are highlighted in bold italics.
Table 1 Porous silicon product development examples across broad application domains.
Domains are grouped as in Fig. 1 by the dominant physical form of porous silicon in targeted
products
Application
domain
Medical
Food and
nutrition
Cosmetics
Consumer care
Energy
conversion
Catalysis
Product/function examples
Brachytherapy, drug
delivery, orthopedics,
tissue engineering,
imaging
Nutrient protection, gum
additive, functional foods
Sunscreen, foundation
excipient, drug delivery
Oral hygiene, shampoo,
antibacterial surfaces
Batteries, solar cells, fuel
cells, thermoelectrics,
acoustics, explosives,
photoelectrodes
Organic pollutant removal,
noble metal salt reduction
Filtration
Biomolecule separation
Adsorbent
Microfluidic
preconcentrator, toxin
removal, heavy metal
remediation
RF isolation, thermal
isolation, micromachining,
gettering
LEDs, lasers, waveguides,
modulators
Photonic crystals, mirrors,
diffraction gratings
Gas sensing, mass
spectrometry, biosensors,
chemical sensors
Electronics
Optoelectronics
Micro-optics
Diagnostics
Academic
activity
level
++++
Industrial
activity
level
++
Microparticles
Microparticles
Nanoparticles
Microparticles
Microparticles
Nanoparticles
Chips
+++++
+++
Membranes
Powders
Membranes
Chips
Membranes
Powders
Chips
Chips
++
Chips
++
Chips
+++
Chips
++++
Dominant
physical form(s)
Microparticles
Nanoparticles
Chips
Blank no known activity, + very low level, +++++ highest level
++
736
L. Canham
Aeronautics
& Space
Electronics
Medical
Agriculture
Plastics & rubbers
Construction
Consumer Care
Foundry
Foods & beverages
Pharmaceutics
Paints & coatings

Catalysis
Cosmetics
Paper &
printing
Diagnostics
Chromatography
Optics
Environmental
Optoelectronics
Energyconversion
Fig. 2 Application domains of silica, porous silica, silicon, and potentially porous silicon,
arranged by typical product values. High-value sectors are to the left; low-value sectors to the
right. Sectors with well-defined and regulated grades of material (silica in most cases) are in light
red circles. Sectors which dominate industrial silica supply are in white circles; those that
dominate industrial silicon supply are in light gray
As silicon is derived from silica and porous silicon can now be derived directly
from porous silica (see handbook chapter Routes of Formation for Porous
Silicon), it is instructive to compare and contrast the application domains of
these specific materials (see Fig. 2). Since solid silica and porous silica are less
expensive than solid silicon and porous silicon respectively, silica-based materials
have penetrated many more low-value application domains than silicon. In the
future, porous silicon will only be utilized in these additional areas if its
manufacturing costs are significantly reduced and additionally it offers compelling
performance improvements (so-called unique selling points).
Porous Silicon Application Survey by Reviews

General reviews covering more than one application domain of porous silicon
include those of Parkhutik (1999), Foll et al. (2002), Lehmann (2002), Granitzer
and Rumpf (2010), Gelloz (2010), Chao (2011) and Langner et al. (2011).
Many specific application areas have been the subject of dedicated reviews in the
past, and this literature database provides another useful survey tool for the handbook reader. Table 2 groups them by application domain, showing the historical rise
737
Table 2 Application domains reviewed in the past and featured in this handbook
Application
Adsorbent
Consumer care
Cosmetics
Diagnostics
Electronics
Energy
conversion
Filtration
Food and
nutrition
Medical
Micro-optics
Microsystems
Optoelectronics
Prior application reviews
Sailor 1997; Ozdemir and Gole 2007; Saha 2008;

Jane et al. 2009; Dhanekar and Jain 2013; Pacholski
2013; Baker and Gole 2014; Gupta et al. 2013
Bomchil et al. 1989; Bondarenko and Yakovtseva
1997; Gautier and Leduc 2014b
Menna and Tsuo 1997; Cho 2010; Ge et al. 2013; Du
Plessis 2013; Manilov and Skryshevsky 2013; Gautier
and Kouassi 2014
2014 handbook
application reviews
1
1
4
3
5
1
1
Canham 1997; Stewart and Buriak 2000; Prestidge
et al. 2007; Anglin et al. 2008; Salonen et al. 2008;
Martin-Palma 2010; Haidary et al. 2012; Kotkovskiy
et al. 2012; Shahbazi et al. 2012; Santos et al. 2012,
2014; Barnes et al. 2013; Ksenofontova et al. 2013;
Savage et al. 2013; Coffer 2014; Santos 2014; Cheng
et al. 2013; Martin-Palma et al. 2014
Thonissen et al. 1997; Pavesi 1997; Arrand
et al. 1998; Wehrspoon and Schilling 2003; TorresCosta and Martin-Palma 2010; Golovan and
Timoshenko 2013
Steiner and Lang 1995; Bell et al. 1996; Lang 1997;
Muller et al. 2010
Hamilton 1995; Fauchet et al. 1995; Kanemitsu 1995;
Canham et al. 1996; Fauchet 1996; Pavesi 1996; Cullis
et al. 1997; Bisi et al. 2000; Khriachtchev 2012
and fall in interest, and which were chosen for new reviews in this handbook. The
regulated consumer-based domains of cosmetics, food, and medicine have received
industrial development as well as academic research over the last decade, and thus a
number of new uses therein were chosen to be highlighted in the handbook. The
medical area in particular is very active currently, with many reviews in the last
2 years and a dedicated textbook (Santos 2014).
Within the energy conversion domain, the most active field currently for porous
silicon research is its use as an anode in lithium batteries. Various solar cell
applications have been explored since 1982 and are reviewed in this handbook,
both from a device performance perspective ( Porous Silicon and Solar Cells)
and from a processing one ( Homoepitaxy on Porous Silicon). More recently
emerged areas include fuel cells, phononics, and hydrogen storage, and each of
these are covered.
738
L. Canham
Diagnostics and sensing via micro-optics and microsystems is another very

active domain of research currently, and thus there are in total ten handbook
reviews dedicated to related topics.
Optoelectronics via porous silicon received multiple reviews during the
19902000 decade. While interest in photoluminescence mechanisms and rising
efficiencies continue unabated, LED development has slowed down, so this field
received less attention in this part of the handbook. There are nonetheless four
relevant reviews in the properties section of the handbook: Photoluminescence
of Porous Silicon, Optical Gain in Porous Silicon, Electrical Transport in
Porous Silicon, and Electroluminescence of Porous Silicon.
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RF Electrical Isolation with Porous Silicon

Gael Gautier
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Coplanar Waveguides (CPW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Planar Inductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Other RF Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
742
744
744
749
749
Abstract
The increasing expansion of telecommunication applications leads to the integration of complete system on chip associating various processing units mixing
passive and active elements. Nevertheless, passive component performances are
limited by the underlying lossy silicon wafer. Then, obviously, the use of
innovative substrates becomes crucial for monolithic RF systems to reach high
performances. So, looking for IC compatible processes, porous silicon seems to
be a promising candidate as it can provide localized isolating regions from
various silicon substrates. In this chapter, we propose a synthesis of RF device
technologies that use porous silicon for reducing losses into the substrate. The
state-of-the-art performances of widespread RF devices, that is to say, inductors
or coplanar waveguides, are then presented. Other RF devices which use porous
silicon as a substrate are also described.
G. Gautier (*)
Universite de Tours, GREMAN, Tours, France
e-mail: gael.gautier@univ-tours.fr
DOI 10.1007/978-3-319-05744-6_76
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G. Gautier
Introduction
The increasing expansion of telecommunication applications leads to the integration of complete system on chip (SOC) associating analog and digital circuits.
These mixed-signal systems integrate active devices, mainly transistors, as well as
key passive components (inductors and/or capacitors), required in many applications as amplifiers, mixers, voltage-controlled oscillators, filters, or resonators.
Nevertheless, passive components performances are limited by the proximity of
the lossy Si substrate. For instance, it is well known that the quality of integrated
spiral inductors is clearly reduced by capacitive effects and eddy current losses into
silicon substrates at high frequencies (Yue and Wong 1998). These limitations can
be partially overcome by design means (Burghartz and Rejaei 2003), but the
development of innovative substrates stays crucial. To have a recent overview of
the challenges related to RF semiconductor devices, one can see the reference
Emam et al. (2013). Looking for IC compatible processes, porous silicon
(PS) seems to be a promising material as it can provide localized isolating regions
from various silicon substrates (Gautier et al. 2012). As a consequence, as
illustrated in Fig. 1, this technique can provide hybrid substrates for highperformance integrated circuits (IC) involving active devices (e.g., diodes or
transistors) as well as passive components (inductors and/or capacitors), required
in many applications.
Fig. 1 Schematic illustration of the hybrid pSi/Si substrate concept and picture of a copper
inductor performed on a localized pSi region
743
To reduce losses into the substrate at high frequencies, the dielectric permittivity
() and the AC conductivity (AC) have to be minimized. Numerous workers
reported studies on mesoporous silicon permittivity measurements generally
made from p-type substrates (for a review, see Canham, 1997). If the material is
not oxidized, a Vegards law between silicon (r 11.7) and air (r 1) can give a
good approximation of the dielectric constant value for a given porosity (p%). In
addition, concerning high porosity samples (6080 %), the measured DC electrical
conductivity varies generally between 1014 and 108 S/cm (Fejfar et al. 1995; Lee
et al. 1996). In the case of mesoporous silicon, with low porosities around 30 %,
values around 107 S/cm have also been measured (Lubianicker and Balberg 1996).
For this material the electrical conductivity decreases with the frequency but stays
up to 103 S/cm even around 1 GHz (Kim et al. 2003).
The first step in the fabrication process of RF circuits, such as coplanar waveguides (CPW) or inductors, consists in anodising silicon on restricted areas. Most of
the time, an efficient substrate isolation is performed using high thickness
mesoporous silicon layers (>10 m) to reduce the couplings with the underlying
silicon substrate. Nevertheless, the mechanical stability of such materials is often
challenging, mainly for large area wafers. Indeed, the stress generated during
porous silicon drying can produce cracks or warpage of the wafers (Ayvazyan
1999). Kim and coworkers reported an effective annealing process to reduce
significantly stress in thick pSi films (Kim et al. 2002). But this technique
requires a precise control of the temperature and annealing ambient (N2 and O2).
In all cases, a compromise must be done to optimize the porosity, the pSi thickness,
the etching area, and the final device electrical performance. Moreover, the localization of the pSi etching is also challenging as the employed mask must be
resistant against HF and must be removed after the anodization process.
Fluoropolymer-based thin films seem to be promising candidates to achieve this
purpose (Defforge et al. 2012).
One alternative solution to obtain very thick porous silicon layers without any
damaging stress of the wafer is to perform the electrical isolation with localized
macroporous silicon. Unfortunately, the surface of such material is inappropriate
for successive layer deposition processes. So, Li et al. (2007) propose a silicon
anodization process of the sample backside and the realization of an RF device on
the remaining crystalline silicon. This layer must be as thinner as possible, i.e.,
less than 10 m, to be efficient. Capelle et al. proposed also a mesoporous/
macroporous bilayer to achieve RF inductors on high thickness pSi (Capelle
et al. 2011).
After the anodization process, most of the time, a stabilization annealing at low
temperature (below 500 C) is performed in an O2 or in a N2 ambient. In some
cases, an oxidation annealing is performed at higher temperature. Afterwards, a thin
oxide cap layer is generally deposited to seal the pores and to ensure a complete DC
isolation between the substrate and the device. Various metal layers can be used for
the strips. To reduce the ohmic losses, low-resistivity metals must be used (Au, Cu,
Al). The thickness of the line must be high enough (some microns) in order to limit
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G. Gautier
the influence of the skin effect at high frequencies. If a second metal strip is
required, in the case of an inductor under-pass, for example, a BCB layer is an
appropriate candidate to perform the isolation.
The performances of typical RF devices on various porous silicon substrates are
presented in the next sections.
Coplanar Waveguides (CPW)

A CPW consists of three conductive strips, that is to say, a conductive line
surrounded by two ground lines. To investigate how efficiently porous Si provides
RF isolation, we can estimate the losses at high frequencies using various means.
We can calculate power losses (PL) by PL 1 |S11|2 |S21|2. The insertion losses
(IL) can be also calculated, only if no reflection occurs, i.e., if s11 equals to zero by
IL(dB) 20 log |S21|. The line attenuation () can be also extracted from the
[S] matrix generally for two different waveguide lengths. Table 1 lists performances of CPW on PS or oxidized PS (OPS) extracted from the literature. The
radiative losses are completely negligible in these structures. In addition, the losses
due to the considered metals are quite low, generally in the range of 35 %.
Therefore, the measured power loss differences are mainly due to the substrate
properties.
Contopanagos and coworkers reported also electrical characterization of copper
micro-strips on 50 m thick macroporous silicon over a p+ substrate. In this case,
power losses of 0.3 at 3 GHz and 0.65 at 5.5 GHz were reported (Contopanagos
et al. 2008b).
Planar Inductors
The main geometrical parameters of a coplanar spiral inductor are the strip width
(W), the spacing between adjacent turns (S), the internal radius (Rint), the number of
turns (Nt), the spacing to the surrounding coplanar ground plane (Sg), and the metal
thickness (tmetal). A relevant frequency-dependent parameter to measure the
overall electrical quality of an inductor is the Q factor obtained when one port is
shorted: the higher the Q factor is, the better the device electrically behaves. The
second parameter, often measured to evaluate inductors, is the self-resonance
frequency. A self-resonance occurs when the inductive reactance of the device is
equal to the parasitic capacitive reactance between the inductor and the substrate,
i.e., if Q 0.
Table 2 summarizes the electrical performances measured for spiral inductors
performed on various porous silicon layers. One can notice that the effect of the
Si substrate removal was clearly demonstrated by Kim et al. (2001). Indeed, for a
5.7 nH inductance and a PS thickness around 100 m, Qmax increases by 50 %, and
the resonant frequency is higher than 17 GHz if the remaining bulk Si under Ps is
fully etched.
70
20
34
20
56
51
85
0.81.2
0.01
1025
10
50
10
66
110
tPS
(m)
25
Porosity
(%)
Si substrate resistivity (
cm)
110
350 C, 30 min, dry

O2
500 C, 30 min, dry

O2
1,100 C, 5 min, dry
O2
500 C, 1 h, wet O2
1,050 C, 2 min, dry
O2
Post-anodization
processes
300 C, 3 h, dry N2
420 C, 1 h, dry N2
47/12/-
15/30/2000
Line geometry
(W/L/G)
80/35/5000
10
135
20
30
30
10
20
10
20
IL 0.4
dB/mm
IL 7 dB/cm
IL 20 dB/cm
2.7 dB/cm
4.1 dB/cm
1.8 dB/cm
2.8 dB/cm
F
(GHz)
10
PL 30 %
28
dB/cm
Losses
PL 80 %
(continued)
Itotia and Drayton

(2002)
You et al. (2003)
Park and Lee (2003)
Molinero et al. (2005)
References
Contopanagos
et al. (2008a)
Table 1 RF electrical characteristics of various coplanar waveguides (CPW) on p-type OPS or mesoporous silicon. All the CPW are made of gold, except for
(Contopanagos et al. 2008a) aluminum. F is the loss measurement frequency and tPS is the PS thickness

745
Porosity
(%)
56
7080
Si substrate resistivity (
cm)
1421
810
13
0.0010.005
Table 1 (continued)
200
1
7
15
Bulk
25
tPS
(m)
26
300 C, 1 h, dry O2
Post-anodization
processes
350 C, 30 min, dry
O2
350 C, 30 min, dry
O2
1,100 C, 5 min, wet
O2
20/80002146/100
5/1000/2.5
100/2000/20
Line geometry
(W/L/G)
94/15000/53
4
10
40
40
40
40
2.9 dB/cm
4.5 dB/cm
7 dB/mm
3 dB/mm
2 dB/mm
13.5
dB/mm
0.19
dB/mm
40
F
(GHz)
4
IL 0.11
dB/mm
Losses
5.1 dB/cm
Sarafis et al. (2013a, b)
Welty et al. (1998)
Nam and Kwon (1997)
References
Peterson et al. (2001)
746
G. Gautier
0 (bulk)
5
50
100
0 (bulk)
200
3050
0.010.05
0.015
tPS
(m)
Bulk
20
50
65
80
100
Si substrate resistivity
( cm)
0.02
60
60
60
60
60
60
30
120
80
78
130
30
150
175
150
75
Rint
180
12
12
6
24
12
12
12
12
30
50
10
50
10
50
50
30
W
30
4
4
4
4
4
4
4
4
10
10
S
10
5.5
5.5
5.5
5.5
2.5
11.5
5.5
5.5
1.5
1.5
3.5
3.5
4.5
5.5
6.5
2.5
Nt
5.5
60
60
50
50
Sg
50
3 (TiAl)
3 (Cu)
1 (1Al)
tmetal
3 (Cu)
4.52
4.52
4.27
5.4
0.89
28.52
3.09
7.91
1
1
7
3.5
12.5
22
28
14
L
(nH)
20
Qmax at f
(GHz)
7.7 (0.2)
9 (0.3)
10.7 (0.4)
11 (0.47)
11.5 (0.5)
6 (4.5)
5.1 (2.5)
2.5 (1.7)
3.6 (1.3)
2 (1)
1.6 (0.25)
1.6 (0.25)
19.92 (3)
21.2 (3.2)
25.5 (4.2)
28 (4.7)
4.2 (1.9)
11.4 (4.86)
10.2 (9)
9.6 (3.1)
16.5 (15.9)
8.7 (1.6)
11 (8)
11.9 (4)
fr
(GHz)
1.2
2.2
2.7
2.9
3
14
14.2
14.4
15.2
5.4
513.4
18.4
8.1
>20
3.4
17.7
8.6
Chong et al. (2005)
Billoue et al. (2011)
Capelle et al. (2011)
References
Gautier et al. (2012)
(continued)
Table 2 Electrical performances, i.e., maximum Q factor (Qmax) and resonance frequency (fr) of coplanar spiral inductors on p-type mesoporous silicon
(except for Capelle et al. 2011). All the dimensions are in microns. The inductance value L is determined for low frequencies (f ! 0)

747
Oxidized porous silicon
0.008
57
510
0.07
Si substrate resistivity
( cm)
0.01
0.015
Table 2 (continued)
tPS
(m)
100a
150
300
54
109
200
0 (bulk)
1
2
50250
25a
50
Rint
150
25
100
W
80
100
25
10
S
80
50
4.5
2
1.5
Nt
4
3.5
Sg
1.5 (Al)
2.3 (Au)
1 (Al)
1 (Cu)
6 (Au)
4 (Al)
tmetal
2 (Au)
3 (Cu)
1.3
1.3
1.3
8
6.3
3.7
7.6
L
(nH)
11.4
Qmax at f
(GHz)
5(2)
6 (0.59)
16 (1)
3.5 (0.57)
6 (1.29)
14 (1.74)
3.4 (3)
3.9 (3)
4.8 (3)
6.5(3)
13.3 (4.6)
15 (3.9)
32 (3.9)
6.5
13.8
4
fr
(GHz)
2.95
3.6
3.7
>10
Xie et al. (1998)

Fang et al. (2005)
Contopanagos and
Nassiopoulou (2007)
Yu et al. (2000)
Kim et al. (2001)
References
Populaire et al. (2004)
Royet et al. (2003)
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G. Gautier
749
In addition, Capelle and coworkers have estimated the surrounding losses

generated by the localization of porous silicon in the neighboring area of spiral
inductors (Capelle et al. 2012).
Other RF Applications
Some complex filter structures have been achieved and characterized on porous
silicon substrates. For instance, Fang et al. (2005) presented a planar integrated LC
filter performed on silicon substrate, which is locally modified using the OPS
technology. The filter consists of two inductors and an MIM (metal-insulatormetal) capacitor on a 30 m thick OPS layer. Measuring the S21 parameter, it can
be found that the 3 dB bandwidth is 2.925 GHz and the midband insertion loss is
0.874 dB at 500 MHz. Billoue et al. (2011) measured also the characteristics of
notch filters on different mesoporous silicon layer thicknesses. The use of PS layers
clearly improves the filter characteristics. The insertion loss is significantly reduced
from 1.05 dB for bulk silicon (3050 cm) to 0.4 dB for a 100 m PSi layer. In
addition, an improvement ratio of 2.5 on the bandwidth was measured. Finally,
Chong and Xie (2005) demonstrated an efficient reduction of capacitive couplings
under bond pads using PS layers.
One can notice that the coherent porous silicon etching technique producing
well-defined macropores arrays can be used as a substrate for 3D capacitors
(Lehmann et al. 1996; Roozeboom et al. 2001). These devices can be for RF
decoupling applications.
References
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Stat Sol (a) 175:R7R10
Billoue J, Gautier G, Ventura L (2011) Integration of RF inductors and filters on mesoporous
silicon isolation layers. Phys Stat Sol (a) 208:14491452
Burghartz JN, Rejaei B (2003) On the design of RF spiral inductors on silicon. IEEE Trans Electr
Dev 50:718728
Canham L (1997) Properties of porous silicon. INSPEC, London
Capelle M, Billoue J, Poveda P, Gautier G (2011) N-type porous silicon substrates for integrated
RF inductors. IEEE Trans Electr Dev 58:41114114
Capelle M, Billoue J, Poveda P, Gautier G (2012) RF performances of inductors integrated on
localized p+ type porous silicon regions. Nanoscale Res Lett 7:523529
Chong K, Xie Y (2005) Low capacitance and high isolation bond pas for high-frequency RFICs.
IEEE Electr Dev Lett 26:746748
Chong K, Xie Y, Yu K, Huang D, Chang F (2005) High performance inductors integrated on
porous silicon. IEEE Elec Dev Lett 26:9395
Contopanagos H, Nassiopoulou AG (2007) Integrated inductors on porous silicon. Phys Stat Sol
(a) 204:14541458
Contopanagos H, Zacharatos F, Nassiopoulou AG (2008a) RF characterization and isolation
properties of mesoporous Si by on-chip waveguide measurements. Solid State Electron
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Contopanagos H, Pagonis DN, Nassiopoulou AG (2008b) Broadband electrical characterization of

macroporous silicon at microwave frequencies. Phys Stat Sol (a) 205:25482551
Defforge T, Capelle M, Tran-Van F, Gautier G (2012) Plasma-deposited fluoropolymer film mask
for local porous silicon formation. Nanoscale Res Lett 7:344350
Emam M, Neve CR, Raskin J-P (2013) RF semiconductor devices. Springer, London
Fang J, Liu ZW, Chen ZM, Liu LT, Li ZJ (2005) Realization of an integrated planar LC low-pass
filter with modified surface micromachining technology. In: Proceedings of IEEE conference
on electron devices and solid state circuits, pp 729732. Hong Kong, CHN
Fejfar A, Pelant I, Sipeck E, Kocka J, Juska G, Matsumoto T, Kanemitsu Y (1995) Transport study
of self-supporting porous silicon. Appl Phys Lett 66:10981100
Gautier G, Capelle M, Billoue J, Defforge T, Leduc P, Poveda P (2012) Porous silicon: application
to RF microelectronic devices. In: Proceedings of EXMATEC conference
Itotia I, Drayton R (2002) Porosity effects on coplanar waveguide porous silicon interconnects.
Proc IEEE MTT-S 2:681684
Kim H-S, Xie Y-H, Devicentis M, Itoh T, Jenkins KA (2003) Unoxidized porous Si as an isolation
material for mixed-signal integrated circuit applications. J Appl Phys 93:42264231
Kim H-S, Zheng D, Becker AJ, Xie YH (2001) Spiral inductors on Si p/p+ substrates with resonant
frequency of 20 GHz. IEEE Electr Dev Lett 22:275277
Kim H-S, Zouzounis EC, Xie Y (2002) Effective method for stress reduction in thick porous
silicon films. Appl Phys Lett 80:22872289
Lee WH, Choochon L, Jang J (1996) Quantum size effects on the conductivity in porous silicon.
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Li C, Liao H, Wang C, Yin J, Huang R, Wang Y (2007) High-Q integrated inductor using postCMOS selectively grown porous silicon (SGPS) technique for RFIC applications. IEEE Electr
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Park J, Lee J (2003) Characterization of 10 m thick porous silicon dioxide obtained by complex
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Integrated RF micro-coils on porous silicon. Proc IEEE Sens 13:10641066
Roozeboom F, Elfrink R, Rijks T, Verhoeven J, Kemmeren A, Van Den Meerakker J (2001) High
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Androula G. Nassiopoulou
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Conductivity of Porous Si at Room Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Temperature Dependence of Porous Si Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Theoretical Determination of Porous Si Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Si Platform for Applications in Si Thermal Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
753
754
754
755
758
759
763
763
Abstract
The exceptionally low thermal conductivity of highly porous silicon has led to
its use as a thermal insulator within microsystems. A comprehensive review of
thermal conductivity literature is provided, together with examples of its use in
microsensing and microphotonic systems.
Introduction
One of the most important physical parameters of any material is its thermal
conductivity (see handbook chapter Thermal Properties of Porous Silicon).
Bulk crystalline Si, the material that is widely used in todays electronics and
sensors, shows moderate thermal conductivity at room temperature (Slack 1964).
A.G. Nassiopoulou (*)

NCSR Demokritos, Institute of Nanoscience and Nanotechnology (INN),
Terma Patriarchou Grigoriou, Athens, Greece
e-mail: A.Nassiopoulou@imel.demokritos.gr
DOI 10.1007/978-3-319-05744-6_77
753
754
A.G. Nassiopoulou
On the other hand, highly porous Si, which is a complex nanostructured Si material,
composed of interconnected nanowires and nanocrystals, shows a much lower
thermal conductivity than that of bulk crystalline Si, which depends strongly on
its structure and morphology. The voids within the porous Si layer and the low
dimensionality of the highly porous Si skeleton serve to inhibit thermal transport
within the layer.
The temperature dependence of thermal conductivity of bulk crystalline Si
follows that of single crystal dielectric materials. It is in general governed by
scattering of phonons with other phonons, the Si isotopes, and crystal boundaries.
At low temperatures, it increases with temperature following a T3 law up to a
maximum situated at around 20 K. Above this maximum, it decreases with
increasing temperature due to the increased phonon-phonon scattering. On the
other hand, nanostructured porous Si shows significantly lower thermal conductivity than bulk crystalline Si due to phonon confinement in the Si nanostructures
composing the Si skeleton. Data available in the literature cover the temperature
range from ~40 K to room temperature. A material with ~60 % porosity shows
more than two orders of magnitude lower thermal conductivity at room temperature than bulk crystalline Si, while this difference increases significantly at
cryogenic temperatures.
Due to its low thermal conductivity, nanostructured porous Si is appropriate for
use as a local substrate for thermal isolation on the Si wafer. It constitutes an
excellent platform for the integration on Si of thermal devices.
In this chapter, we will first review the existing results in the literature on
thermal conductivity measurements on different types of porous Si at room and
low temperatures, and we will then give examples of existing Si devices using
porous Si thermal isolation.
Thermal Conductivity of Porous Si at Room Temperature

General
The thermal conductivity of porous Si depends on its structure and morphology,
which in turn depend on the Si wafer type and resistivity and the electrochemical
conditions used for porous Si formation (1997). Since the thermal conductivity of
porous Si depends on its structure, morphology, and porosity, the experimental
values obtained by different groups in the literature (Drost et al. 1995; Benedetto
et al. 1997; Gesele et al. 1997; Lysenko et al. 1999; Perichon et al. 1999, 2000;
Bernini et al. 1999, 2001; Amato et al. 2000; Lysenko et al. 2002; Shen and Toyoda
2003; Lettieri et al. 2005; Wolf and Brendel 2006; Gomes et al. 2007; Siegert
et al. 2012) show a significant scattering. For mesoporous Si fabricated from
p-type Si with resistivity in the range of 515 cm, the reported values of room
temperature (RT) thermal conductivity range from 0.18 to 1.2 W/m K. On the
755
other hand, for porous Si from (100) p+-type Si wafers with resistivity in the range
of 1020 m cm, the reported values of RT thermal conductivity range from 0.3
to 20.8 W/m K for the grown material, depending on material porosity, the
thickness of the studied porous Si layer, and the measurement technique. For
the slightly oxidized material, the corresponding values are in general slightly
lower. The above values were measured using different techniques, including
the 3 method, micro-Raman scattering, the photoacoustic method, the optical
pump and probe method, scanning thermal probe microscopy, and lock-in
thermography.
Table 1 summarizes the experimental results of RT thermal conductivity of
porous Si, obtained using the abovementioned experimental techniques. The table
is organized per year of publication and the corresponding reference is given.
Temperature Dependence of Porous Si Thermal Conductivity

Contrary to the case of bulk crystalline Si, the temperature dependence of porous Si
is monotonic and does not present any maximum in the investigated temperature
range 35350 K. It is generally governed by phonon confinement in the Si
nanostructures composing the silicon skeleton.
Although there is a lot of work devoted to the room temperature thermal
conductivity of porous Si, little work has been devoted to its temperature dependence in a wide temperature range. Gesele et al. (Gesele et al. 1997) used the 3
method to determine the thermal conductivity of porous Si in the range 35320 K
for samples with different porosities from 64 % to 89 % and different Si wafer
doping levels. They found that for 64 % porous Si layers, the thermal conductivity
of porous Si changed from ~0.15 to 0.8 W/m K for temperatures from 35 K to 350 K
for the material on p+-type Si, while it was much lower and it ranged from 0.03 to
0.15 W/m K in the same temperature range for the p-type Si. The thermal conductivity was found to decrease with increasing porosity. In a more recent paper,
De Boor et al. (2011) determined experimentally the room temperature thermal
conductivity of porous Si of different porosities and through modelling its temperature dependence in the range 150500 K using a simple kinetic model. In a recent
work, Valalaki and Nassiopoulou (2013) used the direct current (dc) method to
determine the thermal conductivity of porous Si formed on a p-type Si wafer in the
temperature range 20350 K. The obtained results were compared to measurements
of the thermal conductivity of pure bulk crystalline Si from the literature
(Glassbrenner & Slack 1964) using the same method. This direct comparison
(illustrated in Fig. 1) showed that the specific 60 % porosity material depicts
more than four orders of magnitude lower thermal conductivity than bulk crystalline Si at cryogenic temperatures. In addition, the thermal conductivity of porous Si
changes monotonically with temperature, and it does not show any maximum as in
bulk Si.
756
A.G. Nassiopoulou
Table 1 Room temperature thermal conductivity of mesoporous Si (250 nm pore diameter) of

different structure and porosity, measured by different groups
Porous Si thermal conductivity at room temperature
Reference
Original Si
wafer (type,
resistivity)
Porosity (%)
Porous Si
layer
thickness (m)
Benedetto
et al. (1997)
p+-type,
0.01 cm
60
23
p+-type,
0.01 cm
50
10
Gesele
et al. (1997)
p-type (100),
0.2 cm
64
3146
3 method
0.8
Lysenko
et al. (1999)
p+-type,
0.01 cm
62
100
Micro-Raman
0.9
Perichon
et al. (1999)
p+-type,
0.02 cm
50
50
Micro-Raman
Bernini
et al. (1999)
n-type, 1 cm
40
Photoacoustic
method
1.03
Amato
et al. (2000)
p+-type, 0.02
cm
55
p+-type,
0.02 cm
75
Perichon
et al. (2000)
p+-type,
0.02 cm
50
50
70
100
Bernini
et al. (2001)
p-type,
(0.71.3) cm
61
19
66
27
73
38
Shen and
Toyoda
(2003)
p (100),
515 cm
23
26.6
3,7
28.2
52
28.3
61
30
40
45 and 170
57
60 and 250
72
40 and 100
27.5
3.2 (free
standing)
37.2
20.8
44.2
20.7
48.4
25.1
8.7
51.7
26.8
6.1
58.8
26.9
4.5
66.2
25.5
2.3
Measurement
technique
Photoacoustic
Method
0.3
72
n-type, 1 cm
Wolf and
Brendel
(2006)
p-type (100),
0.01 cm
2.5
3.9
74
57
Lettieri
et al. (2005)
Thermal
conductivity
(W/m K)
2.93
0.29
26
Photoacoustic
method
1.93
0.74
Micro-Raman
0.7
0.3
Optical pumpprobe technique
0.15
0.13
0.17
Photoacoustic
method
1.2
0.3
0.2
0.18
Photoacoustic
method
2.93
1.03
0.29
Lock-in
thermography
measurement
technique
20.8
12.7
11.3
(continued)
757
Table 1 (continued)
Porous Si thermal conductivity at room temperature
Reference
Original Si
wafer (type,
resistivity)
Porosity (%)
Porous Si
layer
thickness (m)
Gomes
et al. (2007)
p+-type (100),
0.01 cm
30
54
80
30
80
Submicrometer
thickness
20
100
54
Siegert
et al. (2012)
n+-type,
10 m cm
Measurement
technique
Scanning
thermal
microscopy
Thermal
conductivity
(W/m K)
3.6
2.2
1.41
3.8
2.8
1.7
Raman
technique
Electrothermal
finite element
simulation
4.2
Fig. 1 Comparison of the thermal conductivity of porous Si (Valalaki and Nassiopoulou 2013)
with that of bulk crystalline silicon (Glassbrenner and Slack 1964)
The extremely low thermal conductivity of porous Si in a wide temperature

range from 20 K to 350 K makes this material an excellent platform for use as a
local substrate on the Si wafer for the integration of thermal (heating, cooling)
devices.
758
A.G. Nassiopoulou
Theoretical Determination of Porous Si Thermal Conductivity

The thermal conductivity of a porous material is generally modelled using effective
medium theory, which is successful for predicting the thermal conductivity of
macroporous Si but less adequate for the mesoporous material.
Other models use the kinetic theory of phonons through which the thermal
conductivity is expressed as a function of the volumetric heat capacity, the phonon
group velocity, and the phonon mean-free path (De Boor et al. 2011).
Lee et al. (2007) employed a molecular dynamics approach to model the lattice
thermal conductivity of nanoporous Si. They found that its value across pores is
smaller than the bulk value by more than two orders of magnitude at room
temperature and it decreases as a function of pore diameter. This behavior has
been attributed to the reduction of the channels for phonon transport and the
increased phonon scattering at the pore surfaces.
Nonequilibrium molecular dynamics simulations for spherical pores were also
used by Fang and Pilon (2011) for a system length varying from 13 to 30 nm, pore
diameter varying between 1.74 and 5.86 nm, and porosity ranging from 8 % to
38 %. They also developed a physics-based model by combining kinetic theory
and coherent potential approximation. It was found that the effective thermal
conductivity of porous Si is proportional to (11.5fv) and inversely proportional
to the sum (Ai/4 + 1/Lz), with fv, Ai, and Lz denoting, respectively, the porosity, the
pore interfacial area concentration, and the systems length. This last model was
found to be in excellent agreement with the molecular dynamics simulations
results.
Chung and Caviany (2000) used the available two-dimensional porous Si
pore-network simulations along with the Boltzmann transport equation to
determine porous Si thermal conductivity for pore sizes ranging between
1 and 100 nm, which are much less than the bulk phonon mean-free path.
They showed that the hindering effect of the phonon pore scattering due to
reflections from the solid-pore interface is significant for small pore sizes. The
hindering effect of the pore-network randomness is also significant due to the
dendritic structure of the pores.
Randrianalisoa and Baillis (2008) used Monte Carlo simulation to model heat
conduction in porous Si. In their method, an original 3D pore network that
reproduces the morphology of mesoporous Si was developed. The nonlinear
phonon dispersion curves of Si and the phonon mean-free path dependent on
temperature, frequency, and polarization were also considered. The model of
steady-state phonon transport through the pore network was simulated. Their
results were compared with experimental results of porous Si thin films on a
p+-type Si substrate.
Another method used to treat the problem of thermal conductivity of porous Si is
the phonon hydrodynamic approach. Alvarez et al. (2010) applied this method to
the analysis of thermal conductivity of porous Si, considered as a solid matrix with
a random inclusion of small insulating spheres, and they explored the effect of the
pore size on the effective thermal conductivity of the material. They also predicted
759
that the thermal conductivity of porous Si depends not only on porosity but also on
pore radius. It is lower for higher porosity and for smaller pore radius. This was
attributed to phonon ballistic effects.
Porous Si Platform for Applications in Si Thermal Devices

The thermally isolating substrate is one of the most important building blocks of
any thermal device, on which the different active parts of the device are integrated.
It must be composed of a material with sufficiently low thermal conductivity so as
to minimize thermal losses by heat conduction into this substrate. Bulk crystalline
Si wafers are inappropriate for the direct integration on them of this kind of devices
due to the relatively high thermal conductivity of Si (145 W/mK). However, since
Si technology is todays dominant integrated circuit technology, it is very important
to find ways to integrate miniaturized thermal devices on the Si wafer for several
reasons, the most important being the following: (a) Si technology is a batch
technology that allows cost reduction, (b) the integration of sensors with Si electronics opens important new possibilities for the realization of smart devices, and
(c) the size of the sensor and the corresponding system, including its encapsulation
housing, can be significantly reduced. A flexible solution towards the on-chip
integration of miniaturized thermal devices is the fabrication of a local substrate
on the Si wafer, on which the sensor parts can be integrated. The material and
fabrication process of this substrate have to be compatible with Si processing. Such
a material is porous Si. As described above, at high porosity, it demonstrates very
low thermal conductivity, so as a thick such layer can provide sufficient thermal
isolation from the Si substrate. It thus constitutes an excellent local platform on the
Si wafer for the integration on it of different thermal devices (Nassiopoulou and
Kaltsas 1998, 2000). Its fabrication process can be compatible with Si processing if
we avoid the use of any metal in porous Si formation. Furthermore, porous Si
technology offers additional advantages that are the planar topography with the Si
wafer and its tunable properties by the electrochemical conditions used.
The low thermal conductivity membranes used as a substrate for the integration
of thermal devices are usually called micro-hotplates. There are different types of
porous Si micro-hotplates, divided in three categories (Nassiopoulou 2006) as
follows: (a) those using a thick porous Si layer on bulk Si, (b) those using an
open-type freestanding porous Si membrane, and (c) those using a close-type
freestanding porous Si membrane. Fig. 2a shows schematically a cross-sectional
view of the first type of micro-hotplate, while Fig. 2b shows a scanning electron
microscopy (SEM) image of a close-type freestanding porous Si membrane
(reference for (b): E. Michelakaki and A. G. Nassiopoulou, unpublished results
Michelakaki 2008).
Freestanding oxidized porous Si micro-hotplates were first applied in sensor
devices. Tabata (1986) and Tabata et al. (1987) used a 20 m-thick porous Si
membrane, fully oxidized at 1,000 C by wet oxidation, in a fast flow sensor.
However, the oxidized material is in general very sensitive to cracking due to
760
A.G. Nassiopoulou
Fig. 2 (a) Schematic

representation of a crosssectional view of a microhotplate on Si using a thick
porous Si layer. (b) Scanning
electron microscopy (SEM)
image of a close-type
freestanding porous Si
membrane (Reference for (b)
E. Michelakaki and A. G.
Nassiopoulou, unpublished
results (Michelakaki &
Nassiopoulou, 2008))
oxidation-induced stresses, and the corresponding process is quite critical, reducing

the fabrication yield.
The first device using a non-oxidized thick porous Si layer as a local thermal
isolation platform on the Si wafer was a miniaturized gas flow sensor with excellent
performance and high fabrication yield (Kaltsas and Nassiopoulou 1999). It was
using a locally formed 40 m-thick porous Si layer on which the sensor active
elements, composed of a polysilicon heater and two series of thermocouples on its
two sides, were integrated. Both the heater and the hot contact of the thermocouples
were lying on porous Si, while their cold contact was lying on bulk crystalline Si, so
as to assure a fixed reference temperature. Fig. 3a shows a plane-view SEM image
of the sensor, while Fig. 3b shows the resistance increase of the resistor on porous Si
compared to that of a similar resistor on bulk crystalline Si. Due to the thermal
761
Fig. 3 (a) Plane-view SEM image of a gas flow sensor using porous Si thermal isolation. (b)
Temperature increase on the resistor on porous Si compared to a similar resistor on bulk crystalline
Si. The rate of temperature increase is 2.16 /mW for the resistor on porous Si and 0.16 /mW for
the resistor on bulk crystalline Si
isolation by the porous Si layer, the resistor on porous Si shows a resistance increase
with power of 2.16 /mW, while this is only 0.16 /mW on bulk Si. This is
indicative of the effectiveness of thermal isolation provided by the thick porous Si
layer. In addition to its small size and low fabrication cost, the above sensor
exhibited high sensitivity and fast response (Kaltsas et al. 2002). This flow sensor
was used in a high-performance flowmeter for respiration control (Kaltsas and
Nassiopoulou 2004) and in an air flowmeter for use at the air inlet of a vehicle
engine (Hourdakis et al. 2012). Figure 4a shows an optical image of the sensor used
in the air flowmeter for car engine, while Fig. 4b shows the corresponding flow tube
with a bias in it, in which the sensor was mounted. Figure 4c shows the air
flowmeter output as a function of flow.
A thermal flow sensor using porous Si thermal isolation as the one described
above was also used in a Si thermal accelerometer without solid proof mass
(Goustouridis et al. 2007) and in a Si thermoelectric generator (Hourdakis and
Nassiopoulou 2013).
A different device using a thick highly porous Si layer for thermal isolation from
the Si wafer was a Nb film bolometer. In reference (Benedetto et al. 1997), a film
bolometer using an 8 m-thick highly porous Si layer was reported that demonstrated also good sensitivity and fast response.
A photonic device is also found in the literature (Wang et al. 2007) using the
thermal insulation properties of porous Si in a photonic crystal reflector for
mid-infrared applications. It uses an alternate high-porosity/low-porosity multilayer structure with the high-porosity layers fully oxidized and the low-porosity
layers partially oxidized in order to achieve good thermal insulation properties and
at the same time enough contrast of the refractive index.
In order to further improve the thermal isolation provided by the porous Si layer,
freestanding porous Si membranes were used instead of the thick layer directly in
contact with the Si substrate. Two different techniques were employed for their
762
A.G. Nassiopoulou
Fig. 4 (a) Optical image of a flow sensor used in the air flowmeter for car engine developed at
NCSR Demokritos/IMEL, (b) flow tube with a bias in it in which the sensor was mounted, (c) air
flowmeter output as a function of flow
fabrication: In the first one (Tserepi et al. 2003; Tsamis et al. 2003a), the porous Si
membrane is first formed on bulk crystalline Si following a predefined pattern. The
bulk Si underneath the membrane is then etched using selective reactive ion etching
through openings in the patterned film, so as to release the porous Si membrane
from the substrate. Based on this kind of open-type micro-hotplate, a low-power
gas sensor for the detection of hydrogen-containing gases in an explosive environment was designed and realized (Tsamis et al. 2003b; Tsamis and Nassiopoulou
2003). A second type of freestanding porous Si membranes is the close-type
membrane, fabricated in a single two-step electrochemical etching process (Pagonis
et al. 2004a; Nassiopoulou et al. 2003). In the first step, the current density used is
chosen so as to form highly porous Si, while in the second step, the current density
is increased so as to exceed the critical value that leads to electropolishing. In this
way, a porous Si layer is formed on top of an air cavity. An example of freestanding
porous Si membrane, fabricated using this second technique, is illustrated in the
cross-sectional SEM image of Fig. 2b. This second process was used to design and
realize a very sensitive micro-flow sensor (Pagonis et al. 2004b, 2007).
763
Conclusion
Porous Si shows a much lower thermal conductivity than bulk crystalline Si. The
measured difference is more than two orders of magnitude at room temperature,
while it exceeds four orders of magnitude at cryogenic temperatures. This makes
porous Si very appropriate for use as a local thermal isolation platform on the Si
wafer for the integration of sensitive thermal and other devices. Existing devices to
date include flow sensors, accelerometers, bolometers, gas sensors, thermoelectric
generators, and photonic crystal reflectors. Related handbook chapters include
Photolithography on Porous Silicon, Porous Silicon for Microdevices and
Microsystems, Porous Silicon Phononic Crystals, and Porous Silicon
Gas Sensing.
Acknowledgements This work was supported by the EU Network of Excellence FP7
Nanofunction, Contract No 257375.
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Porous Silicon Gettering

Izabela Kuzma-Filipek and Hariharsudan Sivaramakrishnan
Radhakrishnan
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Gettering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
767
771
775
775
Abstract
Gettering, the process whereby unwanted impurities are moved to noncritical

regions of devices, is achievable with porous silicon, as primarily a result of its
very high surface areas. The mechanisms, different techniques, and classification
of gettering in silicon, the methods of characterization, and the gettering performance of mesoporous silicon with regard transition metals are reviewed.
Introduction
Gettering is the process of reducing recombination sites, particularly impurities
from the active regions of the electrical devices into locations where they do not
deteriorate the device performance. It depends on the number of sinks for absorbing
impurities, on segregation coefficients indicating the ability of the getter sites to
adsorb the impurities, as well as on the diffusion coefficients of the impurities in the
bulk and in the getter medium (Perevostchikov and Skoupov 2005; Schroter
et al. 1991; Smith et al. 2000). Temperature is another factor that directly impacts,
e.g., the diffusion coefficients. Gettering can be used to reduce the detrimental
effects of transition metals on the crystal quality. An extensive review on the
I. Kuzma-Filipek (*) H.S. Radhakrishnan
IMEC, Heverlee, Belgium
e-mail: kuzma@imec.be
DOI 10.1007/978-3-319-05744-6_78
767
768
I. Kuzma-Filipek and H.S. Radhakrishnan
mechanisms of transition metal gettering is given by S.M. Myers (Myers

et al. 2000), where the major gettering mechanisms are discussed: (i) metal silicide
precipitation, (ii) segregation into second phases, (iii) atomic trapping by defects,
(iv) interaction with electronic dopants, and finally (v) phosphorus diffusion
gettering and nonequilibrium processes. These were classified by the authors
according to diffusivity thresholds for (i) local atomic processes (1 nm diffusion
distance), (ii) proximity gettering (10 m diffusion distance), and (iii) backside
gettering (0.5 mm distance). E.R. Webers (Hull 1999) review on gettering in
silicon technology gives a magnificent overview on gettering techniques which
are classified into internal and external gettering. Examples of intrinsic gettering
(IG) are intrinsically incorporated defects in the bulk of the wafer that act as
gettering sites, and these can have various proximity natures, although usually
referred to gettering region located inside the wafer. In extrinsic gettering
(EG) the metals are transferred to the back or near the surface of the wafer where
their presence is not influencing the device performance or are removed from the
wafer. In such external/extrinsic gettering, an external treatment such as diffusion,
mechanical damage, or implantation is required to achieve the gettering mechanism. Gettering can be succeeded by different gettering sites that promote various
gettering mechanisms. Examples of it are listed in Table 1. Most of the examples of
gettering by porous silicon reported in the literature are extrinsic, proximity
getterings (PG), and although governed by same gettering mechanism, the division
into porous silicon obtained by stain etching or electrochemical etching is listed.
Examples of the intrinsic gettering are gettering by oxygen precipitates (Falster
et al. 1991), doping-enhanced solubility (Smith et al. 2000), and microdefects and
dislocation gettering (Seibt et al. 1996; Martinuzzi 1996). The recombination
activity of the latter is enhanced by transition metal decoration. These metals are
intrinsically incorporated in the silicon feedstock material especially if produced by
directional solidification from polycrystalline Si chunks (Istratov et al. 2003a;
Ciszek 1996) and have high impact on minority charge carrier recombination
activity (Myers et al. 2000; Rohatgi et al. 1983; Davis et al. 1980; Weber 1983).
There are several parameters influencing the gettering process of crystal defects,
such as the intrinsic solubility and diffusivity of the impurity in the material, and the
duration and cooling rates of thermal processes. During cooling the solubility
drastically decreases and the silicon becomes supersaturated with impurities. The
systems tend to an equilibrium state by precipitation at structural defects or within
the grain and dislocations (Seibt et al. 1998). It was found by the group of
Buonassisi (Buonassisi et al. 2005) that high flux elements, with high solubility
and diffusivity like Cu, and Ni, preferably are found segregated at structural
defects, whereas low flux or medium flux elements like Fe and Ti are often found
within the grains and in much smaller and closer-spaced particles.
External gettering techniques according to Hull (1999) are (i) phosphorus diffusion gettering, (ii) Al gettering, (iii) backside damage and poly-backside seal
gettering, (iv) chemical gettering, and (v) proximity gettering such as implantationinduced cavity gettering and ion implantation gettering, (vi) gettering by heavily
doped substrates, and (vii) gettering by the silicon surface, by Si/SiO2 interface, and
Application
Integrated circuits
(ICs), PV
Microelectronics
Microelectronics,
PV
PV,
microelectronics
Mechanism
Precipitation
Atomic trapping of
defects
Atomic trapping of
defect
P-diffusion gettering
Gettering method
Gettering by dislocations and oxygen

precipitates (IG)
Proximity gettering (PG): cavity

gettering (IG/EG)
PG
P-gettering (EG)
Table 1 Gettering methods

Analysis
Reference
Martinuzzi (1996)
(continued)
Kang and Schroder

(1989)
Morehead and Lever

(1986)
Sopori et al. (1994)
Schindler (1994)
LBIC, Leff maps, IQE, Mossbauer spectroscopy
Skorupa et al. (1995)

Hampel et al. (2013)
Wong-Leung
et al. (1995)
Myers et al. (1994)
Petersen et al. (1997)
Follstaedt
et al. (1996)
Chason et al. (1997)
Seibt et al. (1998)
Seibt et al. (1996)
Falster et al. (1992)
Falster et al. (1991)
Sumino (2003)
SIMS, inductively coupled plasma mass spectrometry

(ICP-MS)
TEM, RBS, SIMS
Electron spin resonance, EBIC, TEM, DLTS, SIRM

769
Application
PV,
microelectronics
PV,
microelectronics
PV,
microelectronics
Mechanism
Segregation into
second phases
Atomic trapping of
defects
Atomic trapping of
defects
Gettering method
AlSi gettering (EG)
Electrochemically etched porous Si

(EG/PG)
Stain-/vapor-etched porous Si
(EG/PG)
Table 1 (continued)
Analysis
Light beam-induced current (LBIC), light IV, hall

effect measurements, capacitancevoltage (C-V), dark
IV, IQE, QSSPC, hall mobility enhancement
Photoconductive decay/photocurrent generation

method
Improved minority carrier diffusion length, BSF

formation
Reference
Jaballah and
Ezzaouia (2007)
Hilali et al. (2001)
Dimassi et al. (2002)
Menna et al. (1998)
Tsuo et al. (1996a)
Lotfi and Hatem

(2012)
Khedher et al. (2009)
Khedher et al. (2004)
Radhakrishnan
et al. (2012)
Kuzma-Filipek
et al. (2009)
Bilyalov et al. (2001)
Borisenko and
Dorofeev (1983)
Borisenko
et al. (1984)
Lamedica
et al. (2002)
Vinod (2007)
Joshi et al. (1995)
McHugo et al. (1997)
Thompson and Tu
(1982)
Martinuzzi
et al. (1995)
770
771
wafer-bonding interface. Examples of external/extrinsic gettering are cavity

gettering (Follstaedt et al. 1996; Chason et al. 1997; Petersen et al. 1997), obtained,
e.g., by ion implantation. Implantation damage forming cavity microstructures and
heavily doped regions can provide efficient traps for metal impurities. These are
often intentionally introduced gettering sites during fabrication of CMOS devices,
like implantation process known as separation by ion implantation of oxygen
(SIMOX). Such buried oxide structure provides a barrier for diffusion of metals
between the device area and the substrate (Istratov et al. 2003b). Hydrogen implantation and subsequent thermal annealing is found to result in a well-defined band of
cavities in Si. Transition metal atoms such as Cu, Ni, Co, Fe, and Au are shown to
be strongly trapped (1.52.2 eV) on the cavity walls by chemisorption-like reaction
(Follstaedt et al. 1996). The band of cavities is an extremely efficient gettering layer
for Cu which is also introduced into the near surface of Si by ion implantations
(Myers et al. 1994; Wong-Leung et al. 1995). A beneficial aspect of implantation
gettering and in general proximity gettering is the close proximity of the gettering
layer and the fact that the gettering can occur with low thermal budgets (Hull 1999)
and much faster than standard techniques such as internal gettering (McHugo
et al. 1998). Additionally, the implant region provides a uniform gettering layer
as compared to internal gettering where the gettering sites are widely dispersed.
Other extrinsic getterings are based on phosphorous diffusion gettering from
gaseous POCl3 or deposited source (Martinuzzi 1996; Schindler 1994; Sopori
et al. 1994; Kang and Schroder 1989; Cuevas et al. 1997; Bentzen et al. 2006;
Morehead and Lever 1986), P- or backside PAl co-gettering (Khedher et al. 2009;
Vinod 2007; McHugo et al. 1997; Joshi et al. 1995; Thompson and Tu 1982). The
efficiency gettering for both are similar (Loghmarti et al. 1993) and also compared
to cavity gettering. Porous silicon stain-etched gettering enhanced with P-diffusion
(Tsuo et al. 1996a, b; Menna et al. 1998; Lotfi and Hatem 2012) or electrochemically etched porous silicon (Lamedica et al. 2002; Borisenko et al. 1984) are
examples of external gettering, achieved by various techniques such as backside
damage (BSD) or chemical gettering in combination with thermal anneal or proximity gettering.

Deliberate surface damage is often introduced at the surface as a source of defects
and strains into Si lattice to which impurities can segregate (Perevostchikov and
Skoupov 2005). Formation of a thin mono- or multilayer with porous silicon serves
to that purpose. The significant increase of the surface area achieved with the
porous silicon (nearly 600 m2/cm3), formation of the dangling bonds on the internal
surface of the nanometer-scale voids, and mismatched lattice parameter of electrochemically and chemically etched porous silicon compared to that of bulk Si greatly
enhance the probability of trapping the contaminants during high-temperature step.
Various publications demonstrate gettering process with the use of the stainetched porous silicon and PAl co-gettering (Khedher et al. 2009; Vinod 2007).
772
Other records are dealing with porous silicon as a gettering method based on its
atomic trapping ability (McHugo et al. 1997; Tsuo et al. 1996b). The group of
Y. Ogata reports that the formation of the dangling bonds in porous silicon starts
after desorption of trihydrides and dihydrides and their presence makes it possible
to reorganize the surface structure and therefore trap contaminants even at temperatures as low as 350 C (Ogata et al. 2001).
The group of Y.S. Tsuo has demonstrated that porous silicon stain-etched layers
formed by simple double-side etching can act as gettering sites, which are very
effective gettering techniques for Fe, Cu, and Cr impurities (Tsuo et al. 1996a, b;
Menna et al. 1998; Lotfi and Hatem 2012). Also the findings of Khedher
et al. (2004, 2005) had proven the gettering ability of stain-etched porous silicon,
where a clear enhancement of the mobility and the minority carrier diffusion length
were measured in comparison to the reference untreated substrate. Also improved
performance of the MOS devices was reported by Khedher et al. (2009) due to
porous silicon gettering.
Electrochemically etched porous silicon is known to introduce lattice distortion
and strain (Lei et al. 2004) as well as dangling bonds and as such was already
demonstrated to be used as an effective gettering side (Poponiak 1975; Borisenko
and Dorofeev 1983; Shieh and Evans 1993). Multilayers of porous silicon etched
into low-cost and low-quality Si substrate were reported to be a good diffusion
barrier for contaminants from the bulk (Bilyalov et al. 2001). Several examples of
such porous silicon multilayer structure, used not as a sacrificial layer but rather
embedded in between low-quality, highly doped p+, electrically inactive substrates
and higher-quality active Si layer grown epitaxially on top, are reported (Bilyalov
et al. 2001; Kuzma-Filipek et al. 2009; Radhakrishnan et al. 2012).
Substrates used in the above examples are highly B-doped silicon considered as
out of spec by microelectronic industry, reclaim, or (upgraded) metallurgical-grade
silicon (UMG), therefore potentially containing high levels of transition metal
impurities (Istratov et al. 2003a; Ciszek 1996). In such monolithic architecture
with porous silicon located between low-quality substrates and high-quality epitaxial layer (see Fig. 2 left), porous silicon has twofold functions: enhancing optical
reflection (while used in thin film epitaxial silicon solar cells, epicell) and
gettering metals with high diffusivity and solubility within the substrate, which
can out-diffuse into the active epitaxial layer being formed during subsequent hightemperature step. Transition metal impurities are minority carrier lifetime killers
(Rohatgi et al. 1983; Davis et al. 1980; Weber 1983), and thus, their out-diffusion
must be restricted to minimum.
In Kuzma-Filipek et al. (2009), the authors show an example of effective
gettering by means of electrochemically fabricated multilayer of porous silicon
etched into UMG Si substrates, intrinsically contaminated with transition metals
impurities. The test structures consisted of a 15-layer stack of a total thickness of
1,300 nm on top of which 300 nm epitaxial silicon was grown by CVD. The
structure was exposed to high-temperature treatment and the metal trapping effect
was monitored by SIMS depth profiling of Cu. The data revealed no trapping effect
of Cu in the case of a reference sample where no porous silicon barrier was
773
Fig. 1 Cu impurity profiles

obtained by SIMS for two
samples: upper one, reference
without PSi layers and
300 nm thin epilayer; sample
below, a 15-layer stack of PSi
layers with total thickness of
1,300 nm with thin epilayer of
300 nm. One line indicates
concentration in at per cm3
and the second line indicates
detection in counts per second
(Kuzma-Filipek et al. 2009)
Table 2 Records on effective metal gettering by porous silicon trapping site

Impurity gettered by
porous silicon
Cu, Au
Analysis technique
PCD pulsed MOS capacitor for active layer
quality, defect etching
Cu, Cr, Fe
SIMS
Cu, Fe
SIMS, TXRF
Cu, Fe, Ni, Cr
SIMS, direct TXRF
Cu, Cr, Fe, B, Al
SIMS, junction profile measurements
Reference
Borisenko and
Dorofeev (1983)
Lamedica
et al. (2002)
Borisenko
et al. (1984)
Bilyalov
et al. (2001)
Kuzma-Filipek
et al. (2009)
Radhakrishnan
et al. (2012)
Tsuo et al. (1996a)
Menna et al. (1998)
implemented. In the case of sample including porous silicon layer, an increased Cu

concentration was observed in the depth corresponding to porous silicon multilayer
stack (see Fig. 1).
The tabulated summary on investigated impurity gettering by porous silicon can
be found in Table 2.
Gettering by embedded PSi layers was also studied theoretically using density
functional theory where large binding energies (1.92.2 eV) for metal segregation
to PSi void surface were calculated for Fe and Cu (Radhakrishnan et al. 2012).
Modelling showed that Fe and Cu both have large average metal-void surfacebinding energies due to the fact that such binding can passivate dangling bonds and
774
Fig. 2 Left: Schematic of an epicell-like test structure, contaminated by spin coating and metal
drive-in after epitaxy, depicting the distribution of metals in cross section as well as on the top
surface (drawing not to scale). Right: Map of the surface concentration of Cu obtained by TXRF
measurement on a sample that was back surface-contaminated to a concentration of 1015/cm2
and annealed at 950 C for 15 min (Radhakrishnan et al. 2012)
relax the disturbed atomic structure on the void surface. Such large binding energies
allow porous silicon to have large gettering coefficients of 104 at 1,000 C.
The experimental vehicles to prove this consisted of a 2-m-thick epitaxial Si
layer grown at 1,130 C for 1020 min on top of a square-like 8.5 8.5 cm2 area of
PSi multilayer with alternating porosity of 28/41 %, etched into the middle of an
800 circular Cz, p+ wafer (see Fig. 2). These wafers were back surface-contaminated
with metals (Fe, Ni, Cu) to 10141015/cm2 and annealed at high temperatures
(9501,000 C) for up to 15 min. This allowed the metals to be distributed
throughout the wafer and getter to preferential sites.
Direct TXRF mapping of Cu on the front side showed that the embedded PSi
reduced the amount of Cu reaching the top surface by 103 times, compared to the
periphery areas without PSi (see Fig. 2 right). A control wafer without porous
silicon showed no such pattern with uniform and high Cu surface concentrations,
confirming barrier properties of porous silicon. Similar TXRF maps were obtained
for Ni and Fe.
The authors (Radhakrishnan et al. 2012) present also the SIMS depth profiling
revealing large metal concentrations (1018 1019 at/cm3) in the depth associated
with PSi, while the metal concentrations were below detection limits in the surrounding area (1015 1017 at/cm3), suggesting a gettering coefficient (defined as the
ratio between the concentration of gettered metal, CMT, and the concentration of
mobile metal, CMi) of 103 104 for all investigated metals (Fe, Ni, Cu). SIMS
profiles presented in Radhakrishnan et al. (2012) additionally confirmed results
obtained by Sumino and Nippon Steel Corporation (1996) showing more Fe atoms
lost from Si matrix in the slow cooled crystal than in the fast cooled crystal. Also
higher metal concentration was measured in the low porosity (28 %) layer compared to the high porosity (41 %) layer due to much higher average metal-void
surface-binding energy present in the pores with smaller radii.
775
Conclusions
In this chapter, porous silicon is reviewed as one of the gettering agents effectively
used in microelectronics. Its gettering abilities result from increased surface area,
formation of the dangling bonds on the internal surface of the nanometer-scale
voids, as well as mismatched lattice parameter. Mainly the external/extrinsic use of
porous silicon as a getter center is reported either for porous silicon used as a
sacrificial layer which is removed after gettering step or embedded in electrically
inactive device regions as mono- or multilayer. The mechanism in all applications
is based on atomic trapping.
The gettering efficiency of cavity gettering (proximity gettering), example of
which is gettering by incorporation of controlled porous silicon single or multilayer
diffusion barrier, is comparable to Al- gettering or phosphorus diffusion gettering.
While the latest will remain dominant in PV industry for the next several years,
proximity gettering could increase its role in the field due to its ability to effectively
getter low impurity concentration substrates with slow diffusing metals (Hull
1999). Such external gettering is effective not only for fast diffusing metals such
as Cu and Ni but also slower diffusing metals such as Fe. This could be also an
advantage over low-cost gettering techniques such as HCl wet or gaseous gettering
as these are less effective to Fe, Au, and Cr (Ohsawa et al. 1984; Honda et al. 1995).
Porous silicon gettering is proven to effectively getter Cr and Fe (Tsuo et al. 1996a;
Radhakrishnan et al. 2012), as well as fast diffusing metals as can be seen in the
given examples in Table 2.
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Porous Silicon Micromachining Technology

Giuseppe Barillaro
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrochemical Micromachining of Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
779
780
783
784
Abstract
In this chapter, silicon electrochemical micromachining (ECM) technology is

reviewed with particular emphasis to the fabrication of complex microstructures
and microsystems, as well as to their applications in optofluidics, biosensing,
photonics, and medical fields. ECM, which is based on the controlled electrochemical dissolution of n-type silicon under backside illumination in acidic
(HF-based) electrolytes, enables microstructuring of silicon wafers to be
controlled up to the higher aspect ratios (over 100) with sub-micrometer
accuracy, thus pushing silicon micromachining well beyond up-to-date both
wet and dry microstructuring technologies. Both basic and advanced features
of ECM technology are described and discussed by taking the fabrication of a
silicon microgripper as case study.
Introduction
Silicon micromachining tools (Kohler 1999) have been developed for over 50 years
with the ambition of sculpting silicon wafers at the microscale, continuously paving
the way toward novel research/market devices and applications. In the 1960s, the
G. Barillaro (*)
Dipartimento di Ingegneria dellInformazione, Universit di Pisa, Pisa, Italy
e-mail: g.barillaro@iet.unipi.it
DOI 10.1007/978-3-319-05744-6_79
779
780
G. Barillaro
market request for microfluidic devices, e.g., chromatographic columns, inkjet

cartridges, etc., drove micromachining research/industry toward the development
of wet etching technology characterized by low-cost, but with limited flexibility in
fabrication and low integration density. In the 1980s, novel challenging applications, e.g., microelectromechanical systems (MEMS), and lab-on-a-chip (LoC),
pushed micromachining research/industry toward the development of dry etching
technology with increased flexibility in fabrication and higher integration density,
although higher cost too. Both wet and dry technologies are still under development, with wet technology being used nowadays for the fabrication of
undemanding microstructures with low density at lower cost, and dry technology
exploited for the fabrication of complex microsystems with increased density at
higher cost. In the 2000s, the new challenge for silicon micromachining has been
the development of high-aspect-ratio technology that allows the etching of microstructures and microsystems with different shapes and micrometer-sized features to
be finely controlled up to very high aspect ratios (over 100), thus enabling the actual
exploitation of the room available in the third (out-of-plane) wafer direction and
breaking novel research/market grounds, e.g., Through Silicon Via (TSV) fabrication for a new generation of three-dimensional chip stacking.
Electrochemical Micromachining of Silicon

Electrochemical micromachining (ECM) (Bassu et al. 2012) of silicon has been
recently demonstrated as a powerful and flexible microstructuring technology that
allows the etching of silicon wafers to be controlled up to the higher aspect ratios
(over 100) with sub-micrometer accuracy, thus pushing silicon micromachining
well beyond any up-to-date both wet and dry microstructuring technology. ECM
technology capitalizes on the experimental and theoretical results reported in the
literature over the last two decades on the electrochemical etching of n-type silicon
under backside illumination in acidic (HF-based) electrolytes (backsideillumination electrochemical etching (BIEE)) (Lehmann 2002). The BIEE was
pioneered, in the 1990s, by Lehman and Foll for the controlled etching of highaspect-ratio macropores (Lehmann and Foll 1990; Lehmann 1993, 2002; Foll
et al. 2000; Barillaro et al. 2002a; Barillaro and Pieri 2005; Barillaro and Strambini
2010), and later, in the 2000s, pushed by a number of scientists to the fabrication of
a multitude of high-aspect-ratio microstructures for different applications (Ottow
et al. 1996; Ohji et al. 1999; Kleimann et al. 2001; Barillaro et al. 2002b, 2003,
2005a, b, 2006, 2007a, b, 2008, 2009a, b; Schilling et al. 2001; Matthias et al. 2004,
2005; Astrova and Nechitalov 2008; Astrova et al. 2009, 2010). For a review of the
fabrication of macropores by anodization, see handbook chapter Macroporous
Silicon. In the 2010s, a novel dynamic control of the electrochemical etching
anisotropy as the etching progresses has allowed the silicon dissolution to be
switched in real time from the anisotropic to the isotropic regime and has enabled
advanced silicon microstructuring to be performed (Bassu et al. 2012; Barillaro
781
Fig. 1 (a) Example (SEM image) of a silicon microgripper fabricated by ECM technology; (b)
main technological steps for advanced silicon microstructuring by ECM technology, with specific
reference to the part highlighted (see circle) of the silicon microgripper in (a).
et al. 2011; Merlo et al. 2012a, b, 2013; Strambini et al. 2012; Surdo et al. 2012,
2013; Carpignano et al. 2012; Polito et al. 2013).
Fabrication of microstructures and microsystems by ECM technology (Bassu
et al. 2012; Surdo et al. 2012, 2013; Polito et al. 2013) is carried out according to the
following main technological steps, which are sketched in Fig. 1b with specific
reference to the microgripper of Fig. 1a. The starting material is n-type silicon,
orientation (100), with a thin silicon dioxide layer on top. The pattern of the
microstructure to be fabricated is defined on a photoresist layer by standard
lithography, transferred to the silicon dioxide layer by buffered HF (BHF) etching
through the photoresist mask (Fig. 1b-1), replicated (seed point formation) into the
silicon surface by potassium hydroxide (KOH) etching through the silicon dioxide
mask (Fig. 1b-2), and finally grooved into the bulk material by BIEE. The BIEE
consists of a single-etching step with an initial anisotropic phase (Fig. 1b-3), used to
etch the seed pattern deep in the substrate and create high-aspect-ratio microstructures, and a final isotropic phase (Fig. 1b-4), used to release part of the etched
microstructures from the substrate and, eventually, yield them freestanding. A
dynamic control of the electrochemical etching anisotropy, which is used to switch
the silicon dissolution in real time from the anisotropic to the isotropic regime, is
synergically combined with the use of both functional and sacrificial structures.
Functional (sacrificial) structures are, by definition, parts of the microsystem that
are anchored (not anchored) to the silicon substrate after the isotropic phase of
electrochemical etching step (and are, hence, removed). The former are indeed
functional to the microsystem operation, while the latter are sacrificed for the
accurate microsystem fabrication. All the microsystem parts visible in the SEM
image of Fig. 1a are functional structures, which are still connected to the substrate
through anchor structures properly designed to withstand the isotropic phase of the
BIEE. Sacrificial structures are removed after the isotropic phase of the BIEE and
hence not visible in Fig. 1a. If needed, a further thermal oxidation step can also be
performed to grow a 100-nm-thick conformal silicon dioxide layer, to be used as an
insulation layer, on which a metal contact for actuation of the microgripper (or, in
782
G. Barillaro
general, of the fabricated microsystem) can be deposited by quasi-conformal metal

sputtering.
Sub-micrometer control of the silicon dissolution at the seed sites, in the X-Y
plane and along the Z-direction, is obtained by properly modulating both the
etching current density, Jetch, and the etching voltage, Vetch, as the etch progresses.
The Jetch and Vetch values are kept within the working region: Jetch < Jpeak and
Vetch > Vpeak, where Jpeak and Vpeak represent the values of the current density and
voltage of the electropolishing peak of the electrochemical system under investigation. In the working region, the silicon mass dissolved per unit time around a
given X-Y position is proportional to the ratio Jetch/Jpeak (also known as the
porosity P), for any etching depth; the Jpeak value also determines the etching rate
in the Z-direction, which is, indeed, proportional to Jpeak. The silicon dissolution
(in terms of both volume and isotropy versus time) is finely tuned as the etching
progresses by properly controlling the Jetch value over time. On the one hand, if the
Jetch value is slowly reduced over time according to HF-diffusion kinetics, it is
possible to compensate for the slight reduction of the Jpeak value with etching depth,
so that by maintaining the Jetch/Jpeak ratio constant over time, the etching results to
be perfectly anisotropic and, in turn, micromachined structures with excellent
straight walls are achieved. The reduction of Jpeak with etching depth is caused
by a reduction in CHF inside the etched trenches, due to stationary diffusion of HF
molecules from the top to the bottom of the etched structures (Barillaro and Pieri
2005). On the other hand, if the Jetch value is suddenly increased over time with
respect to the HF-diffusion kinetics, a dramatic decrease of the Jpeak value occurs,
which dynamically increases the Jetch/Jpeak ratio, and, in turn, the silicon mass
dissolved per unit time. A higher number of HF molecules per unit time, with
respect to that supplied by stationary diffusion, is consumed at the bottom of the
etched trenches as a consequence of the sudden increase of the Jetch value. The
excess of HF molecule consumption leads to a dynamic reduction of the CHF value
and, in turn, of the Jpeak value at the bottom of the etched trenches. The etching
rate in the Z-direction, being proportional to Jpeak, is therefore reduced, and the
increased mass of silicon removed per unit time, Jetch/Jpeak, mainly occurs in the
X and Y directions, thus switching the etching from anisotropic to isotropic.
So far, ECM technology has been successfully applied to the fabrication of highaspect-ratio microstructures and microsystems with application in different fields,
from optofluidics (Barillaro et al. 2009b, 2011; Surdo et al. 2012) to biosensing
(Merlo et al. 2012b, 2013; Surdo et al. 2012) and from photonics (Barillaro
et al. 2007b, 2008, 2009a; Astrova et al. 2010; Polito et al. 2013; Surdo
et al. 2013) to medicine (Merlo et al. 2012a, b; Strambini et al. 2012; Carpignano
et al. 2012; Merlo et al. 2013). Figure 2 shows two examples of high-complexity
microsystems fabricated by ECM technology. Figure 2a, b shows SEM images of
MEMS structures consisting of freestanding inertial masses equipped with highaspect-ratio comb fingers and suspended by high-aspect-ratio folded springs
(AR about 100 for both fingers and springs) that are fixed to an anchor structure
composed of a two-dimensional array of square holes (Bassu et al. 2012). In Fig. 2c, d,
SEM images of an optofluidic platform consisting of two large reservoirs in
783
Fig. 2 Examples (SEM images) of two microsystems fabricated by ECM technology: (a) MEMS
structures consisting of freestanding inertial masses suspended from the substrate by folded
springs and featuring comb fingers for actuation; (b) magnification of a folded spring of the
MEMS structures in (a); (c) optofluidic platform featuring a one-dimensional photonic crystal as
sensing transducer; (d) magnification of the photonic crystal transducer of the platform in (c)
series to a high-aspect-ratio one-dimensional photonic crystal transducer for

biosensing applications (detection of C-reactive protein (CRP) has been demonstrated) are shown (Surdo et al. 2012).
Summary
ECM technology enables the low-cost fabrication of high-complexity silicon
microstructures and microsystems with sub-micrometer accuracy at aspect-ratio
values (about 100) that are well beyond up-to-date, both wet and dry,
micromachining technologies. Among ECM main features there are
(i) fabrication of microstructure with very high aspect ratio, which can be three
times higher than that of state-of-the-art deep etching techniques employed for
microsystem fabrication; (ii) tunability of the etching anisotropy (from zero to one)
in real-time as the etching progresses, which enables 3D freestanding microstructure fabrication by one-step etching; (iii) fine control of the etching features at the
sub-micrometer scale, for both small (features down to 1 m in size) and large
784
G. Barillaro
(length over 1 mm) areas; and (iv) high quality of etched structures in terms of both
verticality (percentage error over a depth of 100 m of about 0.04 %) and surface
roughness (about 20 nm). In the near future, ECM technology is expected to be
greatly exploited at the lab scale, although not limited to, for silicon
microstructuring, with potential impact on both microdevices and applications in
different research fields.
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Astrova EV, Tolmachev VA, Fedulova GV, Melnikov VA, Ankudinov AV, Perova TS (2010)
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Barillaro G, Pieri F (2005) A self-consistent theoretical model for macropore growth in n-type
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Barillaro G, Nannini A, Pieri F (2002a) Dimensional constraints on high aspect ratio silicon
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Barillaro G, Nannini A, Piotto M (2002b) Electrochemical etching in HF solution for silicon
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Barillaro G, Bruschi P, Diligenti A, Nannini A (2005a) Fabrication of regular silicon microstructures by photo-electrochemical etching of silicon. Phys Stat Solid (c) 2(9):31983202
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Barillaro G, Diligenti A, Benedetti M, Merlo S (2006) Silicon micromachined periodic structures
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Barillaro G, Nannini A, Piotto M (2007a) Electrochemical fabrication of buried folded
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Barillaro G, Annovazzi-Lodi V, Benedetti M, Merlo S (2007b) Reflection properties of hybrid
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Barillaro G, Merlo S, Strambini L (2008) Band gap tuning of silicon micromachined 1D photonic
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Barillaro G, Merlo S, Strambini LM (2009b) Optical characterization of alcohol-infiltrated
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Barillaro G, Merlo S, Surdo S, Strambini LM, Carpignano F (2011) Integrated optofluidic
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Bassu M, Surdo S, Strambini LM, Barillaro G (2012) Electrochemical micromachining as an
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Porous Silicon Functionalities for BioMEMS

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Functionalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon in Chip-Based Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
788
788
788
788
793
Abstract
This chapter presents a literature survey of the applications of porous silicon in

BioMEMS (biological/biomedical microelectromechanical systems). This material possesses properties particularly suitable for biomedical purposes: biocompatibility, biodegradability, photoluminescence, ability to precisely control the
pore size and shape, and possibility to easily modify the surface chemistry. Many
applications can, for instance, be found in the fields of sensing and delivery of
therapeutics. It is expected that the number of BioMEMS using porous silicon
will continue to increase in the future with the development of lab-on-a-chip/
microfluidic devices.
J. Schweicher (*)
Department of Chemistry, Universite Libre de Bruxelles, Bruxelles, Belgium
e-mail: julien.schweicher@gmail.com; julien.schweicher@ulb.ac.be
T.A. Desai
Department of Bioengineering and Therapeutic Sciences, University of California, San Francisco,
CA, USA
DOI 10.1007/978-3-319-05744-6_80
787
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J. Schweicher and T.A. Desai
Introduction
Microelectromechanical systems have gained considerable interest in the biological
and biomedical fields (BioMEMS) due to the precise control of their chemical and
physical characteristics combined with suitable biocompatibility. They can be
found in many different applications such as biosensors, lab-on-a-chip devices for
diagnostics, microfluidics, immunoisolation capsules, drug delivery, minimally
invasive surgery tools, pacemakers, stents, NeuroProbes, regenerative electrodes,
and retinal prosthesis (Richards Grayson et al. 2004; James et al. 2008). Other
application chapters in this handbook of direct relevance to such specific topics
include Porous Silicon Optical Biosensors, Porous Silicon Immunoaffinity
Microarrays, Porous Silicon in Immunoisolation and Bio-filtration, and
Drug Delivery with Porous Silicon.
Porous Silicon Functionalities

Since Canhams report about the biocompatibility of porous silicon (pSi) in 1995
(Canham 1995), this material has been increasingly studied by the biomedical
community and numerous BioMEMS have been developed (Salonen and Lehto
2008), mainly for biosensing (Kochergin and Foll 2009; Rendina et al. 2008) and
delivery of therapeutics (Anglin et al. 2008). Table 1 provides an overview of the
porous silicon functionalities applicable to BioMEMS.
Porous Silicon in Chip-Based Systems

Besides these aforementioned applications, porous silicon can also be used as part
of a chip-based system, providing different functionalities. Table 2 presents those
BioMEMS applications, including microfluidic applications (Abgrall and Gue
2007).
Conclusion
As can be seen in both tables, pSi presents numerous applications in the BioMEMS
field due to properties particularly suitable for biomedical purposes (Salonen and
Lehto 2008): biocompatibility, biodegradability, photoluminescence (Canham
1990), ability to precisely control the pore size and shape, and possibility to easily
modify the surface chemistry. It is expected that the number of BioMEMS applications incorporating pSi will continue to increase in the future with the further
development of lab-on-a-chip devices.
Thin film
Microparticles
Microparticles
Microparticles
Detection of integrin-expressing cells

Biomolecular screening
Encoded microcarrier
Degradable support for solid-phase synthesis and

release of oligonucleotides
Delivery of insulin
Delivery of bovine serum albumin and interferon

2b
Delivery of antipyrine, ibuprofen, griseofulvin,
ranitidine, and furosemide
Thin film
Thin film
Thin film
Thin film
Thin film
Thin film
Thin film
Sensor for triglycerides

Sensor for atrazine (pesticide)
Sensor for L-glutamine
Sensor for DNA
Sensor for intimin-ECD
Sensor for prostate-specific antigen
Sensor for opiates in urine
Microparticles
Thin film
Microparticles
Electrochemical etch
Thin film
Thin film
Electrochemical etch + ball milling
Photolithography + electrochemical
etch
Electrochemical etch +
ultrasonication
Electrochemical etch +
ultrasonication
Photolithography + electrochemical
etch
Photolithography + micromachining
Gas etch
Fabrication method
pSi
morphology
Thin film
pSi function
Sensor for DNA oligomers, streptavidin, and
immunoglobulin G
Sensor for immunoglobulin G
Sensor for DNA and viral DNA
Table 1 pSi functionalities applicable to BioMEMS
Salonen et al. 2005
Martin et al. 2005
Foraker et al. 2003
McInnes and Voelcker 2012
Meade et al. 2004
(continued)
Dancil et al. 1999; Tsang et al. 2012

Chan et al. 2000a, b; Archer and Fauchet
2003; Archer et al. 2004
Reddy et al. 2001
Rotiroti et al. 2005
De Stefano et al. 2006
Tessier et al. 2006
Ouyang et al. 2007
Choi et al. 2009
Bonanno et al. 2010; Bonanno and
DeLouise 2010
Worsfold et al. 2006
Cunin et al. 2002
References
Lin et al. 1997

789
Delivery of insulin and bovine serum albumin

Delivery of camptothecin
Delivery of emodin
Delivery of ethionamide
Delivery of indomethacin
Delivery of peptide YY3-36
Encapsulation of 32P (brachytherapy)
Immunoisolation of pancreatic cells/delivery of
insulin
Separation of macromolecules
Hemofiltration
Cell viability assessment
Cancer photothermotherapy
pSi function
Delivery of doxorubicin
Delivery of ghrelin antagonist
Delivery of melanotan II
Delivery of daunorubicin
Table 1 (continued)
Membrane
Membrane
Thin film
Nanoparticles
Microparticles
Thin film
Thin film
Microparticles
Microparticles
Microparticles
Microparticles
Membrane
pSi
morphology
Thin film
Microparticles
Microparticles
Microparticles
Electrochemical
etch + ultrasonication
Fabrication method
Electrochemical
etch + ultrasonication
Electrochemical etch + milling
Pastor et al. 2011

McInnes et al. 2012
Hernandez et al. 2012
Vale et al. 2012
Tahvanainen et al. 2012
Kovalainen et al. 2012
Zhang et al. 2005
Desai et al. 1998, 2004; Leoni and Desai
2004
Striemer et al. 2007
Fissell et al. 2009
Schwartz et al. 2006
Hong et al. 2011
References
Vaccari et al. 2006
Kilpelainen et al. 2009
Kilpelainen et al. 2011
Wu et al. 2011
790
791
Table 2 BioMEMS applications using pSi as part of a chip-based system

Application
Micro enzyme reactor
for continuous glucose
monitoring
Microreactor for
heterogeneous and
enzymatic catalysis
reactions
Bioreactor within a
microfluidic chip
Microfluidic chip for

solid-phase extraction
of DNA
Microfluidic chip with
filtering capabilities
Membrane that can be

integrated into a
microfluidic system
Diagnostic chip probing

the stratum corneum of
the skin
Transdermal drug
delivery with Si
microneedle arrays
Drug delivery capsule

with adjustable release
Integration of pSi
pSi is fabricated on high
aspect ratio Si
microstructures of the
reactor by
electrochemical etch
Nanostructured peaks
are created in Si
substrate by deep
reactive ion etching
(black silicon)
pSi is fabricated on
microchannels by
cryogenic deep reactive
ion etching
micromachined
channels of Si substrate
by electrochemical etch
Lateral pSi membranes
are fabricated within
microchannels by
anodization with local
electrodes
Uniform conical pores
of 100 nm or smaller are
created in Si by
interferometric
lithography
Si interface layer
(in between the skin and
MEMS) is
micromachined and
electrochemically
etched to produce pSi
pSi is fabricated on top
of Si microneedles by
(the rest of the
microneedles being
protected)
pSi is used as drugcontaining structure in
the reservoir and/or as
membrane covering the
reservoir
Added value of pSi

Surface enlarging effect,
100-fold increase in
enzyme activity
References
Drott
et al. 1998
Increased reaction rates

in the microreactor due
to increased surface
areas
Roumanie
et al. 2008
Various applications
possible (sensing,
actuation, study of
biological reactions),
fabrication technique
amenable to scale-up
Increased surface area
for DNA extraction
Retterer
et al. 2010
Chen
et al. 2006,
2007
Facile integration of
membranes in fluidic
devices
Dubosc
et al. 2012
Enhanced transport of
pyridine as compared to
commercial filters
Ileri
et al. 2009
Minimally invasive
sampling from the skin
Bhansali
et al. 2002
Biodegradability: useful
in case top of
microneedles breaks off
and remains in the skin.
Enhanced drug loading
capability
Electrically adjustable
release via pH
modulation inducing
pSi erosion
Ji
et al. 2006
Leong
et al. 2007
(continued)
792
Table 2 (continued)
Application
Microelectrodes for
recording neuronal
activity
Microcantilever
biosensor
Biomolecular analysis
(peptides,
carbohydrates,
glycolipids, etc.) by
laser desorptionionization mass
spectrometry on pSi
Determination of
enzyme kinetics by laser
desorption-ionization
mass spectrometry on
pSi
Manipulation of liquid
droplets using photonic
crystal chaperones
Stationary phase in
liquid chromatography
chips
Electroosmotic pump
fabricated from pSi
membrane
Electrical insulation
within on-chipelectrophoresis
separation systems
Integration of pSi
pSi is fabricated by
electrochemical etch of
the Si microelectrode
surface
pSi is fabricated on the
surface of crystalline Si
microcantilevers by
vapor phase stain etch
crystalline Si by
and is used to trap the
analyte molecules
pSi microfluidic
channels are fabricated
by electrochemical etch,
and after reaction
between enzyme and
substrate, a droplet
residue is deposited on
the channel walls before
analysis
Nanoparticles of Fe3O4
are incorporated into
microparticles of pSi,
allowing pSi to
chaperone liquid
droplets under
application of a
magnetic field
pSi is fabricated around
Si micropillars by
pSi membrane is
integrated into a
custom-built acrylic
housing with Pt wire
electrodes wound into a
spiral
pSi is fabricated on top
of Si substrate by
and subsequently
covered by Pyrex by
anodic bonding
Added value of pSi

Improved
biocompatibility for
chronically implanted
microelectrodes
Improved sensitivity of
sensor
References
Moxon
et al. 2007
Stolyarova
et al. 2008
In comparison with
MALDI-TOF:
simplified sample
preparation, no matrix
background ions
Wei
et al. 1999
Same advantages as
above and no need for
an internal standard
Nichols
et al. 2008
Possibility to
manipulate and monitor
small volumes of liquids
without the use of
pumps, valves, or a
microfluidic container
Dorvee
et al. 2004
Significant increase of
the retention factors in
comparison with
nonporous Si
micropillar arrays
Increased maximum
flow rate as compared to
porous glass pumps
Tiggelaar
et al. 2009
Enhanced insulation
properties after
silanization of pSi
Yao
et al. 2006
Mery
et al. 2007
793
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Porous Silicon for Microdevices

and Microsystems
Luca De Stefano and Ilaria Rea
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sacrificial Use of Porous Silicon in Microsystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon-Based Sensing Microsystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microdevices and Microsystems Incorporating Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
797
798
799
800
801
Abstract
A literature survey is made of the various uses of both macroporous and

mesoporous silicon in individual microdevices and complex microsystems.
The material has been used as a silicon wafer processing tool where it is
sacrificial: in a passive role where it provides, for example, thermal or electrical
isolation and in an active role where it performs a range of functions. Examples
include delivering drugs, sensing, emitting light, storing hydrogen, providing
filtration, or having a catalytic role.
Introduction
The incredible explosion of solid-state technologies in the last 30 years has made
the consumer electronics as we know it nowadays: sophisticated electronic equipment are largely available in entertainment, communications, and office productiv-
L. De Stefano (*) I. Rea

IMM-CNR Institute for Microelectronics and Microsystems Unit of Naples, National
Research Council, Naples, Italy
e-mail: luca.destefano@cnr.it; luca.destefano@na.imm.cnr.it; ilaria.rea@na.imm.cnr.it
DOI 10.1007/978-3-319-05744-6_81
797
798
L. De Stefano and I. Rea
ity. The ability of material science in fabricating, and also mixing together, very
different materials, both organic and inorganic, has launched what is expected to be
the next technology revolution: the integrated microsystems. Micro (or even nano)opto-electro-mechanical systems, M(N)OEMS, or micro total analysis systems,
micro-TAS, are the acronyms that can be found so often in scientific production
(Gad-el-Hak 2010). These devices will combine sensing, processing, actuation, and
power management functions in order to achieve multispectral functionality, adaptability in response to a changing environment, and real-time data analysis. Beyond
its peculiar and exciting electrooptical and chemical properties, porous silicon has
shown, from the beginning of its discovery, very interesting features for integrated
microsystems fabrication and applications. Both macroporous structures from
n-type silicon and mesoporous layers created from heavily doped silicon are
currently used in a wide set of devices, from chemical and biological analytical
sensors to micro fuel cell, and many other microsystems can be found in academic
literature and industrial patents. In the following, main experiences about porous
silicon structures as functional elements in microsystems are grouped; porous
silicon-based optical or electrical transducers as sensing part of microsystems
devoted to biological and chemical monitoring are then presented, and finally a
miscellaneous of devices is summarized.
Sacrificial Use of Porous Silicon in Microsystems

Macroporous silicon technology found its principal application in integrated
microsystems as sacrificial layer: multilayered and suspended structures, such as
bridges, membranes, and cantilevers, often require fabrication, almost always by
isotropic etching and removing, by alkaline-based water solution, of a porous layer.
The thickness of this layer can be up to 100 m, or more, which is very much greater
with respect to those obtained by thin film deposition techniques (<10 m): in this
sense, porous silicon passive layer is an exclusive technology. In Table 1 are
reported some references of porous silicon sacrificial layers together with the
functionalities of the resulting microsystems.
Silicon on insulator technology and thermal insulation are other important fields
where porous silicon morphology plays a key role, and thus, it is often used in
complex microsystems: thermal properties of porous silicon layers can be strongly
modulated by changing the porosity, i.e., the amount of air present in the silicon
volume. On the other hand, pores can be completely filled by silicon dioxide, so that
a nanocrystalline film can be transformed by thermal oxidation in an oxide layer
preserving the desired geometry. Quite few works on this subject can be found in
literature (Bomchil et al. 1988; Perichon et al. 2001; Friedberger et al. 2001;
Lysenko et al. 2002; Mondal et al. 2009). Chapters in this handbook of relevance
include RF Electrical Isolation with Porous Silicon, and Thermal Isolation
with Porous Silicon.
799
Table 1 Porous silicon as sacrificial layer

Structure
Free-standing film
Bridge
Thin films, wires
Cantilever
Wick
Cantilever
3D plates
Membrane
Cantilevers, disks
Nanoporous structures
Sacrificial layer
1 m layer
Sacrificial layer
Nanoporous structures
Sacrificial layer
Thick layers
Patterned layer
Sacrificial layer
Thin film
Functionality
Flow channels
Flow sensor
Bolometer, anemometer
Micromachining
Wall of heat pipe
Accelerometer
MEMS
Microelectrodes
MEMS
MEMS
Microphone
MEMS
Microcoils
Transducers
Microphone
MEMS
Microneedles
Micro turbine
Microresonator
Reference
Lang et al. 1994
Lang et al. 1995
Steiner and Lang 1995
Bischoff et al. 1997
Holke et al. 1998
Sim et al. 1998
Lammel and Renaud 2000
Kalinowski et al. 2000
Lee et al. 2000
Benecke and Splinter 2001
Kronast et al. 2001
Dantas et al. 2008
Liu et al. 2003
Mescheder 2004
Ning et al. 2004
Valera et al. 2005
Rajaraman and Henderson 2005
Rajta et al. 2009
Olivares et al. 2010
Porous Silicon-Based Sensing Microsystems

Mesoporous silicon is by far the most intriguing material for optical and electrical
monitoring of chemical and biological molecular interactions. The integration of
porous silicon transducers in microsystems is not trivial or straightforward: each
step of the fabrication process (photolithography, etching, bonding/sealing, inlet/
outlet) should be designed and realized, just preserving the physical and chemical
characteristics of the sensing material. In case of porous silicon, pores accessibility,
surface chemical features, and signal readout (both optical and electrical) should be
maintained, if not optimized in microsystems fabrication. The utilization of biological bioprobes, which can recognize specific analytes in complex mixtures, thus
enhancing the selectivity of the sensor systems, makes things even more difficult:
biological molecules works in the so-called physiological conditions that could not
match technological requirements. On the other hand, microsystems can really
boost sensing features through electronics and microfluidic circuits. Onboard electronics allow signal amplification, restoration, storage, and transmission, which
correspond to higher sensitivity, low drift, and possibility of actuation.
Microfluidics ensure small volume consumption, safe operations, rapid analysis
time, and protection of the transducer against the environment. For all these
reasons, a great effort has been spent in porous silicon integration in microsystems
800
Table 2 Porous silicon sensing microsystems

Transduction
Electrical
Electrical
Optical
Optical
Optical
Optical
Electrical
Electrical
Optical
Optical
Optical
Optical
Optical
Optical
Electrical
Mechanical
Electrical
Optical
Electrical
Optical
Optical
Mechanical
Optical
Sensing application
Humidity
Bacteria
Volatile compounds
Liquids/gases
DNA
Liquids/gases
Gases
Gases
DNA
DNA
Gases
Liquids/gases
Gases
Protein/ligand
DNA
Antibody/antigen
NO2
DNA
Gases
DNA
Liquids
Liquids
Liquids
Reference
Rittersma et al. 2000
Misra et al. 2001
De Stefano et al. 2004
De Stefano et al. 2006a
De Stefano et al. 2006b
De Stefano et al. 2006c
Barillaro et al. 2007
Zellers et al. 2007
Rendina et al. 2007
De Stefano et al. 2007a
De Stefano et al. 2007b
De Stefano et al. 2007c
De Stefano et al. 2007d
De Stefano et al. 2007e
Chen et al. 2007
Stolyarova et al. 2008
Barillaro and Strambini 2008
Rea et al. 2010
Rea et al. 2011
Surdo et al. 2012
Strambini et al. 2012
for substances monitoring: Table 2 reports many successful applications of chemical and biological sensing that can be found in literature together with the method
of transduction exploited in the device. Chapters in this handbook of particular
relevance include Porous Silicon Gas Sensing, Porous Silicon
Immunoaffinity Microarrays, and Porous Silicon Optical Biosensors.
Microdevices and Microsystems Incorporating Porous Silicon

Spongelike or ordinated ensembles of pores have been attractive for a lot of
on-microsystems applications that span on a wide range of interesting field. Porous
silicon membranes for hydrogen storing and release have been studied and characterized; mechanical properties of these membranes have been used in integrated
microphones; micro-turbine and field-emission devices are among the most
advanced MEMS structures that can be obtained by porous silicon micromachining
technique: from all those experiments, it results to the conclusion that researchers
fantasy and imagination are the real limits for porous silicon application in
microsystems. Table 3 shows the references on this heterogeneous subject. The
801
Table 3 Porous silicon in microdevices and microsystems

Structure
Active layer
Layer
Multilayer
Membrane
Array
Membrane
Membrane
Channel
High-porosity layer
Membrane
Membrane
Micro-column
Buried contact
Application
LED
MALDI-TOF-MS
MEMS spectrometer
Electro-catalysis
Ultrasounds
Particles filter
Micro-propulsion
Gas concentration
Field emission device
H2 storage
Micro fuel cell
Chromatography
Solar cells
Reference
Hirschman et al. 1996
Ekstrom et al. 2000
Lammel et al. 2002
DArrigo et al. 2003
Hirota et al. 2005
Wallner and Bergstrom 2007
Lazaruk et al. 2007
Camara et al. 2007
Dantas et al. 2008
Nagayama et al. 2008
Torres et al. 2009
Mery et al. 2009
Vitanov et al. 2009
chapters in this handbook on related topics include Porous Silicon in

Immunoisolation and Bio-filtration, Porous Silicon Photonic Crystals,
Porous Silicon and Micro-fuel Cells, and Porous Silicon-Based Mass
Spectrometry.
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Porous Silicon Photonic Crystals

J. Octavio Estevez and Vivechana Agarwal
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1D Photonic Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
810
810
811
811
811
812
Abstract
Porous silicon based one, two and three dimensional photonic crystals (PCs) have
been reviewed. Apropriate selection of the fabrication parameters can be used to
form a photonic band gap of tunable width in the required spectral region. Due to
the ease of fabrication of 1D PCs, it has been shown to be useful for the
demonstration of some physical phenomenon and numerous works have been
dedicated to photonic and sensing applications. The fabrication of 2D PCs requires
the prestructuring of the silicon surface and the structures with the defects for the
incorporation of different materials have opened a wide range of applications.
Although the fabrication of 3D PCs, needs the combination of more than two
tehniques, the fabrication of perfect mirrors in the infrared region has been shown.
J.O. Estevez
CIICAp-UAEM, Av. Universidad, Col. Chamilpa, Cuernavaca, Morelos, Mexico
e-mail: jestevez@ifuap.buap.mx
V. Agarwal (*)
Centro de Investigacion en Ingenieria y Ciencias Aplicadads, Universidad Autonoma del Estado
de Morelos, Col. Chamilpa, Cuernavaca, Mexico
e-mail: vagarwal@uaem.mx
DOI 10.1007/978-3-319-05744-6_82
805
Adapted from Estevez

et al. (2008)
Adapted from de la Mora

et al. (2010)
Photonic system
Typical Scanning
electron microscopy
images
1D PSi structures
Omnidirectional mirror,
chirped DBR, Gaussian
profiles
Distributed Bragg
reflector (AB)N
Name, refractive index

profile
Relevant characteristics
Perfect mirrors (high

reflectivity); broad-range
DBR with smooth
interfaces; solar reflectors
Tunable mirrors; dichroic

mirrors; sensing;
negative refraction
Image detectors
Secondary reflectors for
solar concentration
systems
Tunable, broadband PBG

surrounded by sidelobes,
superposition of PBGs
Superposition of PBGs
Application areas
Optical properties
Table 1 Examples of photonic structures and principal characteristics
Visible,
IR
UV,
visible,
IR
Far-IR
VisNIR
Optical
range
(David Ariza-Flores
et al. 2012; Pavesi and
Turan 2010)
(Zheng et al. 2004;

MIAO et al. 2009; de la
Mora et al. 2009;
Palestino et al. 2007;
de la Mora et al. 2010;
Pacholski et al. 2006;
Pavesi and Turan 2010;
Estevez et al. 2008)
Reference
806
J.O. Estevez and V. Agarwal
Adapted from Agarwal

et al. (2004)
Adapted from Ishikura

et al. (2010)
Microcavity ((AB)NB
(AB)N); coupled
microcavities, ((AB)NB
(AB)N)n
Dual period
Rugate filters (sine or

cosine profiles)
Corrugated rugates
One or multiple optical

modes allowed inside
PBG; tunable optical
properties by
incorporation of LCs
Narrow FWHM, PBG

without sidelobes
Optical diffraction and
PBGs
Interference filters;
sensing; mutliplexing;
switching; second- and
third-harmonicgeneration using
birefringence; tunable
ferroelectric PCs; giant
second and third
harmonic generation
Mirror; band-pass filters,

optical barcodes; sensing
Diffraction gratings with
band-pass filters
Visible,
IR
Vis
Visible,
IR
Vis
(continued)
(Barthelemy et al. 2007;

Ouyang et al. 2006;
Palestino et al. 2007;
Weiss et al. 2005a; Li
et al. 2011; Pacholski
2013; Pavesi and Turan
2010; Murzina
et al. 2007; Weiss
et al. 2005a; Perez
et al. 2012; Dolgova
et al. 2001, 2002; Octavio
Estevez et al. 2012; Perez
et al. 2012; Ghulinyan
et al. 2003; Sapienza
et al. 2003; Agarwal
et al. 2004; Octavio
Estevez et al. 2012;
Ghulinyan et al. 2005)
(Ishikura et al. 2010;

Ciampi et al. 2008; Cunin
et al. 2002; Ruminski
et al. 2013; Pacholski
2013; Li et al. 2003)
(Kilian et al. 2007; Pavesi
and Turan 2010; Matthias
et al. 2005b)

807
Adapted from Birner

et al. (2001)
Adapted from Dang

et al. (2012)
Adapted from Leonard

et al. (1999)
Photonic system
Typical Scanning
electron microscopy
images
2D PSi structure
Table 1 (continued)
Waveguides: line defects

introduced in 2D
photonic
Microcavities;
introduction of point or
line defects in 2D
photonic systems
(lithography + alkaline
etching on n-type Si
wafer)
Square lattice with

silicon pillars or airholes
in silicon matrix (proton
beam writing +
electrochemical etching
on p-type Si wafer)
Name, refractive index

profile
Macropores with
triangular lattice
structure, 2D periodicity
in refractive index
perpendicular to pore axis
(lithography + alkaline
etching on n-type silicon
wafer)
Strong confinement,
control of light
propagation; tunable
optical properties on
incorporation of
QDs/LCs into the
microcavity or free
carrier injection optically
or electrically
Guided modes for optical

communication; sensing
Interference filters;
sensing; microresonators,
resonance peaks with
high-quality factor in
transmission spectra
Mirrors; birefringent PCs

(n 0.366); electrical
tuning after incorporating
liquid crystals (LCs);
biosensing; internal
emitter on incorporation
of quantum dots (QDs)
into macropores;
tunability of photonic
bandgaps
2D PBG effect for the

in-plane direction
2D transverse magnetic
or transverse electric
PBG effect for the
in-plane direction
Application areas
Optical properties
Mid IR
Mid IR
Mid IR
Mid IR
Optical
range
(Mertens et al. 2003;

Birner et al. 2001)
(Mertens et al. 2003;

Wehrspohn et al. 2008;
Wehrspohn 1995;
Leonard et al. 1999;
Wehrspohn and Schilling
2003; Weiss et al. 2005b;
Recio-Snchez
et al. 2012a; Dang
et al. 2012; Haurylau
et al. 2006; Genereux
et al. 2001; Martn-Palma
et al. 2006; M
uller
et al. 2000; Birnera
et al. 2000; Lee and
Fauchet 2007; RecioSnchez et al. 2012b)
Reference
808
Adapted from Braun

et al. (2006)
Adapted from Matthias

et al. (2005a)
3D PSi structure
High-resolution 3D
fabrication technique and
high-dielectric-constant
materials are required
Partial PBG PCs;
periodic refractive index
in 3D (n-type
macroporous silicon +
alkaline etching + etching
with HF modulation of
light intensity)
Microcavity, periodic
refractive index in 3D;
Waveguides
Complete PBG PCs;

periodic refractive index
in 3D (macroporous
silicon with n-type Si
wafer + alkaline etching
+ anisotropic
posttreatment) or (proton
beam writing +
electrochemical etching
on p-type Si wafer)
Complete confinement of
light; strong confinement
(or control) of photons
due to defects in 3D
system; planar defects
Partial or complete PBG

extended to all
3 dimensions
Tunable optical
properties with
incorporation of LCs
3D interference filters;
p-n diode for betavoltaics
and photovoltaics
Perfect mirrors (high

reflectivity); switch;
could be used to realize
novel atom traps
Mid IR
NIR
(Wang et al. 2000; Braun

et al. 2006; Mertens
et al. 2003 ; Birner
et al. 2001)
(Matthias et al. 2005a;

Recio-Snchez
et al. 2012b; Aristov
et al. 2000; Hillebrand
et al. 2003; Schilling
et al. 2005)
(Wehrspohn and
Schilling 2003; Schilling
et al. 2001; Matthias
et al. 2005b)

809
810
Introduction
Porous silicon (PSi)-based photonic crystals (PC) are attractive optical structures to
control the propagation of light with the possibility to design many new siliconbased optical devices compatible with standard industry processes by relatively
economical technique compared with other fabrication methods (Wehrspohn
et al. 2008; Prasad 2004; Wehrspohn 1995). A periodic dielectric multilayered
system, typically consisting of two alternated dielectric materials with periodic
variation in refractive indices, is the simplest PC (Joannopoulos et al. 1995). The
propagation of electromagnetic (EM) radiation in PCs is forbidden in specific
wavelength ranges (photonic bandgaps or PBGs) due to the scattering of the light
wave at the interfaces of the layers, so the multiple-scattered waves interfere
destructively in the material (Prather et al. 2009). The behavior of light in a periodic
scattering media can be described by Bloch states. In addition, localized modes can
appear into the PBGs by breaking the periodicity of the dielectric multilayer, i.e., by
introducing a defect within a PC (Joannopoulos et al. 1995) that allows a narrow
range of light wave frequencies to propagate through the whole structure. Other
interesting features of PCs are the local field enhancement, anomalous group
velocity dispersion, and anomalous refractive index dispersion (Prasad 2004).
Selecting appropriately the fabrication parameters, PSi-based photonic structures
can be designed to form PCs with a required width and location of the PBGs with
one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) periodic
dielectric lattices, as illustrated in Table 1. The size scale and geometry of the
refractive index periodicity determine the region of the EM spectrum where the
PBGs exist.
1D Photonic Crystals
PSi-based 1D photonic superlattices have allowed the demonstration of interesting
optical analogs of electronic phenomena, such as photonic Bloch oscillations, Zener
tunneling, Anderson localization, and optical switch (Sapienza et al. 2003; Agarwal
et al. 2004; Octavio Estevez et al. 2012; Ghulinyan et al. 2005; Bertolotti
et al. 2005; Barthelemy et al. 2007). Besides periodic photonic multilayers
(Zheng et al. 2004; MIAO et al. 2009; de la Mora et al. 2009; Palestino
et al. 2007; Ghulinyan et al. 2003; Dolgova et al. 2001, 2002; Ouyang
et al. 2006; Li et al. 2011; Pacholski 2013; Murzina et al. 2007; Weiss
et al. 2005a; Perez et al. 2012; Estevez et al. 2008; David Ariza-Flores
et al. 2012; Ishikura et al. 2010; Ciampi et al. 2008; Cunin et al. 2002; Ruminski
et al. 2013; Li et al. 2003; Kilian et al. 2007; Pacholski et al. 2006; Pavesi and Turan
2010), quasiperiodic and aperiodic structures have been analyzed (Dal Negro
et al. 2003; Moretti et al. 2006; Estevez et al. 2012). Considering the light propagation close to the bandgaps in PS multilayers, an interesting effect like negative
refraction has also been reported (Lugo et al. 2009; de la Mora et al. 2010).
811
Fabrication of 2D PSi PBG structures requires prestructuring of the silicon surface
prior to electrochemical etching, i.e., using interferometric lithography to define a
square or triangular lattice of nucleation pits on the surface of moderately doped
silicon. 2D PBG structures can be also obtained using a variation of applied
potential on the backside of the sample during electrochemical formation of the
multilayers. This technique allows a fabrication of spatially distributed filters on the
millimeter size scale (Wehrspohn et al. 2008; Prasad 2004; Wehrspohn 1995;
Leonard et al. 1999; Wehrspohn and Schilling 2003; Weiss et al. 2005b; RecioSnchez et al. 2012a; Dang et al. 2012; Haurylau et al. 2006; Genereux et al. 2001;
Martn-Palma et al. 2006; Muller et al. 2000; Birnera et al. 2000; Lee and Fauchet
2007; Mertens et al. 2003; Recio-Snchez et al. 2012b; Birner et al. 2001).
As high-resolution 3D fabrication technique and high-dielectric-constant materials
are prerequisites for a complete PBG in visible region, 3D PCs are more complicated
to fabricate. Hence, 3D photonic structures have been realized using a combination of
different techniques. Several processing routes to form partial or complete PBG
materials and defects in 3D structures have been identified. Designing 3D systems
with defined defect structures for the incorporation of materials with advanced
functionalities has been realized (Weiss et al. 2005b). Although lithographic
approaches have a number of shortcomings, from cost and practical limitations to
the number of layers, the infrastructure for lithographic approaches is extraordinarily
well developed and, for some device applications, will probably be the method of
choice for integrating 3D PCs with microelectronics (Wehrspohn et al. 2008; Prasad
2004; Wehrspohn 1995; Wang et al. 2000; Aristov et al. 2000; Hillebrand et al. 2003;
Schilling et al. 2001, 2005; Braun et al. 2006; Matthias et al. 2005a, b). The handbook
chapters Porous Silicon Multilayers and Superlattices and Photolithography
on Porous Silicon provide more details on fabrication and such processing.
Conclusions
In conclusion, high-optical-quality PSi PCs have been fabricated and found to
exhibit several optical properties resulting in many applications, such as dielectric
mirrors, FabryPerot optical microcavities, rugate filters, corrugated freestanding
PSi multilayers, and several other devices that have been particularly effective in
various types of optical processing and biosensing. Other promising applications
such as secondary reflectors for solar concentration systems, dielectric reflectors for
far infrared image detectors, giant second- and third-harmonic-generation devices,
large birefringence, photonic devices for producing terahertz modulation frequencies, optical switches based on capillary condensation, and structures with defects
812
for the incorporation of materials with advanced functionalities have also been
realized, opening a wide range of applications of silicon technology. Apart from
that, many composite photonic crystals have also been demonstrated for tunable/
enhanced optical properties (Murzina et al. 2007; Weiss et al. 2005a; Li et al. 2005;
Gutman et al. 2008; Leonard et al. 2000). For related application chapters in this
handbook, see Porous Silicon Optical Biosensors, Porous Silicon and Solar
Cells, Porous Silicon Phononic Crystals, and Porous Silicon for
Microdevices and Microsystems.
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Porous Silicon Optical Waveguides

Sharon M. Weiss and Xing Wei
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Waveguide Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Waveguide Geometries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
Porous silicon optical waveguides have attracted attention for applications

ranging from optoelectronics to chemical and biological sensors. This chapter
describes various waveguide geometries that have been achieved in porous
silicon, including single and multilayer architectures. Depending on the
processing parameters, oxidized porous silicon waveguides can be fabricated
with losses below 0.5 dB/cm. While these losses are a challenge for some
optoelectronics applications, sensor applications of porous silicon waveguides
have flourished. Recent innovations have led to demonstrations of the label-free
detection of nucleic acid molecules, proteins, and toxins with sensitivities as low
as 106/RIU.
S.M. Weiss (*) X. Wei

Department of Electrical Engineering and Computer Science, Vanderbilt University, Nashville,
TN, USA
e-mail: sharon.weiss@vanderbilt.edu
DOI 10.1007/978-3-319-05744-6_83
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816
S.M. Weiss and X. Wei
Introduction
Waveguides are one of the many multilayer thin film optical structures that can be
fabricated in a straightforward manner using porous silicon. Unlike many other
multilayer structures, such as the Bragg mirror, rugate filter, and microcavity (see
handbook chapters Porous Silicon Multilayers and Superlattices and
Porous Silicon Photonic Crystals), light incident on a waveguide can couple
into a propagating in-plane mode under the proper excitation conditions. In this
section, waveguide theory is first briefly reviewed. Next, various porous silicon
waveguide geometries are introduced. Finally, applications ranging from optoelectronics to sensors are discussed.
Waveguide Theory
A waveguide structure consists of a high refractive index layer surrounded by
lower refractive index media. In porous silicon, waveguides can be achieved by
fabricating single-layer, double-layer, or triple-layer structures (Rong
et al. 2008a, b; Loni et al. 1996; Takahashi and Koshida 1999), as illustrated in
Fig. 1; graded-index profile waveguides are also achievable. Conceptually, in
traditional step index waveguides, light remains trapped in the high refractive
index (low porosity) layer due to total internal reflection at the interfaces with the
adjacent lower refractive index materials. Photonic crystal mirrors have also been
utilized to provide light confinement in a porous silicon waveguide (Xifre-Perez
et al. 2006). Very recently, three-layer porous silicon antiresonant reflecting
optical waveguides (ARROW) have been demonstrated (Haji et al. 2012). A
waveguide structure can support a discrete number of modes, each with a characteristic effective index (neff), based on the thickness and refractive index of each
layer of the waveguide (Pollock 1995). While light is only guided in the
low-porosity waveguide layer, an exponentially decaying field does exist in the
regions directly above and below the low-porosity waveguide layer. This evanescent field is critical for allowing light to be efficiently coupled into and out of the
waveguide, as discussed in the following section, and is also important to consider
for sensing applications, as discussed later in the Applications section. Scanning near-field optical microscopy has been used to directly probe the evanescent
field and measure the propagation constant of a porous silicon waveguide
(Bruyant et al. 2005). If a secondary material is incorporated into one or more
of the porous silicon layers constituting the waveguide structure, then the field
distribution, neff of each mode, and possibly the number of modes is changed.
Note that while porous silicon double-layer structures, in general, have been
intensively investigated over the past few years for size-selective and environmentally robust sensing applications (Pacholski et al. 2005, 2006; Orosco
et al. 2009), many of these structures are not waveguides because the appropriate
refractive index profile is not achieved and only the reflectance spectrum is
interrogated.
817
c
a
Low porosity porous silicon
High porosity porous silicon
Fig. 1 Schematics of porous silicon waveguides consisting of (a) one, (b) two, or (c) three porous
silicon layers. Light is confined in a high refractive index (low porosity) porous silicon layer when
surrounded by lower refractive index media, which can include a higher porosity porous silicon
layer, air, or another low index solid, liquid, or gaseous substance
Silicon substrate
Silicon substrate
High porosity porous silicon

Low porosity porous silicon
Low refractive index polymer
Fig. 2 Common porous silicon waveguide configurations: (a) grating-coupled two-layer waveguide, (b) prism-coupled two-layer waveguide in the Otto configuration with an air gap between
the waveguide and the prism, and (c) prism-coupled single-layer waveguide in the Kretschmann
configuration using a low index polymer layer or low index fluid to attach the porous silicon
membrane to the prism. End-fire coupling using a microscope objective and butt coupling using an
optical fiber (not shown) have also been employed
Porous Silicon Waveguide Geometries

Figure 2 illustrates some common porous silicon planar waveguide configurations.
Rectangular waveguide geometries, such as rib or ridge waveguides, including
Mach-Zehnder interferometer configurations, have also been studied and achieved
in porous silicon using standard lithography techniques or direct laser writing (Loni
et al. 1996; Arrand et al. 1997; Xia et al. 2012; Hiraoui et al. 2012a; Kim and
Murphy 2013; Hutter et al. 2013). In a few cases, porous silicon has been used as the
cladding layer for a polymer or bulk silicon waveguide (Lahoz et al. 2008; NavarroUrrios et al. 2009; Teo and Xiong 2013). Guided modes of a waveguide cannot be
directly excited by light incident from above or below the waveguide. For light to
couple into a waveguide, it is necessary that both the energy of the light and the
component of the wave vector along the propagation direction must be identical for
the incident light outside the waveguide and guided mode inside the waveguide.
Thus, light may be injected from the side into the waveguiding layer using techniques such as butt coupling or end-fire coupling, or, alternatively, a coupling
818
element, such as a prism or diffraction grating, may be used to couple light into the
waveguide from above or below via an evanescent wave.
Important considerations for achieving efficient coupling include the mode
mismatch between a butt-coupled fiber and the porous silicon waveguide, the
numerical aperture of a lens used for end-fire coupling, the distance between a
prism and the porous silicon waveguide, and the grating pitch of a diffraction
grating coupler. The efficiency of grating coupling also depends on the grating
shape, fill factor, and refractive index. Grating couplers on porous silicon waveguides have been fabricated by standard lithographic techniques (Wei and Weiss
2011a; Wei et al. 2008; Rea et al. 2009) as well as by the direct imprinting of porous
substrates (DIPS) technique (Wei and Weiss 2011b). The handbook chapters
Photolithography on Porous Silicon and Imprinting Porous Silicon provide more detail on these two routes.
Applications
In the early years, porous silicon waveguides held great promise for becoming the
necessary link between porous silicon light-emitting diodes and traditional silicon
electronic components on chip (Loni et al. 1996; Arrand et al. 1997, 1998a; Bondarenko
et al. 1995; Canham et al. 1996; Araki et al. 1996; Mihalcescu et al. 1997; Balucani
et al. 2000, 2001; Oton et al. 2006; Najar et al. 2007; Chouket et al. 2009). While the
dream of monolithic optoelectronic functionality on silicon endures, porous silicon
waveguides are no longer considered the most attractive option; moreover, the necessary efficiency of light emission from porous silicon for integrated applications has not
been realized (see handbook chapter Electroluminescence of Porous Silicon).
Losses in porous silicon waveguides are typically between 10 and 20 dB/cm, while
traditional silicon waveguides using standard CMOS lithography and etching techniques have been demonstrated with losses below 0.3 dB/cm near 1550 nm (Vorozov
et al. 2000; Charrier et al. 2000a, b; Dong et al. 2010; Rossi et al. 2001). Several studies
have been performed examining the origin of the losses in porous silicon and oxidized
porous silicon waveguides with the following sources considered to be the most
significant origins of loss: (1) scattering due to interface roughness and porosity
fluctuations on micron length scales and (2) absorption (Takahashi and Koshida
1999; Pirasteh et al. 2007; Ferrand and Romestain 2000). In general, oxidized porous
silicon waveguides experience reduced losses, with losses of 0.5 dB/cm reported near
1550 nm and losses as low as 0.2 dB/cm reported in the visible for fully oxidized
waveguides (Pirasteh et al. 2007; Balucani et al. 2005; Charrier et al. 2012).
More recently, porous silicon waveguides have attracted a great deal of attention
for their potential applications in chemical and biomolecular sensing. Arrand
et al. first recognized that porous silicon waveguides may be advantageous for
sensing applications, showing that the waveguide interfacial scattering losses were
reduced significantly when solvents were infiltrated in the pores (Arrand et al.
1998b). Detection of various chemicals was later demonstrated with reported
sensitivities typically on the order of 104/RIU, but with sensitivities as low as
819
Fig. 3 (a) SEM image of grating-coupled porous silicon waveguide (scale bar 200 nm) and (b)
measured reflectance spectra during operation as a sensor. The waveguide resonance shifts in
response to the addition of various molecules. Detection of a 16mer nucleic acid sequence is
demonstrated (Adapted with permission from Wei and Weiss (2011a). Copyright 2011, Optical
Society of America)
106/RIU achievable (Xia et al. 2012; Rea et al. 2009; Arrand et al. 1998c; Rivolo
et al. 2004). For the specific detection of molecules, care must be taken to passivate
the surface and functionalize (see handbook chapter Silicon-Carbon Bond
Formation on Porous Silicon) the waveguide with the appropriate receptor molecules to ensure that the waveguide does not corrode during exposure to various
solutions and only the desired target molecule is captured by the sensor. Label-free
detection of nucleic acid molecules (Rong et al. 2008a, b; Wei and Weiss 2011a;
Lawrie et al. 2010; Wei et al. 2012; De Tommasi et al. 2008), proteins (Hiraoui
et al. 2012b), and toxins (Lawrie 2012) has been demonstrated. Figure 3 shows an
example of nucleic acid detection in a two-layer, grating-coupled porous silicon
waveguide. When light is incident on the waveguide at the proper angle to allow
coupling of diffracted light into the waveguide, a resonant feature is observed in the
reflectance spectrum (Wei and Weiss 2011a). This resonance angle depends
directly on neff. Hence, when molecules are attached inside the waveguide, neff
increases and the resonance position shifts to higher angle. Quantification of the
molecules attached in the waveguide can be performed by considering the magnitude of the resonance angle shift. DNA detection limits for porous silicon waveguides are typically in the micromolar range with limits in the nanomolar range
achievable. Increasing the probe DNA molecule density inside the porous silicon
waveguide by in situ DNA synthesis using sequential phosphoramidite reactions
was found to be an effective approach for achieving low detection limits (Lawrie
2012; Lawrie et al. 2009). Moreover, for multimode waveguides, lower-order
modes at higher resonant angles were shown to give a slightly higher detection
sensitivity (Jiao and Weiss 2010). Theoretical calculations suggest that based on the
figure of merit of resonance shift divided by full-width at half-maximum of the
resonance, porous silicon waveguides have the potential to outperform traditional
surface plasmon resonance sensors by a factor of 60 (Saarinen et al. 2005).
820
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Porous Silicon Diffraction Gratings

Adrian Keating
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Grating Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diffraction Gratings on PS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fabrication Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
This work reviews progress in the fabrication of high-resolution porous silicon

gratings. A comparison of the various fabrication methods is presented, including prepatterning of silicon, stamping, laser writing, and photolithographic and
photo-assisted dissolution. Various types of sensors incorporating gratings are
discussed which use either intensity and/or spatial (angular) measurement. The
sensing capabilities, features, and limitations of these types of gratings are
presented.
Introduction
Porous silicon (PS) diffraction gratings were reported in 1970 and remain the first
devices ever to be made from PS, even before its nanoscale porosity and luminescent properties were realized. This work reviews progress since then toward highA. Keating (*)
The Microelectronics Research Group, School of Mechanical and Chemical Engineering,
The University of Western Australia, Crawley, WA, Australia
e-mail: adrian.keating@uwa.edu.au
DOI 10.1007/978-3-319-05744-6_84
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A. Keating
resolution PS gratings, as there is now increasing interest in such structures for

sensing and other applications. A comparison of the various fabrication methods is
presented, including prepatterning of silicon, stamping, laser writing, and photolithographic and photo-assisted dissolution.
Grating Theory
Diffraction of light from a grating is caused by periodic changes in the amplitude or
phase of the incident light Kress and Meyrueis (2000). The incident light interacts
coherently with the grating to create regions of constructive or destructive interference in the spatial far field of the reflected and transmitted light. When monochromatic light of wavelength is incident on the grating, the angular diffraction of light
can be described by the diffraction equation given by:
nin sin nout sin
(1)
where is the grating pitch; m is the diffraction order (m 0,1,2,. . .); nin, are
the medium index and angle of the incident beam, respectively; and nout, are the
medium index and angles of the mth-order diffracted beam, respectively (Palmer
and Loewen 2000). Figure 1a illustrates the general structure of diffraction gratings
formed on multilayer PS films. The refractive index (n) and height (h) of the grating
and underlying layers strongly affect the operation of the device. For instance,
where gratings are formed over a waveguide (Wei et al. 2008; Wei and Weiss 2011;
Sipe et al. 2010; Liscidini et al. 2009; Rea et al. 2008a, b, Rea et al. 2009; Marino
et al. 2008; Wei et al. 2009), (n1,h1) defines the grating index and height, while (n2,
h2) and (n3 < n2, h3 >> h2) define the waveguide core and cladding layers,
respectively. Simple diffraction gratings may be formed on silicon (h2 h3 0)
(Lerondel et al. 1997; Sirbuly et al. 2003; Gargas et al. 2006; Lai et al. 2012) or in
the top layer of a porous film (n1 n2, h3 0) (Ryckman et al. 2010a, 2011a).
Relevant grating configurations to consider are:
Reflection or transmission diffraction gratings which diffract light into angles
defined by the grating equation (Eq. 1) where these angle are defined by the
wavelength-to-pitch ratio (/). The diffraction efficiency is the intensity of the
mth-diffracted mode normalized to the incident intensity. The diffraction efficiency of PS gratings has been measured and shown to be a function of the
grating height (h1) and index (n1) (Jia et al. 2007; Mangaiyarkarasi et al. 2008)
and / (Jia et al. 2007; Dalisa et al. 1970), consistent with grating theory
(Palmer and Loewen 2000).
Grating couplers which are designed to maximize the diffracted light into a
waveguide or plane. High-diffraction-order (m 17) grating couplers as demonstrated by Rea et al. (Rea et al. 2008b) are easier to fabricate than lowdiffraction-order grating couplers (m ! 1) but have very low coupling
825
Fig. 1 (a) Definition of parameters (angles, mode numbers, layers, and indices) for a porous
silicon (in-plane) diffraction grating and (b) comparison with Bragg gratings
efficiency. By extending the length of the grating over the entire waveguide, a
resonant waveguide grating is formed (Rosenblatt et al. 1997). Both PS (Wei
et al. 2008; Wei and Weiss 2011; Sipe et al. 2010; Liscidini et al. 2009; Wei
et al. 2009) and oxidized PS (Rea et al. 2008a, b, 2009; Marino et al. 2008)
resonant waveguide gratings have been reported. The Weiss group showed that
forming both the grating and waveguide from PS contributes to a high sensitivity
(Wei and Weiss 2011).
Littrow gratings reflect light back along the direction of the incident light so that
. The Littrow configuration is typically used as a retroreflector but has also
been investigated as a PS sensor (Golub et al. 2010).
Bragg gratings: The Bragg equation can be obtained directly from the general
grating equation. Bragg gratings illustrated in Fig. 1b use specular reflection
defined by in Eq. 1. The Sailor group combined both (surface relief)
diffraction gratings and a multilayer ruggate mirror stack (Ruminski et al. 2008),
combining elements of both to investigate the effect on detection sensitivity.
Diffraction Gratings on PS
Figure 2 shows the progress in PS gratings using the metric of wavelength-to-pitch
ratio (/). A large ratio of / indicates a move to smaller pitch () and/or longer
wavelength () and is a key parameter of the grating equation (Eq. 1). The earliest
reported grating in porous silicon was reported by Dalisa et al.(Dalisa et al. 1970)
who achieved a pitch of 0.4 m using holographic photoelectrodissolution.
Some 22 years later, the Sailor group renewed interest in PS gratings by using
photoelectrodissolution to create gratings with a 50 m pitch. Progress on PS
diffraction gratings remained slow and largely stopped in the 6 years between
1997 and 2003. In 2005, the Weiss group began an investigation into PS grating
waveguides as sensors based on photoresist gratings and so they cannot be
826
A. Keating
Fig. 2 Published PS grating research using the metric of /, a key parameter in the grating
equation (Eq. 1). The highest reported results are circled; however, the data indicated by the
squares ( ) used photoresist to form the gratings on PS rather PS itself
categorized as a true PS grating (squares in Fig. 2). However, they developed a

complete PS grating over a PS waveguide in 2011 using E-beam lithography and
RIE etching techniques.
Table 1 lists the relevant work in this area, detailing the key fabrication methods
and published grating properties. These areas are summarized below.
Fabrication Methods
Prepatterning of Silicon: Several authors have reported the fabrication of gratings
by first patterning silicon followed by subsequent anodization to form PS (Golub
et al. 2010; Ruminski et al. 2008; Ruminski 2009; Mangaiyarkarasi et al. 2008;
Volk et al. 2005). Ruminski et al. (Ruminski 2009) showed that multilayer Bragg
gratings could be fabricated under a grating fabricated by first patterning silicon and
that the layers could be lifted off by electropolishing. The remaining silicon
substrate retained the shape of the grating (with some loss of fidelity) allowing
repeated anodization. Mangaiyarkarasi et al. (Mangaiyarkarasi et al. 2008) has used
this concept of repeated anodization and PS removal (through dissolution) to
control the shape of the underlying silicon features which had been previously
implanted with high-energy protons. The color and contrast of the images patterned
into multilayer stacks of porous silicon changed dramatically with viewing angle
due to the PS grating ( 6 m) whose features range from nearly square to
triangular. A major advantage of prepatterning of the silicon wafer is that standard
microelectronic photolithography and etching processes can be leveraged to produce high-quality PS gratings (Golub et al. 2010). Further, by combining microelectronic etching and doping processes to implant both n-type (phosphorous) and
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Table 1 Review of grating fabrication methods, institutions, and key grating parameters
Fabrication
method
Prepatterning
of silicon
Stamping
Photo-assisted
dissolution
Laser writing
First author
institution
UC, San Diego,
USA
Period
(m)
8
Index
(n1)
Depth
(d1)
(nm)
0
Research Institute
for Technical
Physics and
Materials Science
MFA, Hungary
National
University of
Singapore
Tel Aviv
University, Israel
UC Santa
Barbara, USA
Vanderbilt
University, USA
0.375,
1
Philips
Laboratories, NY,
USA
UC, San Diego,
USA
Universite Joseph
Fourier CRNS,
France
Xinjiang
University, China
National Institute
for Laser, Plasma
and Radiation
Physics, Romania
Odessa State
University,
Ukraine
Istituto
Elettrotecnico
Nazionale
Galileo
Ferraris, Italy
University of
Naples Federico
II, Italy
Institute for
Microelectronics
and Microsystems,
Italy
8.5
200
1.59,
1.682
1.81
132,
325, 340
0.48
50
0.67,
22.71
2,500
References
(Ruminski
2009)
(Volk et al. 2005;
Nagy et al. 2005)
(Mangaiyarkarasi
et al. 2008; Breese
et al. 2006)
(Golub et al. 2010)
(Sirbuly et al. 2003;
Gargas et al. 2006)
(Ryckman
et al. 2010a, b, 2011a,
b)
(Dalisa et al. 1970)
(Doan and Sailor

1992)
(Lerondel et al. 1997;
Chamard et al. 1998)
(Jia et al. 2007)
5.9
1.6
1,000
(Vlad et al. 1996)
20
(Alexeev-Popov
et al. 1996)
0.05
(Rossi et al. 2003)
10
1,000
(Marino et al. 2008)
2,500,
4,000
(Rea et al. 2008a, b,

Rea et al. 2009;
Marino et al. 2008)
10
(continued)
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A. Keating
Table 1 (continued)
Fabrication
method
Lithographic
First author
institution
Vanderbilt
University, USA
Period
(m)
Index
(n1)
Depth
(d1)
(nm)
The University of
Western
Australia,
Australia
1.78
500, 890
References
(Wei et al. 2008; Wei
and Weiss 2011; Sipe
et al. 2010; Liscidini
et al. 2009; Wei
et al. 2009)
(Lai et al. 2012)
p-type (boron) regions, Volk et al. (2005) demonstrated that PS could be formed
laterally (in-plane) to various depths in p-type silicon. Modulation of the current
during anodization allowed nearly pure phase gratings to be formed in PS; however,
the uniformity of the gratings was poor and the lateral extent of gratings formed was
limited.
Stamping: Two stamping methods have been applied to produce PS gratings
based on either hard or soft stamps. Imprinting of PS using a hard Si stamp has been
investigated by Ryckman et al. to produce diffraction gratings with various pitches
as short as 1.5 m and grating heights (controlled by the applied pressure)
ranging 29615 nm (Ryckman et al. 2010a, b, 2011a, b and handbook chapter
Imprinting Porous Silicon). Imprinting of gratings provides a simple, fast, and
effective method to produce gratings, and the stamps can be reused many times.
However, in addition to the PS/air grating formed, the PS is crushed where the
stamp contacts the PS, densifying the material, introducing a periodic increase in
the refractive index of the layer under the grating. This densified layer may affect
analyte infiltration as well as the optical performance of the grating. Stamps of
PDMS have been used for dry-removal soft lithography on PS films (Sirbuly
et al. 2003; Gargas et al. 2006). When the PDMS contacts a thin layer of PS, the
weak adhesion to the substrate allows the PS to be lifted off where it contacts the
soft stamp. Both the stamped (patterned) PS layer and the lifted off PS layer are
functional gratings. However, thick films (>1 m) cannot easily be removed
through dry-removal soft lithography, preventing the use of this approach to pattern
multilayer DBRs or waveguides with thick cladding.
Photo-assisted Dissolution: Gratings in PS can be formed either using a combination of light and electric current during the anodization of silicon (photoelectrodissolution) or by illumination of a uniform film of PS in an HF electrolyte
(photodissolution). The latter technique has a dedicated review in this handbook
Porous Silicon Formation by Photoetching. In this work,both photodissolution
and photoelectrodissolution are referred to by the more general term photo-assisted
dissolution. Sailors initial work on n-type photoelectrodissolution of Si (Doan and
Sailor 1992) was followed by Lerondel et al. (Lerondel et al. 1997) who studied
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both photoelectrodissolution and photodissolution on p-type silicon over a range of

doping levels. While gratings formed by photodissolution were independent of
doping, a resistivity higher than 0.1 .cm was required to produce gratings via
photoelectrodissolution of silicon.
Holographic methods can potentially produce very short grating periods over a
wide (lateral) extent. The earliest work by Dalisa et al. (1970) was based on
holographic formation of the grating during anodization; however, removal of the
PS layer was required to achieve a measurable diffraction efficiency from the Si
layer underneath. To achieve short grating periods (), a large angle between the
interfering lasers (2) and short exposure wavelength are required. Unfortunately,
large angles are difficult to achieve in an anodization tank ( 16 (Jia et al. 2007)
and 15 (Lerondel et al. 1997)) while short wavelengths scatter more light and
have larger absorption in the PS, leading to short penetration depths. PS gratings
with a period of 0.67 m have been achieved by holographic photodissolution
(Lerondel et al. 1997), where feature resolution was limited by a combination of the
carrier diffusion length, incidence angle, scattering, and/or bubble formation (Jia
et al. 2007). The first-order diffraction efficiency from a holographic grating formed
by photoelectrodissolution of PS with a value of / 0.5 was low, at around 1.2
% from PS-layer grating (Jia et al. 2007) and 4 % once the PS layer was removed
(Dalisa et al. 1970). An interesting observation was made by the Sailor group who
found that the top surface after photoelectrodissolution remained flat to within
20 nm (on 1 m thick PS) indicating that the grating resulted only from spatial
index and depth variations of the PS. Such a grating may have very low surface
scattering; however, these details were not further investigated.
Laser Writing: The absorption of short wavelength light in PS and its low
thermal conductivity (see handbook chapter Thermal Isolation with Porous
Silicon) allow high temperatures to be achieved upon exposure to focused laser
light, leading to selective area oxidation, pore restructuring, or ablation of the PS
depending on the laser power. Alexeev-Popov et al. used a pulsed laser at
337 nm focused down to 50 m to expose the PS through a chromium mask
with a pitch of 20 m (Alexeev-Popov et al. 1996). Relative diffraction
efficiencies (normalized to the intensity of the beam reflected from the initial PS)
were found to be ~1 %. The scan speed of 0.2 mm/s required a scan time of around
7.3 min for a 2.1 2.1 mm2 sample. Coherent optical interference of two beams at
530 nm has also been used to form gratings with a depth of up to 1 m (Vlad
et al. 1996). Marino et al. (2008) and Rea et al. (Rea et al. 2008a, b, 2009) have
selectively oxidized PS using a laser at 406 nm, removed the oxide in HF, and
then fully oxidized the PS film to reduce scattering. This was achieved by reducing
the scan speed to 10 m/s, requiring around 1.5 h to pattern an area of 1 mm2
(Marino et al. 2008) which may pose issues when scaling this approach to larger
dimensions.
Lithographic Methods: Both electron beam lithography and UV photolithography have been utilized to form gratings in PS. E-beam-written gratings on PS have
been demonstrated down to a pitch of 50 nm (Rossi et al. 2003), and E-beam
lithography combined with RIE etching has been used to achieve patterned porous
830
A. Keating
silicon gratings with one of the highest report ratios of / ~ 1 (Wei and Weiss
2011). E-beam techniques required PMMA (positive) resist which could be
removed in acetone; however, UV photolithography using standard positive UV
photoresists requires an alkaline developer which has previously prevented direct
photolithography on PS. Lai et al. demonstrated that passivated PS could be directly
patterned using standard microelectronics photolithography (Lai et al. 2011), demonstrating multilayer PS gratings with a pitch of 4 m (Lai et al. 2012). More
information can be found in the handbook chapter Photolithography on Porous
Silicon.
Sensing
There has been limited quantitative evaluation of PS gratings for sensing applications. Rea et al. (Rea et al. 2009) characterized the sensing capability of a grating
coupler over a slab waveguide by measuring the spectrum of the transmission
through the waveguide. The transmission null at 1,540 nm was shifted slightly in
response to solvent vapor penetrating the waveguide. Based on a wavelength
resolution of 0.1 nm, the best estimate for the limit of detection (LOD) was
4.8 103 RIU (refractive index units). Wei et al. (Wei and Weiss 2011) measured
the reflection from a grating coupler over a slab waveguide as a function of the
incident angle of the light and found an LOD in the order of 104 RIU, requiring
either an angular resolution of 0.13 mrad or an optical resolution of 0.1 nm for a
spectral measurement. Measurements of the change in the diffraction efficiency due
to solvent vapor penetrating the diffraction grating have been reported (Ruminski
2009) which suggest an LOD of 1.2 104 RIU can be achieved. For application in
biological testing, the size of the molecule has a large impact on the sensitivity. Wei
et al. (Wei and Weiss 2011) showed good sensitivity and agreement with models for
small, 0.8 nm 3-APTES molecules; however, low sensitivity was achieved for
larger 3.5 nm probe DNA into the 20 nm pores.
Analyte index changes around the grating can significantly alter the power in
each diffraction order, providing a simple means of signal detection compared with
spectral measurements of film optical thickness (Dancil et al. 1999), resonance dips
in microcavity reflectance (Wu et al. 2011), or angular resolved measurements (Wei
and Weiss 2011). Ruminski et al. (2008) found the relative diffraction efficiency
changed by 100 % in the presence of ~40 g/m3 of solvent, suggesting highly
efficient and simple detection is possible from such gratings. Similar measurements
by Lai et al. (2012) demonstrated the complementary change in the 0th-order and
1st-order diffraction efficiency can be used to enhance detection. The temperature
variation and aging characteristics of PS diffraction gratings have not been studied;
however, it has been shown that even when fully oxidized, the DE can still change
over 10 weeks from 1.3 % to 1.1 % (Jia et al. 2007).
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Modeling
Finite-difference time-domain (FDTD) models and beam propagation methods
(Chung and Dagli 1990) provide insight into the field distribution in 2D or 3D,
while computation models based on solving rigorous coupled wave analysis
(RCWA) (Lai et al. 2012; Breese et al. 2006) enable rapid calculation of diffraction
angles and efficiencies. Wei et al. used COMSOL models to determine that an
all-PS waveguide grating could enhance detection sensitivity by optimizing the
confinement of the electric field and RCWA to quantify the reflectivity variation
with angle and wavelength (Wei and Weiss 2011). While a number of commercial
modeling tools exist, there are also a variety of open-source FDTD tools such as
MEEP (Oskooi et al. 2010) and code segments to implement an RCWA (Wei and
Weiss 2011; Harper 2003) based on published computational models. A systems
level approach to developing PS grating-based sensors offers significant opportunity to improve performance by leveraging models to explore and optimize designs.
Summary
A selection of grating fabrication techniques has been reviewed and the performance of each discussed. For sensing applications, a small number of diffraction
orders and low scattering are desirable to prevent crosstalk and achieve a high
diffraction efficiency. Processes to achieve low roughness, high resolution, and a
large wavelength-to-pitch ratio are desirable for such applications. Long-term aging
studies and designs optimized through modeling are opportunities for investigation
in the next generation of PS-based diffraction sensors.
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Wei X, Kang C, Liscidini M, Rong G, Retterer ST, Patrini M, Sipe JE, Weiss SM (2008) Grating
couplers on porous silicon planar waveguides for sensing applications. J Appl Phys 104
(12):123113-1123113-5
Wei X, Kang C, Rong G, Retterer ST, Weiss SM (2009) Porous silicon waveguide with integrated
grating coupler for DNA sensing. In: Fauchet PM (ed) Frontiers in pathogen detection: from
nanosensors to systems, vol. 7167, SPIE
Wu C, Rong G, Xu J, Wang G (2011) An intensity-interrogated sensing technique based on porous
silicon microcavity, 2011. In: International conference on nanotechnology and biosensors
(IPCBEE), Singapore, pp 3943

Paul Snow
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Theoretical Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Historical Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
836
836
839
839
839
840
842
Abstract
Work on phononic crystals in porous silicon is first put in context of the more
general interest in controlling wave behavior in periodic media in both photonic
and phononic crystals. The condition for a stop band for acoustic waves is
derived by analogy with the Bragg condition with optical multilayers and then
also obtained from the Rytov theory of layered acoustic media. The modeled
acoustic bandgap in porous silicon is then defined and examined with the
parameters used to model acoustic velocities in the material. A historical overview of papers covering theory and experiments on acoustic bandgaps in porous
silicon is then given with an emphasis on their hypersonic nature and phoxonic
properties. Finally, applications of acoustic distributed Bragg reflectors
(ADBRs) with integrated transducers for high-performance bulk acoustic resonators (BAW) and possible applications for thermoelectric devices are
presented.
P. Snow (*)
Department of Physics, University of Bath, Bath, UK
e-mail: p.a.snow@bath.ac.uk
DOI 10.1007/978-3-319-05744-6_85
835
836
P. Snow
Introduction
During the 1990s, the investigation of photonic crystals, three-dimensional periodic
dielectric media demonstrating a full band structure with a complete bandgap for
light, was an active research field (Joannopoulos et al. 2008). In parallel with this,
work was resuming on modeling band structure for elastic and acoustic waves in
periodic inhomogeneous media (Sigalas and Economou 1992). In analogy, these
became known as phononic crystals. The early review of Kushwaha is comprehensive and contrasts the origin and details of the bandgaps in electronic, photonic, and
phononic crystals (Kushwaha 1996), while a later overview gives good comparisons of phononic theory and experiment (Sigalas et al. 2005).
In porous silicon, work has focused on one-dimensional periodic systems, which
are normally referred to as acoustic Bragg mirrors or acoustic distributed Bragg
reflectors (ADBRs) in comparison to optical Bragg mirrors that have been extensively studied (Bjork et al. 1995) and exploited in porous silicon (see chapter
Porous Silicon Photonic Crystals). Equivalent acoustic systems were extensively studied in the 1980s to examine the folding of acoustic phonon branches in
semiconductor superlattices (Colvard et al. 1980) and analyzed using the Rytov
model (Rytov 1956), which is carefully reviewed in Jusserand and Cardona (1989).
Additionally, acoustic multilayers have a well-established history of use in piezoelectric resonators (Newell 1965), an application which has been resurgent in recent
years (Lakin et al. 1995; Satoh et al. 2005) for hypersonic devices, i.e., those
operating at frequencies greater than 1 GHz.
In this chapter, theories used to model bandgaps and dispersion relations in
porous silicon ADBRs are discussed and recent experimental results are reviewed
in anticipation of future applications.
Theoretical Overview
In a distributed Bragg reflector, as shown in Fig. 1a, multiple alternating layers
of material with contrasting physical properties give a high reflectivity for
certain wavelengths due to the net effect of the multiple partial reflections at
the interfaces between layers. The reflector consists of N repeats of an [a, b]
layer pair.
Some insight into physics can be obtained by considering, at normal incidence,
the net phase delay for a partially reflected plane wave executing a round trip
around a layer pair. By requiring this delay to be an integer multiple of 2 radians,
the condition for a reflectivity stop band can be deduced. For light, this gives the
relation that
m B 2na da nb db ,
(1)
where m is the order of the stop band, B is the Bragg wavelength and the center of
the bandgap, and da and db are the thickness of layers a and b in the repeating
N =1
N =2
837
N =3
Pa
Pb
Pa
Pb
Pa
Pb
da
db
da
db
da
db
ra
rb
ra
rb
ra
rb
na
nb
na
nb
na
nb
Va
Vb
Va
Vb
Va
Vb
Transmittance (dB)
20
40
60
80
100
Transmittance (dB)
0.5
20
1.5
Frequency (GHz)
2.5
40
60
80
160
0.5
1.5
Frequency (GHz)
2.5
Fig. 1 Bragg mirror structure and spectra. (a) Schematic diagram of layers [a, b] repeating
N times. Physical parameters depending on the porosity, P, are identified in the text. (b) Acoustic
transmission spectra for pSi Bragg mirror (darker line experimental data, lighter line transfer
matrix model). (c) Modeled and measured transmission data for pSi rugate filter. (b, c) (From
Thomas et al. (2010) reprinted with permission from Applied physics letters by American Institute
of Physics, Copyright (2010), American Physical Society)
layers with refractive indices na and nb, respectively. For elastic waves in a solid,
the same phase considerations lead to stop band frequencies given by

m da d b 1
fB
2 Va Vb
(2)
where fB is the stop band frequency and Va, Vb are the elastic wave velocities in the
layers.
The Rytov theory (Rytov 1956) gives the dispersion relation for waves in an
infinite Bragg mirror

da db
e2
da
db
cos qD cos
sin
sin
Va Vb
2
Va
Vb
(3)
where, in addition to variables defined above, the modulation distance D da + db, q

is the wavevector of the wave in the multilayer, more formally the phononic Bloch
838
P. Snow
wave of the periodic system, and is the angular frequency. e is the gap parameter
which represents the mismatch of the acoustic impedance, V, at the interfaces in the
multilayer and controls the size of the bandgaps. It is given by
b V b a V a
:
e p
b V b a V a
(4)
The theory is valid if each layer is an elastic continuum with a given mass
density and a sound velocity V, which does not depend on frequency but which
can represent either longitudinal or transverse acoustic waves. For porous silicon, it
is assumed that thickness of any layer and the wavelengths involved are much
greater than the pore size so that the elastic properties can be considered as an
effective elastic continuum (for the typical variation of elastic properties with
porosity, see chapter Mechanical Properties of Porous Silicon).
Solving Eq. 3 in the limit of small mismatches in acoustic impedance, hence
negligible e, shows the effect of the periodicity of the mirror. Considering the
wavevectors for which q m/D, representing the boundaries of the Brillouin
zone for a system with the periodicity of the Bragg mirror, more formally yields
Eq. 2 for the frequencies at which bandgaps will be observed.
For porous silicon, Si (1 P) for any layer with a porosity P. Assuming
the standard form of semiempirical formula for the dependence of velocity of
porosity used for porous silicon, V VSi (1 P) where depends on the micromorphology of the porous layers, gives a gap parameter that depends only on the
porosities and ,

e
1

1
1 Pb 2
1 Pa 2

,
1 Pa
1 Pb
(5)
where Pa and Pb are the porosities of the layers. Using typical values for pSi Bragg
mirrors gives values for e much larger than those obtained in other crystalline
semiconductor systems such as GaAs/AlGaAs or Si/Ge. Furthermore, Eq. 5 shows
that the ratio of porosities in the layers determines the band splitting rather than the
absolute difference of impedances suggested by Eq. 4, as is also shown in the
version of the Rytov equation used for porous silicon in Parsons and Andrews
(2012). Calculation shows that although porous silicon has a relatively low absolute
value for acoustic impedance, the porosity ratios available can theoretically match
the bandwidths available in commercial acoustic mirrors using layers such as
Mo/SiO2 or W/SiO2 (Satoh et al. 2005).
Moving away from the dispersion relation for infinite layers, the transmissivity
or reflectivity of an N-repeat ADBR can be calculated using the theory of Mizuno
and Tamura (Mizuno and Tamura 1992) which extracts the net transmission from
transfer matrix theory for waves passing from a mirror substrate to a detector. For a
fuller model that can include the details of transducer layers and coupling fluids
used to couple acoustic waves into an ADBR, the matrix model of Mitsas and
839
Siapkas has been used (Mitsas and Siapkas 1995). At normal incidence for acoustic
waves and when only pure longitudinal waves exist, as when waves are coupled
into a sample through a liquid, the same matrix method can be used for both optic
and acoustic waves by replacing the refractive index, n, with the acoustic admittance, 1/V.
Historical Overview
Theory
The possibility that porous silicon multilayers could be used to observe acoustic
stop bands was first proposed by Kiuchi et al. (2005), who used the Rytov equation
to investigate the bandgaps available by varying bilayer thicknesses and varying
average porosity. Independently, Reinhardt and Snow (2007) used a scattering
matrix method (Reinhardt et al. 2003) to study acoustic bandgap structures. They
demonstrated that the transmission coefficient will fall more rapidly with the number
of layer repeats for acoustic stop bands compared to optical stop bands because of the
higher impedance ratio between high and low porosity layers and investigated the
effect of drift of porosity with etch time that can occur with the etching of thick
multilayers. Additionally, they presented the first analysis of apodized acoustic rugate
filters (Lorenzo et al. 2005) that are possible with porous silicon because it permits
the smooth modulation of acoustic impedance with depth. More recently, work has
looked at broadening bandgaps by combining mirrors with different porosities and
indicated that a bandgap could be obtained for both longitudinal and transverse waves
at up to 62 GHz (Moctezuma-Enriquez et al. 2011).
Experiment
The first evidence for hypersonic phononic crystal effects was observed in porous
silicon superlattices using Brillouin light-scattering experiments (Parsons and
Andrews 2009). Comparison between experiment and theory using the Rytov
model indicated that the bulk longitudinal phonon branch had been folded. One
of the samples exhibited a spectrum consistent with a bandgap of 3.3 GHz for a first
gap located at 13.4 GHz.
Aliev et al. (2010) used acoustic transmission spectroscopy to measure directly
the bandgap of an ADBR showing a first-order bandgap at 0.65 GHz with a stop
band depth of at least 50 dB and a weaker second-order gap at 1.3 GHz. The sample
was also characterized using both its photonic and phononic stop band properties,
i.e., consistently using Eqs. 1 and 2, which demonstrates the phoxonic nature
(Sadat-Saleh et al. 2009) of porous silicon superlattices.
Other work with acoustic multilayers has demonstrated that rugate filters can
successfully be fabricated with the anticipated suppression of higher-order stop
bands in the transmission spectrum (Thomas et al. 2010). This also demonstrates
840
P. Snow
Fig. 2 Normalized dispersion relation for pSi superlattices showing composite data from large set
of superlattice samples obtained by Brillouin scattering experiments. The solid (dashed) curves are
theoretical longitudinal (transverse) modes obtained from the Rytov model. The horizontal line
identifies a localized surface mode lying within the phononic bandgap of the bulk longitudinal
mode, trapped at the surface of the phononic crystal. Full details of the samples and acoustic
branch identification in Parsons and Andrews (2012) (Reprinted with permission from Journal of
applied physics by American Institute of Physics, Copyright 2012, American Institute of Physics)
that it is possible to create other porous silicon acoustic devices with smoothly
varying acoustic impedance profiles to be used, for example, as antireflection coatings for transducers, index-matching layers, or filters that have apodization functions.
Figure 1b, c shows the predicted and measured difference between an acoustic Bragg
and rugate filter, where the rugate filter has a half-period sinusoidal impedance profile
replacing the constant impedance for layers [a, b] in the Bragg structure.
For the ADBR, four bandgaps are visible with the highest at 2.8 GHz. The rugate
filter shows only the fundamental bandgap associated with the period of the
sinusoidal modulation of the acoustic impedance.
Parsons and Andrews (2012), building on their earlier work (Parsons and Andrews
2009), have presented a comprehensive analysis of the complex phononic structure
observable in porous silicon superlattices. This fully integrates the modeling of the
photonic and phonic nature of the ADBRs including a consideration of off-axis
propagation through the layers. Figure 2 shows the effective dispersion relation
obtained from their samples with data showing agreement with the model up to
~40 GHz.
Applications
Porous silicon structures can be successfully combined with integrated transducers
produced by thin-film deposition methods to create high-performance bulk acoustic
841
Fig. 3 TEM cross section of BAW transducer stack showing the metallic layers of the electrodes
and the SiO2 coupling layer above a single layer of 75 % porous silicon of thickness 1,950 nm. The
bars show the scale with the inset showing more details of the pore structure and interface with the
Si substrate (Micrographs by H. Heinrich and B. Yuan of AMPAC, University of Central Florida)
wave (BAW) resonators. This has been used to demonstrate an integrated Bragg
reflector at a frequency of 2 GHz (Aliev et al. 2012a) and has shown that pSi has
potential for application as a low-impedance low-loss acoustic material in hypersonic acoustic devices (Aliev et al. 2012b). Figure 3 shows a TEM image of a
transducer (AlCu/W electrodes sandwiching an AlN piezo layer) produced to
generate bulk acoustic waves resonating between the upper surface and the Si
substrate. Analysis estimates the acoustic attenuation in the pSi to be less than
75 dB/cm/GHz2 (Aliev et al. 2012b). This value places the propagation loss in the
same range as metals such as copper and supports earlier preliminary values
(Thomas 2011). The ability to produce smooth porosity gradients in pSi means
that it could be applied for impedance matching between acoustic devices, and the
capability to produce short-period structures, demonstrated and already optimized
for photonic Bragg mirrors, shows that all-pSi ADBRS could be produced at
frequencies of ~30 GHz for niche application microwave BAW-devices.
BAW filters for wireless communication applications require the tight confinement of acoustic energy by the ADBR isolating the resonator from the substrate.
For a slab layer, as shown in Fig. 3, the electrical reflectivity of the device (the S11
scattering parameter) shows sharp modes associated with waves resonating across
the whole pSi layer. This offers the opportunity for sensing applications where an
interaction with the pSi in a slab or microcavity changes the acoustic impedance of
the layer by means of mass loading or altering the elastic properties of the material.
Recently, there has been a surge of interest in thermoelectric applications for
phononic crystals based on the control of thermal conductivity in phononic devices
(Hopkins et al. 2011) including periodically porous silicon nanodevices (Marconnet
et al. 2012, 2013). These porous silicon devices are arrays of large ~200 nm pores,
thus being a designed macroporous structure, in the form of a porous nanobridge.
The phononic bandgap in such a device alters the phonon dispersion in addition to
size effects in the 200 nm thick bridge. This can be used to reduce the thermal
conductivity, with thermal conductivities predicted (Hopkins et al. 2011) and
842
P. Snow
measured (Marconnet et al. 2012) down to 3 % or 4 % of the Si value. This is

desirable as the standard figure of merit for thermoelectric materials, Z, is given by
Z 2/kR where is the Seebeck coefficient, k is the thermal conductivity, and R is
the electrical resistivity (Riffat and Ma 2003; see also chapter Thermal Isolation
with Porous Silicon).
Most generally, the periodicity of phononic structures influences heat transport
in two ways (Ma et al. 2013). Viewed at diffusive length scales, lines of heat flux
bend as they flow around the large pores thus giving a higher thermal resistance.
From a microscopic perspective, phonons percolating through the structure scatter
at new surfaces and grain boundaries, thus reducing the thermal conductivity of the
material. Recent modeling has shown that room-temperature heat transport in
silicon is dominated by phonons with wavelengths of less than 5 nm and with
mean-free paths of less than ~300 nm (Esfarjani et al. 2011). Thus, while
mesoporous phononic crystals offer control of phonons, it may also be that
enhanced phonon scattering in microporous pSi is an alternative way to reduce
thermal conductivity and find an ideal porosity and micromorphology for optimizing the thermoelectric figure of merit.
References
Aliev GN, Goller B, Kovalev D, Snow P (2010) Hypersonic acoustic mirrors and microcavities in
porous silicon. Appl Phys Lett 96:124101
Aliev GN, Goller B, Snow PA, Heinrich H, Yuan B, Aigner R (2012a) Porous silicon bulk acoustic
wave resonator with integrated transducer. Nanoscale Res Lett 7:378
Aliev GN, Goller B, Snow PA, Heinrich H, Yuan B, Menendez O, Aigner R (2012) Porous silicon
as an acoustic material for BAW. IEEE Int Ultrason Symp Proc. doi: 10.1109/
ULTSYM.2012.0553
Bjork G, Yamamoto Y, Heitman H (1995) Spontaneous emission control in semiconductor
microcavities, 5: a Bragg mirror primer. In: Burstein E, Weisbuch C (eds) Confined electrons
and photons new physics and applications. NATO Advanced Study Institute, Erice. July
1993. Plenum, London, pp 481487
Colvard C, Merlin R, Klein MV, Gossard AC (1980) Observation of folded acoustic phonons in a
semiconductor superlattice. Phys Rev Lett 45:298301
Esfarjani K, Chen G, Stokes HT (2011) Heat transport in silicon from first principle calculations.
Hopkins PE, Phinney LM, Rakich PT, Olsson RH III, El-Kady I (2011) Phonon considerations in
the reduction of thermal conductivity in phononic crystals. Appl Phys A 103:575579
Joannopoulos JD, Johnson SG, Winn JN, Meade RD (2008) Photonic crystals: molding the flow of
light, 2nd edn. Princeton University Press, Princeton
Jusserand B, Cardona M (1989) Raman spectroscopy of vibrations in superlattices. In:
Cardaona M, Guntherod G (eds) Light scattering in solids V. Springer, Berlin, pp 49152
Kiuchi A, Gelloz B, Kojima A, Koshida N (2005) Possible operation of periodically layered
nanocrystalline porous silicon as an acoustic band crystal device. Mater Res Symp Proc 832:
F3.7.1F3.7.6
Kushwaha MS (1996) Classical band structure of periodic elastic composites. Int J Mod Phys
10(9):9771094
Lakin KM, Kline GR, McCarron KT (1995) Development of miniature filters for wireless
applications. IEEE Trans Microwave Theory Tech 43(12):29332939
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Lorenzo E, Oton CJ, Capuj NE, Ghulinyan M, Navarro-Urrios D, Gaburro Z, Pavesi L (2005)
Porous silicon-based rugate filters. Appl Opt 44(26):54155421
Ma J, Prajuli BR, Ghossoub MG, Mihi A, Sadhu J, Braun PV (2013) Coherent phonon-grain
boundary scattering in silicon inverse opals. Nano Lett 13:618624
Marconnet AM, Kodama T, Asheghi M, Goodson KE (2012) Phonon conduction in periodically
porous silicon nanobridges. Nanoscale Microscale Thermophys Eng 16(4):199219
Marconnet AM, Asheghi M, Goodson KE (2013) From the Casimir limit to phononic crystals:
20 years of phonon transport studies using silicon-on-insulator technology. J Heat Transf
135:061601
Mitsas CL, Siapkas DI (1995) Generalized matrix method for analysis of coherent and incoherent
reflectance and transmittance of multilayer structures with rough surfaces, interfaces and finite
substrates. Appl Opt 34(10):16781683
Mizuno S, Tamura S (1992) Theory of acoustic-phonon transmission in finite-size superlattice
systems. Phys Rev B 45(2):734741
Moctezuma-Enriquez D, Rodriguez-Viveros YJ, Manzanares-Martinez MB, Castro-Garay P,
Urrutia-Banuelos E, Manzanares-Martinez J (2011) Existence of a giant hypersonic elastic
mirror in porous silicon superlattices. Appl Phys Lett 99:171901
Newell WE (1965) Face-mounted piezoelectric resonators. Proc IEEE 53:361366
Parsons LC, Andrews GT (2009) Observation of hypersonic phononic crystal effects in porous
silicon superlattices. Appl Phys Lett 95:241909
Parsons LC, Andrews GT (2012) Brillouin scattering from porous silicon-based optical Bragg
mirrors. J Appl Phys 111:123521
Reinhardt A, Snow PA (2007) Theoretical study of acoustic band-gap structures made of porous
silicon. Phys Stat Solid (a) 204(5):15281535
Reinhardt A, Pastureaud T, Ballandas S, Laude V (2003) Scattering matrix method for modeling
acoustic waves in piezoelectric, fluid, and metallic multilayers. J Appl Phys 94(10):69236931
Riffat SB, Ma X (2003) Thermoelectrics: a review of present and potential applications. Appl
Therm Eng 23:913935
Rytov SM (1956) Acoustical properties of a thinly laminated medium. Sov Phys Acoust 2:6880
Sadat-Saleh S, Benchabane S, Baida FI, Bernal M-P, Laude V (2009) Tailoring simultaneous
photonic and phononic band gaps. J Appl Phys 106:074912
Satoh Y, Nishihara T, Yokoyama T, Ueda M, Miyashita T (2005) Development of piezoelectric
thin film resonator and its impact on future wireless communication systems. Jpn J Appl Phys
44(5A):28832894
Sigalas MM, Economou EN (1992) Elastic and acoustic-wave band-structure. J Sound Vib
158(2):377382
Sigalas M, Kushwaha MS, Economou EN, Kafesaki M, Psarobas IE, Steurer W (2005) Classical
vibrational modes in phononic lattices: theory and experiment. Z Krisstallogr 220:765809
Thomas L-A (2011) Porous silicon multilayers for gigahertz bulk acoustic wave devices.
PhD thesis, University of Bath
Thomas L, Aliev GN, Snow PA (2010) Hypersonic rugate filters based on porous silicon. Appl
Phys Lett 97:173503

Giuseppe Barillaro
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Gas Sensing with Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sensing Platforms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
846
846
847
850
851
Abstract
In this chapter, the state of the art on porous silicon gas sensors, both electrical
and optical, is reviewed by paying special emphasis on the advancement of gas
sensor architectures that has occurred over the two last decades, as well as on the
different functionalization approaches implemented in and chemical species
sensed with such architectures. Ten main architectures, five for the electrical
domain (capacitor, Schottky-like diode, resistor, FET-like transistor, and
junction-like diode) and five for the optical domain (single layer, waveguide,
Bragg mirror, resonant cavity, and rugate filter), have been proposed so far for
improving gas sensor features. Several functionalization schemes have been
integrated in such architectures to improve sensor performance, and more than
50 different chemical species have been sensed using porous silicon gas sensors.
The latest trends on multiparametric sensing on single devices as well as on
multisensor integration in a single chip, for both optical and electrical domains,
are also discussed.
G. Barillaro (*)
Dipartimento di Ingegneria dellInformazione, Universit di Pisa, Pisa, Italy
e-mail: g.barillaro@iet.unipi.it
DOI 10.1007/978-3-319-05744-6_86
845
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G. Barillaro
Introduction
Gas sensors, which are a subset of the broader family of chemical sensors, allow
inferring on the chemical species present in the surrounding environment. An ideal
gas sensor should have high sensitivity, high specificity, small limit of detection,
high resolution, high accuracy, high precision, large dynamic range, null offset,
high linearity, null hysteresis, short response time, and long operation life (see
Korotcenkov (2013)). Of course, no current gas sensors meet all these requirements
simultaneously, which are, on the other hand, neither achievable nor necessary at
the same time in real-world applications.
The analysis of the state of the art of porous silicon gas sensors highlights how
the early studies were mostly focused on the development of suitable readout
approaches with the aim of investigating the sensing properties of porous silicon
layers in sensor structures featuring both basic architecture (e.g., capacitor, monolayer) and simple surface chemistry (e.g., native surface or oxidized surface). On
the other hand, the latest studies are mostly focused on the integration of porous
silicon layers in sensor structures featuring advanced architectures (e.g., FET-like
transistors, stacked rugate filters, etc.) and sophisticated surface chemistry
(e.g., silanization, carbonization, metallization, etc.) with the aim of improving
sensitivity, selectivity, and reliability performance. Finally, optical and electrical
sensing platforms integrating array of porous silicon sensors with advanced features
on the same chip are envisaged in the near future, though still in their infancy today
(see handbook chapter Porous Silicon for Microdevices and Microsystems)
(Fig. 1).
Gas Sensing with Porous Silicon

In the last two decades, micro-, meso-, and nanostructured forms of silicon, namely,
porous silicon, have been demonstrated to be very effective for the fabrication of
integrated gas sensors with low-cost process and room temperature operation (see
Mizsei (2007), Ozdemir and Gole (2007), Saha (2008)). The increased specific
surface (by definition, accessible surface to volume ratio) of porous silicon, up to
107 times larger than bulk materials, ensures a stronger interaction between material
Fig. 1 Sketch of a
multilayered optical device
(on the left) and a FET-like
electrical device (on the right)
representative of the
last-generation architecture of
porous silicon gas sensors
847
surface and gas molecules and allows high sensitivity and good limit of detection to
be achieved for a large number of gaseous species (e.g., NOx and other inorganic
gases, organic compounds, among which explosives, hydrocarbons, alcohols,
halides, amines, ketones, etc.). Optical, electrical, and electrochemical approaches
have been established to be valuable for the detection of a multitude of different gas
species (both inorganic and organic). Changes in optical (e.g., refractive index,
radiative recombination processes, etc.) and electrical (e.g., dielectric constant,
conductivity, etc.) properties of the porous silicon material upon interaction
(adsorption and/or condensation processes) with the specific gas species have
been demonstrated through quantitative monitoring of the variation of different
parameters (e.g., photoluminescence spectrum; reflected, transmitted, and
diffracted optical power; capacitance; current; resistance; etc.) as a function of
the gas concentration. A number of architectures have been proposed for both
electrical (e.g., metal-based devices, among which capacitor, resistor, and Schottky
diode, and pn junction-based devices, among which diode, transistor, etc.) and
optical (e.g., monolayer-based devices, among which waveguide, and multilayerbased devices among which Bragg mirror, resonant cavity, rugate filter, etc.) gas
sensors with the aim of improving sensor performance (e.g., improve sensitivity,
limit of detection and selectivity, compensate for baseline drift, compensate for
measurement angles, etc.). An equivalent large number of readout approaches (e.g.,
spectrometry, interferometry, ellipsometry, birefringence, conductometry, impedance spectroscopy, etc.) have been reported for monitoring the sensor parameters,
by using both single-parameter and multiparameter approaches. Besides, a number
of functionalization schemes (e.g., oxidation, hydrosilylation, carbonization, metallization, etc.) of the porous silicon surface have been proposed with the aim of
reducing aging and interfering effects while improving reliability, sensitivity, and
selectivity. See, for example, the handbook chapter Silicon-Carbon Bond
Formation on Porous Silicon. Tables 1 and 2 provide the main architectures of
porous silicon electrical and optical gas sensors, respectively, since 1990. The
porous silicon physical parameters that mainly account for the variation of the
sensed quantity for the specific sensor architecture are also indicated along with
the gas species sensed (Table 3).
Sensing Platforms
More recently, in addition to mere sensor devices exploiting either single-parameter
or multiparameter monitoring, miniaturized sensing platforms integrating a number
of porous silicon optical sensors featuring different surface chemistry on the same
chip, as well an array of porous silicon electrical sensors together with CMOS
electronic driving/readout circuits on the same chip, have been demonstrated to be
feasible, thus envisaging the realization of a new class of electronic and photonic
system-on-chips with gas sensing capability.
Table 4 provides study examples on up-to-date sensing platforms exploiting
porous silicon either electrical or optical gas sensors.
Timeline
Aliphatic and aromatic organic substances
Inorganic gases
(Andersson
et al. 1990;
Ben-Chorin and Kux
1994; Rittersma
et al. 2000; Foucaran
et al. 2000; Belhousse
et al. 2004;
Bjorkqvist
et al. 2004a, b, 2009;
Gabouze et al. 2005)
(Gabouze et al. 2005; Bjorkqvist et al. 2009;

Motahashi et al. 1995; Taliercio et al. 1995;
Angelucci et al. 1999, 2000; Mulloni et al.
2000; Di Francia et al. 2000; Baratto et al.
2000, 2001; Boarino et al. 2000; Setkus et al.
2001; Seals et al. 2002; Oton et al. 2003;
Chakane et al. 2003; Galeazzo et al. 2003;
Massera et al. 2004; Amato et al. 2004;
Gaburro et al. 2004b; Lewis et al. 2005, 2007;
Luongo et al. 2005; Rahimi and Iraji zad
2007; Sankara Subramanian et al. 2007; Gole
et al. 2007; Galstyan et al. 2008; Kovacs and
Meister 2009; Peng et al. 2009, 2012;
Ozdemir and Gole 2010; Moshnikov
et al. 2012; Laminack and Gole 2013)
Chronological order of exploitation of the different architectures for gas sensing since 1990
Aliphatic and
aromatic organic
substances
(Ben-Chorin
et al. 1994; Schechter
and Ben-Chorin 1995;
Mares et al. 1995;
Stievenard and
Deresmes 1995;
Bilenko et al. 1997;
Foucaran et al. 1997;
Zhang et al. 2000;
Pancheri et al. 2003;
Gaburro et al. 2004a,
2006; Razi et al. 2010;
Kanungo et al. 2010)
Aliphatic organic
substances
Study
examples
Inorganic gases
Inorganic gases
Sensed
species
Resistance
Conductivity
Current
Capacitance
Resistor
Conductivity
Schottky-like diode
Energy barrier
Sensed
quantity
Electrical Sensors
Metal-based devices
Sensor
architecture Capacitor
Physical
Dielectric constant
parameter
Table 1 Main architectures of porous silicon electrical gas sensors since 1990
(Barillaro et al. 2003,

2004, 2005; Archera
et al. 2005; Barillaro
et al. 2006, 2010a, b;
Lazzerini et al. 2013)
Aliphatic organic
substances
Dielectric constant
Current
Impedance
Inorganic gases
FET-like transistor
Conductivity
Junction-based devices
Inorganic
gases
Aliphatic
organic
substances
(Barillaro
et al. 2007a,
2008;
Prabakaran
et al. 2008)
Junction-like
diode
Energy
barrier
Conductivity
Current
848
G. Barillaro
Timeline
Study
examples
Sensed
species
Sensed
quantity
Sensor
architecture
Physical
parameter
Optical sensors
Monolayer-based device
Multilayer-based devices
Single layer
Waveguide
Bragg mirror
Resonant cavity
Radiative recombination efficiency
Refractive
Refractive index
Refractive index
index
Refractive index
Photoluminescence spectrum/intensity
Transmission
Reflectance spectrum
Resonance peak
losses
position
Reflectance spectrum
Inorganic gases
Aliphatic
Aliphatic and aromatic
Aliphatic and
organic
organic substances
aromatic organic
Aliphatic and aromatic organic
compounds
substances
substances
(Ben-Chorin et al. 1994; Baratto
(Arrand
(Zangooie et al. 1998;
(Mulloni et al. 2000;
et al. 2000; Lauerhaas et al. 1992;
et al. 1999;
Snow et al. 1999;
Zangooie et al. 1999;
Lauerhaas and Sailor 1993; Coffer et al. Rea
Allcock and Snow 2001;
De Stefano
1993; Lee et al. 1995; Rehm et al. 1995; et al. 2009)
Torres-Costa et al. 2005;
et al. 2003, 2004a, b)
Rehm et al. 1996; Harper and Sailor
Moretti et al. 2007;
1996; Kelly et al. 1996; Song and Sailor
Descrovi et al. 2007;
1997; Kelly and Bocarsly 1998; Content
Kim et al. 2010, 2011;
et al. 2000; Holec et al. 2002; Chvojka
Jalkanen et al. 2010)
et al. 2004; Salcedo et al. 2004; Dian
et al. 2005, 2010; Vrkoslav et al. 2006,
2007; Jelnek et al. 2007; Bjorklund
et al. 1996; Zangooie et al. 1997; Gao
et al. 2000, 2002a, b; Letant and Sailor
2000; Letant et al. 2000; Wang and
Arwin 2002; Liua et al. 2002; Lin
et al. 2004; Geobaldo et al. 2004;
Torres-Costa et al. 2009)
Chronological order of exploitation of the different architectures for gas sensing since 1990
Table 2 Main architectures of porous silicon optical gas sensors since 1990
Inorganic gases
Aliphatic and aromatic
organic substances
(Li et al. 2003; King
et al. 2008, 2010;
Chapron et al. 2007;
Shang et al. 2011a;
Kelly et al. 2011a, b)
Reflectance peak
position
Rugate filter
Refractive index

849
850
G. Barillaro
Table 3 Sensed species with electrical and optical porous silicon gas sensor architectures of
Tables 1 and 2
Substances sensed with electrical and optical porous silicon gas sensors
Inorganic gases
Hydrogen, oxygen, water, carbon monoxide (CO), nitric oxide (NO),
nitrogen dioxide (NO2), halogens (F2, Cl2, Br2, I2), hydrofluoric acid
(HF), hydrochloric acid (HCl), ammonia (NH3), hydrogen sulfide
(H2S), sulfur dioxide (SO2), phosphine (PH3)
Aliphatic organic
Methane, ethane, propane, butane, pentane, hexane, heptane, liquified
substances
petroleum gas (LPG), cyclohexane, ethylene, methanol, ethanol,
1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, glycerol
(1,2,3-propanetriol), diethyl ether, tetrahydrofuran, acetone,
metylethylketone (2-butanone), n-propylamine, n-butylamine,
n-pentyamine, triethylamine, tri-n-propylamine, ethyl acetate,
acetonitrile, dimethylformamide, chloroform (trichloromethane),
methylene chloride (dichloromethane), trichloroethylene (C2HCl3),
cyclohexyltrichloroethylene
Aromatic organic
Benzene, toluene, chlorobenzene, nitrobenzene, 1,4-dinitrobenzene,
substances
dinitrotoluene (DNT), trinitrotoluene (TNT)
Table 4 Electrical and optical sensing platforms with porous silicon

Porous silicon sensing platforms
Electrical Array of
On-chip
FET-like
electronics
transistor
sensors
Optical
Array of
Different
rugate filter
surface
sensors
chemistries
on chip
NO2 detection
Study examples
(Barillaro et al. 2007b;
Barillaro and Strambini
2008)
HF, HCl,
aliphatic organic
substance
detection
(Ruminski et al. 2011;

Shang et al. 2011b;
Sweetman and Voelcker
2012)
Summary
Over the last two decades, electrical and optical gas sensors based on porous silicon
have been tremendously improved, in terms of architectures, performance, and
sensed species. On the one hand, single devices with high sensitivity, low limit of
detection, and good selectivity have been achieved for different analytes, although
reliability and lifetime still remain among the major challenges for both electrical
and optical sensors. On the other hand, multiparametric sensing on single devices
and multisensor integration in a single chip have been very recently reported for
both optical and electrical approaches, thus pushing porous silicon gas sensors to a
new generation of miniaturized sensing platforms. As to the latter, tremendous
improvement due to simultaneous integration of sensors with electronic and photonic silicon circuits is expected for both approaches, respectively, in the next
future.
851
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Porous Silicon Optical Biosensors

Giorgi Shtenberg and Ester Segal
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photoluminescence-Based Transducers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reflectance-Based Transducers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Targeting of Small Molecules (Short Peptides, Low Molecular Weight Drugs) . . . . . . . . . .
Detection and Recognition of Moderate-Size Biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sensing of Complex Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions and Future Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
The rapidly developing field of porous silicon-based biosensors that utilize

optical transduction is comprehensively reviewed by distinguishing the differing
strategies for small- and moderate-size biomolecular analytes and the challenges
with analysis of complex biofluids. A number of topics are identified for future
research that should lead to one-shot disposable chip-based systems becoming
commercially avialable.
G. Shtenberg
The interdepartmental Program of Biotechnology, Department of Biotechnology and Food
Engineering, Technion Israel Institute of Technology, Haifa, Israel
e-mail: giorgi3@gmail.com
E. Segal (*)
Department of Biotechnology and Food Engineering, The Russell Berrie Nanotechnology
Institute, Technion Israel Institute of Technology, Haifa, Israel
e-mail: esegal@tx.technion.ac.il
DOI 10.1007/978-3-319-05744-6_87
857
858
G. Shtenberg and E. Segal
Introduction
Biosensors are analytical devices that incorporate a biological or a biomimetic
recognition element (e.g., enzyme, antibody, antigen, nucleic acid, imprinted polymers, etc.) with a physiochemical transducer (Vo-Dinh and Cullum 2000; Borisov
and Wolfbeis 2008). Thus, the major function of a biosensor is to convert the
biological recognition event into a measurable and quantifiable signal (Lim 2003).
Biosensors are generally classified into subgroups according to the signal transduction mode such as optical, electrochemical, and mass-sensitive measurements
(Vo-Dinh and Cullum 2000; Mello and Kubota 2002; Nirschl et al. 2011). Optical
biosensors offer significant advantages over both conventional analytical
techniques (Nirschl et al. 2011) and other types of sensors for multi-target sensing
and continuous monitoring (Ligler 2008). Thus, these powerful detection
and analysis tools have vast applications in biomedical research, healthcare,
pharmaceuticals, food safety, environmental monitoring, and homeland security
(Ligler 2008).
The application of porous Si (PSi) substrates for biosensing was first described
by Thust et al. (Thust et al. 1996; Schoning et al. 1997), demonstrating a
potentiometric biosensor for the detection of penicillin. However, it is the
pioneering work of Sailor and co-workers on PSi-based optical biosensors (Lin
et al. 1997; Janshoff et al. 1998; Dancil et al. 1999) that has inspired the extensive
research in the field (Kilian et al. 2009a; Weiss et al. 2009; Jane et al. 2009;
Pacholski 2013). Indeed, over the past decade, PSi has emerged as a promising
nanomaterial for label-free optical biosensing applications as its optical properties, i.e., photoluminescence (PL) and reflectance, are highly sensitive to the
presence of chemical and biological species inside the pores (Kilian
et al. 2009a; Cullis et al. 1997; Massad-Ivanir et al. 2011; Sailor and Wu 2009).
PSi offers a unique combination of versatile photonic architectures with large
volume and surface area, which can be easily functionalized with a wide repertoire surface chemistries, allowing the design of sophisticated biosensing platforms (Jane et al. 2009; DeLouise et al. 2005; Orosco et al. 2009; Miller 2010;
Bonanno and DeLouise 2010; Bonanno and Segal 2011; Massad-Ivanir
et al. 2010; Dhanekar and Jain 2013).
This chapter reviews the work on PSi nanomaterials for optical
biosensing application. We discuss the basic sensing concepts and describe
different strategies for detecting a wide dynamic range targets from small
molecules to whole cells. Other handbook chapters of most relevance
include Porous Silicon Multilayers and Superlattices, Photolithography on Porous Silicon, Refractive Index of Porous Silicon,
Photoluminescence of Porous Silicon, Functional Coatings of
Porous Silicon, and Porous Silicon for Microdevices and
Microsystems.
859
Photoluminescence-Based Transducers
The seminal discovery of visible light emission from PSi has sparked innovative
research toward PSi-based optical sensing methodologies (Jane et al. 2009). Both
theoretical and experimental works have demonstrated the versatility of PSi
nanostructures as biosensing platform for a multitude of biologically relevant
targets (Cullis et al. 1997; Chan et al. 2001a; Reardon et al. 2009; Saar 2009;
Singh et al. 2009; Dian et al. 2010).
The photoluminescent properties of PSi may be employed for sensing or
biosensing by exciting a sample and directly looking for the PL spectrum of the
analyte or by indirectly observing changes in the PL of PSi as affected by the
analyte (Sailor and Wu 2009). For example, it has been observed by a number of
different groups that the PL emission from PSi is quenched upon exposure to
specific solvent vapors and/or biomolecules (Cullis et al. 1997; Sailor and Wu
2009; Lauerhaas et al. 1992). Quenching of the PL may be due to binding of the
molecule (i.e., DNA, protein, enzyme, antibody) to the surface of the PSi nanostructure (Starodub et al. 1999, 2009; Di Francia et al. 2005; Chaudhari et al. 2005),
which introduces a site for non-radiative recombination of excitons, interfacial
charge, energy transfer, or modification of the dielectric constant of the surrounding
medium (Cullis et al. 1997; Sailor and Wu 2009). Chan et al. have shown that a
luminescent porous silicon layer (inserted between two Bragg reflectors in order to
alter the broad luminescence band into multiple narrow peaks) allows the detection
of short oligonucleotides of DNA as well as full-length viral DNA (Chan
et al. 2001a). Recognition and binding of the viral DNA to a partial complementary
DNA sequence, which is immobilized in the porous matrix, is confirmed through
PL spectral shifts. Thus, DNA hybridization produces a change in the effective
refractive of the PSi film, inducing a redshift in the PL spectra. The same group has
also introduced the first Si analogue of the Gram stain by using the same PSi
optical structure (Chan et al. 2001b; Pal et al. 2012). By functionalizing the inner
surface of the PSi layer with highly selective synthetic receptor molecules aimed at
the target bacteria lipid A, a redshift in the PL spectrum was observed only in the
presence of Gram ( ) bacteria. In recent years, PL-based biosensors are less studied
in comparison to sensors relying on reflectance-based interferometry (Bonanno and
Segal 2011). This is related to the comparative greater error associated with
measuring photoluminescence intensity changes (Sailor and Wu 2009).
Reflectance-Based Transducers
Biosensors relying on reflectance-based interferometry have become a widespread
technique for the detection of a variety of target analytes, e.g., small molecules
(Orosco et al. 2009; Sciacca et al. 2009, 2011), DNA (Borisov and Wolfbeis 2008;
860
Fig. 1 A schematic illustration of a reflectivity-based biosensor based on a single-layer PSi film

and the sensing concept. The PSi nanostructure is illuminated with white light perpendicular to
sample surface, while the reflected light is captured and detected by a spectrometer. The obtained
reflectance spectrum is Fourier transformed (FFT) into an effective optical thickness (EOT) . The
biorecognition event, between the bioreceptor and its analyte, manifests changes in the reflectivity
spectra
Lin et al. 1997; De Stefano et al. 2007; Rong et al. 2008; Rea et al. 2010), proteins
(Dancil et al. 1999; Pacholski et al. 2005, 2006; Ouyang et al. 2005; Latterich and
Corbeil 2008), enzyme activity (DeLouise et al. 2005; Orosco et al. 2009; Starodub
et al. 1999; Kilian et al. 2007, 2009b; Sailor 2007; Shang et al. 2010, 2012; Qiao
et al. 2010; Shtenberg et al. 2012), bacteria (Massad-Ivanir et al. 2010, 2011, 2012;
Alvarez et al. 2007), and mammalian cells (Schwartz et al. 2006). The simplest
structure for reflectivity-based sensing measurements consists of a single-layer PSi
film. Under perpendicular white light illumination, reflectance interference fringes
are observed in the visible and near infrared, and the fringe maxima are determined
by the effective optical thickness (EOT) of the film; see Fig. 1. Upon penetration of
molecules into the pores, the average refractive index of the film changes accordingly, resulting in a shift of the spectral position of the fringes (Fig. 1). More
complicated photonic structures, e.g., rugate filters (Lorenzo et al. 2005), dielectric
mirrors (Pacholski 2013; Allcock and Snow 2001), and microcavities (DeLouise
et al. 2005; Bonanno and DeLouise 2007a), have been utilized for biosensing,
providing sharp spectral features for improved spectral sensitivity. However, the
basic principle of sensing in each of these structures remains the same. One of the
main advantages of PSi in comparison to planar optical transducers is the ability of
the nanostructure to separate the analytes based on their intrinsic characteristics
(physical dimensions). The concept is schematically illustrated in Fig. 2, while
861
Fig. 2 A schematic illustration of the PSi nanostructure-sensing concept. The PSi nanostructure
physically separates a variety of target analytes and specific detection is facilitated by the
incorporation of appropriate capture pores on the surface. Whole cells and microorganisms are
excluded from the pores and may be immobilized onto the PSi surface (a), while moderate- (b) and
small-size (c) molecules are captured within the pores
specific detection of target analytes is achieved by appropriate surface chemistry

and immobilization of biorecognition elements as will be discussed in the following
sections.
Targeting of Small Molecules (Short Peptides, Low Molecular

Weight Drugs)
Direct binding assays for small molecules detection inherently suffer from low
sensitivity. The small-size analytes produce EOT changes that are barely noticeable
by typical PSi transducers (Fig. 2c). Two methods are usually employed to enhance
the optical signal generated by specific attachment of a small analyte: conformational change of the bioreceptor after binding event and competitive assay (binding/
displacement of a larger molecule) (Miller 2010; Bonanno and DeLouise 2010).
The latter strategy is reported by Bonanno et al. for detecting opiates in urine by PSi
Bragg mirror transducer. Improved detection limits (approx. 3 orders on magnitude) are facilitated by antibody interaction with the immobilized opiate covered
PSi surface (Bonanno and DeLouise 2010). An alternative strategy for signal
amplification is by applying more sophisticated optical design (e.g., multilayered
devices, waveguides, responsive elements) (Weiss et al. 2009; Miller 2010;
Bonanno and Segal 2011). Orosco et al. have shown a self-reporting double-layer
nanoreactor capable of isolating and quantifying proteolytic reaction products
(short peptides) and assessing the kinetic parameters in a volume of 5 nL (Orosco
et al. 2009). DeLouises group has employed PSi microcavities as substrate for
short oligopeptide synthesis. Systematic monitoring of optical sensor responses
offers means for validating reaction completion (e.g., maximum EOT value after
each amino acid loading) (Furbert et al. 2008). A key challenge in PSi biosensors is
to effectively stabilize the nanostructure for operating in biological solutions, as PSi
862
oxidation and dissolution in aqueous environments lead to significant signal baseline drifts and signal loss (Kilian et al. 2009a; Tsang et al. 2012; Gupta et al. 2013;
Jalkanen et al. 2012). This step is crucial for the detection of small analytes, where
the produced signal is low. Sciacca et al. have demonstrated the use of PSi/chitosan
hybrids, in which chitosan oligomers are covalently attached to the PSi surface.
Exploiting polymer intrinsic properties resulted in improved baseline signal stability during the detection of small carboxylic acid-containing drugs in aqueous
solutions (caffeine, ibuprofen, and -hydroxybutyric acid, a model molecule for
gamma hydroxybutyrate, which is illegal drug known as a date rape drug) (Bonanno
and Segal 2011; Sciacca et al. 2011). Responsive PSi/hydrogel hybrids can also be
employed for amplifying the original detection signal, to increase the sensitivity of
the biosensor (Bonanno and Segal 2011). To demonstrate this concept, Krepker and
Segal have fabricated a bifunctional nanostructured platform for label-free optical
detection and quantification of organophosphorus compounds (OPCs) in aqueous
solutions (Krepker and Segal 2013). The biosensor is constructed from two
conjugated interacting compartments, i.e., the pH-responsive oxidized PSi (PSiO2)/
hydrogel hybrid, used as the optical transducer element, and organophosphorus
hydrolase-modified PSiO2 region, which functions as an array of nanoreactors for
the hydrolysis of OPCs. Exposure to the target analyte results in a rapid and
reproducible change in the optical reflectivity spectrum of the hybrid, allowing for
a label-free detection and quantification of OPCs in a simple and reliable manner.
Detection and Recognition of Moderate-Size Biomolecules

Moderate-size biomolecules, including DNA, proteins, antibodies, and enzymes,
represent the most widespread subcategory of targets that are studied by PSi-based
biosensors (Fig. 2b; Pacholski 2013; Gupta et al. 2013). Table 1 lists common
PSi-based transducers for detecting these families of biomolecules, the
biorecognition species, and the corresponding limit of detection of the biosensors.
The configuration of the majority of these biosensors relies on immobilization of
the biorecognition element to the PSi surface. The vast majority of studies employ
organosilanes to functionalize an oxidized PSi surface (Furbert et al. 2008;
Estephan et al. 2011; Szili et al. 2011) or hydrosilylation to react the hydrogenterminated silicon with alkenes or alkynes (Kilian et al. 2009a; Dian et al. 2010;
Guan et al. 2011a, b). An alternative biosensing configuration, which is most
relevant to enzymes, is to immobilize the enzyme substrates to the PSi surface
rather than the enzyme itself (Orosco et al. 2006, 2009; Kilian et al. 2007). This
biosensing strategy is particularly suitable for monitoring enzymatic activity.
Sensing of Complex Samples

Biosensor analyses of complex biological solutions remain challenging due to high
background levels, baseline drift or signal instability, and altering sensitivity which
863
Table 1 Moderate-size biomolecule detection by different PSi optical transducers

Analyte
family
Protein/
enzyme
DNA
Antibody
Analyte type
Horseradish
peroxidase
Trypsin inhibitor
Bioreceptor
DNA
Glutathione-Stransferase
Subtilisin
Organic
substrate
Gelatin
Lectins: Con A,
RCA60, UEA I,
LTL
25
oligonucleotides
24
oligonucleotides
24
oligonucleotides
Human IgG
Glycan
Human, rabbit,
goat IgG
Rabbit IgG
Human IgG
Trypsin
ssDNA
ssDNA
ssDNA
Antihuman
IgG
Protein A
Biotinstreptavidin
Organic
substrate
Limit of
detection
2.6 M
Transducer
Single PSi
layer
Double
layer
Microcavity
10 ng
mL 1
2 M
Bloch
surface
Waveguide
0.01 mg
mL 1
0.5 M
Single PSi
layer
Bragg
reflector
Waveguide
6 M
0.26 M
0.05 M
Single PSi
layer
Double
layer
Microcavity
0.2 g
mL 1
0.17 M
Waveguide
0.67 M
70 g
mL 1
References
Shtenberg
et al. (2012)
Shang
et al. (2010)
DeLouise
et al. (2005)
Qiao
et al. (2010)
Shang
et al. (2012)
De Stefano
et al. (2007)
Rea
et al. (2010)
Rong
et al. (2008)
Szili
et al. (2011)
Schwartz
et al. (2007)
Bonanno and
DeLouise
(2007b)
Pal et al. (2011)
arises from cross-reactivity of interfering species present in the sample (Byrne and
Diamond 2006). By exploiting the size-exclusion filtering capabilities of the PSi,
we can enhance the optical signal differentiation. Cells and proteins larger than the
nanoscale pores are size-excluded from penetrating the pores, resulting in minuscule interaction with the transducer surface (Fig. 2a). Bonanno et al. have developed label-free optical biosensors for the detection of rabbit IgG in whole blood
samples using PSi microcavity (Bonanno and DeLouise 2007a). Biotin-streptavidin
chemistry is utilized for antibody (anti-rabbit IgG) immobilization onto the porous
scaffold. Several whole blood and serum samples are tested for quantification of
target analyte via wavelength shift of the optical reflectance spectrum. The sensor
exhibits high target binding specificity, minimal cross-reactivity, and linear detection range <10 mg mL 1. Massad-Ivanir et al. have recently demonstrated a
biosensor design for direct cell capture (Escherichia coli) via intensity changes
with no prior sample processing (Massad-Ivanir et al. 2011). The real-time observation of bacteria attachment and detection of low concentrations (the current limit
of detection 103 cells mL 1, within a few minutes) may be used for rapid identification and quantification of food- and waterborne pathogens (Massad-Ivanir
864
et al. 2010, 2012). Pace et al. have also used intensity changes for monitoring the
formation of a planar phospholipid bilayer on PSiO2 thin film (Pace et al. 2012). A
double-layer Fabry-Perot interference model is used to validate the experimental
measurements performed in situ. The experimental data indicate a two-step reaction: the vesicles initially adsorb to PSiO2 surface as a monolayer, followed by
vesicle fusion and conversion to a lipid bilayer. This simple, nondestructive, realtime method can be extended for screening and characterizing more complex
biological reactions based on solid support (e.g., liposome, proteasome, mammalian cancer cells proliferation, and tissue culturing).
Conclusions and Future Outlook

Despite the major advancements in PSi-based biosensors over the past decade, we
have not yet witnessed the translation of this technology into commercial applications. The biosensor technology discussed in this chapter has all been laboratorybased research. In the near future, we expect to see further research aimed to
overcome sensitivity and specificity challenges posed by diagnostic testing in
complex fluids. This may be achieved by (i) integration of PSi biosensors with
advanced microfluidic manipulation techniques, which can accelerate the rate of
mass transfer and enhance the sensitivity, (ii) advancing the long-term stability and
robustness of PSi biosensors in biological media, and (iii) as the heart of any
biosensor is the biological recognition element, the incorporation of new
bioreceptors, such as aptamers and aptazymes, holds promise to improve both
selectivity and sensitivity while increasing the number and types of analytes that
can be detected.
Other key concerns that impede the commercialization of PSi-based biosensors
are related to their reusability and shelf life. These issues are overlooked in most
studies and are critical for the realization of a reliable biosensing device. Although
it is desirable to have biosensing schemes that can be regenerated and reused
repeatedly, we envisage PSi biosensors to be implemented as one-shot and
disposable devices. We believe that adaptation of existing microarray technologies
and integration with microfluidic systems will lead to PSi biosensing systems that
can meet the demands of healthcare diagnostics, food safety, and environmental
monitoring and detection.
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Porous Silicon-Based Mass Spectrometry

Yannick Coffinier and Rabah Boukherroub
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Desorption/Ionization Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mass Spectrometry Detection of Proteins on PSi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Atmospheric Pressure Mass Spectrometry on PSi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nanostructure-Initiator Mass Spectrometry (NIMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mass Spectrometry Imaging (MSI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Measuring Enzymatic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Affinity Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
870
871
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Abstract
The literature on the use of porous silicon as a matrix to capture and assist in
mass spectroscopy of molecular species is comprehensively reviewed. The
different analytical techniques are first described; then the range of compounds
analyzed and the different application areas that utilize such mass spectrometry
are covered.
Keywords
Mass spectrometry porous silicon applications
Y. Coffinier R. Boukherroub (*)

Parc de la Haute Borne, Institut de Recherche Interdisciplinaire (IRI), Groupe NanoBiointerfaces,
Villeneuve dAscq Cedex, France
e-mail: rabah.boukherroub@iri.univ-lille1.fr; rabah.boukherroub@univ-lille1.fr
DOI 10.1007/978-3-319-05744-6_88
869
870
Y. Coffinier and R. Boukherroub
Introduction
Invention of matrix-assisted laser desorption ionization (MALDI) for high molecular weight compound analyses by Karas and Hillenkamp (1988) was concomitant
with the development of a similar mass spectrometry method by Tanaka and
co-workers (Tanaka et al. 1988), which relies on metal nanoparticles mixed with
glycerol instead of organic UV-absorbing molecules, to promote ion formation.
This technique has been considered as the forerunner of laser desorption ionization
(LDI) methods that are now based on the single use of inert substrates. The
application of micro- and nanostructured materials as inorganic matrix was proposed to overcome problems encountered with classical MALDI analysis. Particularly, co-crystallization of the sample with an appropriate organic matrix is not
required, and subsequently, intense matrix peaks responsible for strong background
in the low-mass range of the spectra hampering sensitive detection of small
molecules are suppressed (Okuno et al. 2005; Peterson 2007; Walker et al. 2009).
One of the most significant development in this area has certainly been desorption/
ionization on porous silicon (DIOS), achieved by Siuzdak and co-workers (see
Fig. 1) (Wei et al. 1999). At least for certain classes of analytes, DIOS and related
techniques, the so-called surface-assisted laser desorption/ionization (SALDI),
amounted or even exceeded the sensitivity of conventional MALDI-MS and constituted a promising strategy for analyzing compounds in the low-mass range
(Trauger et al. 2004). Since such organic matrix-free LDI methods afford several
advantages, such as easy sample preparation, low background level, high salt
tolerance, and fast data collection, many laboratories have investigated this strategy
as an innovative analytical tool in chemistry and biology. Although a buoyant
literature is available on the development of a vast array of LDI-promoting substrates with very different physicochemical properties, only a very few ready-to-use
LDI target plates are present on the market. Among them, DIOS chips, which are
based on chemically modified porous silicon (MassPREPTM-DIOS targetTM from
Waters), and more recently nonporous germanium thin films (QuickMassTM from
Shimadzu) and nanowires silicon-based surfaces (NALDITM from Bruker
Daltonics), have been made available to the scientific community.
LDI-MS plate
Etched
Photopatterned
Spots
Porous Silicon
Laser Pulse
Mass Analysis
LDI-MS Cocaine
MH+
304
CH3 O
N
O CH3
O
O
182
Smalll Molecules
50
Fig. 1 Principle of DIOS (Reprinted from Lowe et al. 2009)
m/z
1000
871
Desorption/Ionization Mechanism
Although elucidation of ion production is possibly the most controversial and
elusive area of LDI mass spectrometry, the mechanism can be subdivided into
absorption, retention, radiation coupling and transfer, desorption, and ionization
reactions. Optical properties (UV-absorption, anti-reflective properties) as well as
thermal conductivity are very important features to take into account for the design
and synthesis of efficient LDI surfaces displaying high surface area/volume ratios.
It was reported that pore size and depth, surface porosity and roughness, could
affect LDI efficiencies (Wei et al. 1999; Shen et al. 2001; Lewis et al. 2003; Shenar
et al. 2008; Xiao et al. 2009; Piret et al. 2010, 2012; Chen et al. 2011; Dupre
et al. 2012).
Indeed, to perform LDI-MS analyses, the interfaces should primarily be able to
absorb photons from the pulsed laser, and the length of the porous layer should be
high enough to correctly absorb photons from pulsed laser irradiation. For example,
the laser penetration depth in silicon nanowires at the wavelength of 355 nm is
lower than 100 nm, considering the nanostructure optical absorption and reflection
in this energy range (Street et al. 2008). Secondly, analytes have to be correctly and
uniformly distributed inside the nanostructured layer to be efficiently desorbed and
ionized. Indeed, it was shown that the electrowetting process can be performed to
force analytes to penetrate inside porous silicon and silicon nanofilament surfaces
(Tsao et al. 2008). Applying higher voltages caused different degree of penetration
of analytes inside the nanostructured layer, thus increasing the signal to noise (S/N)
ratio of the MS detection. However, when the thickness of the layer was too high,
analytes could also be trapped deeply inside the nanostructured layer. Then,
although the energy was appropriately transferred to analytes, the desorption
stage (plume formation and expansion) could be less efficient and thus led to a
decrease of the detection sensitivity (Kang et al. 2005). Finally, the surface porosity
is known to contribute to a change in thermal conductivity of silicon and that
surface thermal conductivity decreased rapidly with an increasing porosity (Xiao
et al. 2009; Benedetto et al. 1997; Attaf et al. 2001; Shen and Toyoda 2003). Indeed,
the introduction of additional dangling bonds at defect sites ultimately leads to
disruption of continuous single crystalline structure and slows down phonon propagation and thermal electron movement. Then, thanks to a thermal mechanism
relaxation via non-radiative recombination (phonons) of electrons and holes,
desorption/ionization of analytes can occur.
Mass Spectrometry Detection of Proteins on PSi

Although these interfaces are primarily limited to the detection of small molecules,
some attempts concerning the detection of proteins on such matrix-free LDI
methods have been described in the literature. Roussel et al. made a direct
872
comparison of IR and UV soft laser desorption/ionization on a commercial MALDI

instrument with identical sample preparations on a silicon surface. It was found that
peptides and proteins in the mass range between 1 and 17 kDa could be desorbed
and ionized from a room temperature target using a 2.94 m IR laser with no
organic matrix (Rousell et al. 2004). The resulting IR matrix-free mass spectra are
similar to IR and UV-MALDI mass spectra in the m/z range below 6,000, and the IR
desorption/ionization mass spectra were characterized by a low level of interference
from low-mass ions. However, it was found that the detection limit is ten times
higher for the IR matrix-free method (300 fmol) compared to UV-MALDI
(30 fmol) and considerably higher IR laser fluence was required for ionization,
particularly for the larger analytes. By using a mid-IR laser (1.454.0 m) irradiation, Bhattacharya et al. studied by MS small and large size molecules by desorption/ionization on crystalline silicon (Bhattacharya et al. 2002). In that case, no
need to structure the Si wafer in contrary to UV-DIOS because under these
conditions (IR irradiation), bulk silicon is transparent and water and/or solvent
acts as matrix allowing ion production process.
Atmospheric Pressure Mass Spectrometry on PSi

Most of the mass spectrometry analyses are conducted under vacuum environment.
However, ambient mass spectrometry is a rapidly growing field that provides fast
and direct analysis of solid sample surfaces or liquid samples introduced on a
suitable surface (Alberici et al. 2010; Weston 2010; Huang et al. 2010; Chen
et al. 2010). For that, different ambient ionization MS methods, such as atmospheric
pressure desorption/ionization on porous silicon (AP-DIOS) (Huikko et al. 2003),
desorption electrospray ionization (DESI) (Takts et al. 2004), direct analysis in
real time (DART) (Cody et al. 2005), desorption atmospheric pressure chemical
ionization (DAPCI) (Takts et al. 2005), and desorption atmospheric pressure
photoionization (DAPPI) (Haapala et al. 2007), have been successfully used in
the direct analysis of compounds from various samples, such as body fluids (Cody
et al. 2005; Chen et al. 2006), fruits, plant leaves (Luosujarvi et al. 2010), milk
(Yang et al. 2009), banknotes (Cody et al. 2005), textiles (Cody et al. 2005; Chen
et al. 2007), and pharmaceutical formulations (Ifa et al. 2009; Green et al. 2010),
just to mention a few, without any sample pretreatment.
The most used ambient MS technique is DESI that employs a pneumatically
assisted charged spray to desorb and ionize the analytes (Takts et al. 2004). In most
cases, the desorption/ionization in DESI occurs by so-called droplet pickup mechanism where the charged droplets dissolve and desorb solid analytes from the
surface (Takts et al. 2004; Venter et al. 2006), followed by emission of ions
from the charged droplets in a similar process to conventional ESI (Kebarle and
Tang 1993). DESI provides good sensitivity, down to pgng (fmolpmol) range, for
polar compounds (Kauppila et al. 2006; Ifa et al. 2008), but the ionization efficiency
for nonpolar compounds may be poor (Haapala et al. 2007; Luosujarvi et al. 2010).
Variations of DESI, such as reactive DESI (Chan et al. 2010) and desorption
873
Fig. 2 Principle of DESI
ionization by charge exchange (DICE) (Chan et al. 2010), have been developed for
improving the ionization efficiency for nonpolar compounds. DESI-MS has been
used in many bioanalytical applications, including direct analysis of urine (Chen
et al. 2006; Chan et al. 2010; Manicke et al. 2009; Lin et al. 2008), blood (Wiseman
et al. 2010), skin (Zhao et al. 2008), hair, plants (Takts et al. 2004), and bacteria
(Song et al. 2007).
The electrocharged aerosol particles interact with the surface, and as a result of
their impact, the analyte is desorbed from the surface and ionized. Then, ions are
transferred to the mass spectrometer by an ambient pressure sample transfer line,
and mass spectra are recorded using an unmodified commercial mass spectrometer
equipped with an atmospheric pressure interface (see Fig. 2). DESI ionize both
small and large molecules (up to small proteins), and the efficiency of the desorption/ionization depends mainly on three factors: (i) physicochemical properties of
the analytes; (ii) the spray mixture, i.e., the solvent composition, pH, viscosity,
volatility, etc.; and finally (iii) DESI surface on which the analyte is deposited.
Indeed, the chemical composition, roughness, surface energy, and conductivity of
the surface are all factors that determine the behavior of a DESI surface.
DESI analyses can be routinely performed directly from the surface to be analyzed
within a few seconds without any sample pretreatment. These features make DESI of
potential interest as a method for in situ analyses in a wide variety of particular
instances. One such application is the analysis of explosives from surfaces that can
commonly be in the possession of airline passengers or can be used in airport security
inspections (plastics, floppy discs, glass, paper, metal, cotton swabs, etc.) (Takts
et al. 2005; Cotte-Rodriguez et al. 2005). However, if the sample exists in a form of
solution, analyte should be first deposited on dedicated surface. Among them we can
find etched glass, smooth glass, PTFE, PMMA, ITO, filter paper, TLC, PSi, and
874
silicon nanowires (Pol et al. 2008). It has been shown that the large surface area of PSi
allows application of a larger amount of sample than the other common surfaces.
Another ambient method, called AP-DIOS-MS, was also used for the identification of amphetamines and fentanyls in forensic samples. The principle is similar to
that of DIOS, but occurs at atmospheric pressure. The use of tandem mass spectrometry (MS/MS) allowed unambiguous identification of the amphetamines and
fentanyls (Pihlainen et al. 2005). AP-DIOS-MS/MS was also successfully applied
to the identification of authentic compounds from drug seizures. Common diluents
and tablet materials did not disturb the analysis and compounds were unequivocally
identified. The limits of detection (LODs) for amphetamines and fentanyls with
AP-DIOS-MS/MS were 13 pmol, indicating excellent sensitivity of the method
(Pihlainen et al. 2005). Protein digest analysis (250 fmol of bovine serum albumin) by
AP-DIOS-MS was also performed and gave better peptide coverage than the
AP-DIOS-MS method in the 2001,000 Da mass range (Laiko et al. 2002).
Nanostructure-Initiator Mass Spectrometry (NIMS)

NIMS was developed from the original DIOS technology but uses a liquid initiator
to facilitate desorption. As a result, the NIMS surface is stable in ambient air, has
improved reproducibility, enables direct biofluid analysis and tissue imaging, and
allows for a significantly expanded mass range (Northen et al. 2007; Greving
et al. 2011). NIMS initiators (silane, siloxane, or disiloxane based) are fundamentally different from MALDI matrices in that the initiators do not absorb UV energy,
most do not ionize, and the analytes are not co-crystallized with the initiator (Woo
et al. 2008). During NIMS desorption/ionization, the porous silicon absorbs laser
energy that results in rapid surface heating, vaporization of the trapped initiator, and
desorption/ionization of the adsorbed analyte without fragmentation (Northen
et al. 2007; Greving et al. 2011).
Mass Spectrometry Imaging (MSI)

Mass spectrometry imaging (MSI) of biological tissues is becoming a popular tool
within the scientific community, mainly as a routine complement of proteomic
workflows and also as a valuable source of information in drug-development,
metabolomics, and pharmacokinetics studies (Stoeckli et al. 2001; Franck
et al. 2009; Hsieh et al. 2010). It complements techniques such as immunochemistry and fluorescence microscopy for the study of the spatial arrangement of
molecules within biological tissues (see Fig. 3). In particular, small molecule
MSI can dramatically speed up the drug-development phase for novel drugs,
through the ability to rapidly and efficiently collect valuable information about
the distribution of drugs and metabolites in various organs after in vivo administration (Ronci et al. 2012). PSi combines the advantage of generating clean
spectra in the low-mass range with very limited analyte diffusion across the PSi
875
Fig. 3 Principle of MSI (Adapted from Stoeckli et al. 2001)
surface. This could ultimately lead to an improvement in the achievable lateral

resolution compared to conventional MALDI-MSI.
The possibility to selectively extract different classes of compounds by changing
the surface chemistry of the substrate, together with fast sample preparation,
acquisition times, high sensitivity, and longer source cleaning intervals, makes
DIOS-MSI an attractive alternative for metabolomics and drug-development studies. Furthermore, chemical modifiers can be covalently bonded to the PSi surface,
thus enhancing or modulating the affinity for target compounds in an analogous
fashion to conventional solidliquid extraction (Trauger et al. 2004; Lowe
et al. 2009; Go et al. 2007). Therefore, the PSi matrix acts simultaneously as a
support, an adsorption substrate, and an ionizing agent thereby facilitating extraction, enrichment, and detection in a single step. However, a major challenge for
effective implementation of MSI on PSi is the development of a suitable mechanism for transferring the small molecules from biological tissue sections onto the
PSi surface, without significant contamination from large biological molecules.
Yanes et al. investigated a MSI approach using PSi functionalized with
perfluorinated siloxane [bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl) tetramethyldisiloxane] which was coined nanostructured initiator mass spectrometry called
NIMS (Yanes et al. 2009; Patti et al. 2010). However, surprisingly, the potential of
NIMS imaging for the detection of small molecules in biological tissue has not been
thoroughly evaluated (Calavia et al. 2012). This may be related to the need for
extremely thin tissue sections of <5 m which are difficult to prepare and require
special cryosectioning skills (Yanes et al. 2009).
876
Measuring Enzymatic Activities

Thomas et al. have reported, for the first time, the monitoring of enzymatic activity
and enzyme inhibitor screening that have been successfully performed directly by
DIOS-MS (Thomas et al. 2001a). A number of enzyme systems were investigated
such as esterase, glucosidase, lipase, and exo- or endoprotease. Acetylcholine
esterase (AChE) was allowed to react with its naturally occurring substrate acetylcholine to produce choline. They reported that the presence of the enzyme on the
surface (in the concentration range investigated) did not interfere with the detection
of the small molecules of interest. The strength of this approach was further
demonstrated by its ability to directly determine the selectivities of enzyme
inhibitors. Three different inhibitors of AChE (huperzine A, tacrine, and
2,6-dimethoxyphenyl-N-butylcarbamate) were studied. Their inhibition potentials
were found to correlate with their relative inhibition constant values. MALDI and
ESI were also employed for comparison, but neither was found to produce a strong
and reproducible signal for choline. In addition, improvements to allow timeresolved kinetic analysis for reaction systems were reported by Nichols
et al. (2008). They used an integrated digital microfluidic system based on
electrowetting liquid droplet actuation with a PSi microchannel to perform a
chemical reaction in a continuous flow regime and an in-line investigation of
product formation by DIOS-MS in order to study an arginase system. The basic
idea of the microfluidic system is that the device first mixes an enzyme droplet and a
substrate droplet. This combined enzyme/substrate droplet then travels down a PSi
microfluidic channel, depositing a trace amount of reaction substrate and product
into the silicon pore walls. Because the pore size is tuned to be larger than the
substrate and product, but smaller than the mean diameter of the enzyme, the
enzyme is therefore sterically hindered from entering the pores. This not only
allows continuous substrate diffusion into the pores and the reaction to continue
down the line but also eliminates the need for quenching. Then, the whole device is
submitted to mass spectrometry, and the relative concentrations of the reactant and
product are monitored.
Affinity Mass Spectrometry

In 1993, Hutchens and co-workers described surface-enhanced laser desorption/
ionization (SELDI) technique, an affinity technology, which has progressed over
the last decade to become a powerful analytical an on-plate approach (Hutchens
and Yip 1993). SELDI is a distinctive form of laser desorption/ionization (LDI)
mass spectrometry in which the LDI probe plays an active role in the homogenization, preconcentration, amplification, purification, extraction, enrichment digestion, derivatization, synthesis, separation, and detection with complementary
techniques, prior to the desorption and ionization of the analytes by MALDI
(Merchant and Weinberger 2000). The principle of this approach is very simple.
877
Biomolecules are captured by adsorption, partition, electrostatic interaction, or

affinity chromatography on a solid-phase protein chip surface. Although SELDI
provides a unique sample preparation platform, it is similar to MALDI-MS in that a
laser ionizes samples that have been co-crystallized with a matrix on a target
surface. There are many examples of such SELDI plates and there also exist a
number of commercial lab-on-plate products for applications such as sample
focusing, selective concentration, purification, separation, and desalting, which
are mainly intended for use in proteomics and biomarker discovery (Tanaka
et al. 1988; Nelson et al. 2000). Indeed, akin concepts have been developed by
different research groups, inventors, and companies, e.g., Applied Biosystems, BD,
BioRad, Bruker Daltonics, high-throughput screening (HTS), Qiagen, or
Sequenom. It is clear the analytical on-plate surface became the heart of the
MS technology. Because the analyses of complex biological samples and sample
preparation play a critical role in obtaining good-quality mass spectra, methods
enhancing the throughput of the analytical process are still needed. In LDI-MS,
signal suppression from multiple components present in biological samples is a
significant disadvantage making sample focusing, selective concentration, purification, separation, and desalting steps crucial, notably for using in proteomics and
biomarker discovery. Few attempts concerning affinity SALDI-MS interfaces
porous silicon based have been described in the literature. Lowe et al. have
exploited the presence of certain functional groups and, in particular, fluorinated
species, such as pentafluorophenyl groups on the PSi surface, for the detection of
small hydrophobic molecules from complex biological samples by means of selective capture of hydrophobic species from aqueous solution and removal of abundant
hydrophilic species such as salts (Patti et al. 2010). While this development clearly
sets the stage for selective analysis in matrix-free LDI-MS, further advances will
depend particularly on surface modifications yielding specific molecular affinity.
Inroads have certainly been made to incorporate affinity capture in PSi LDI-MS
using immobilization of protein receptors (Zou et al. 2002; Hu et al. 2007; Meng
et al. 2004) or surface functionalization with fluorosilanes in combination with
perfluoroalkyl affinity tagged analytes (Calavia et al. 2012). However, these studies
have not yet demonstrated sensitive and selective capture of target analytes from a
mixture of structurally similar molecules in aqueous solution. Recently, Lowe
et al. performed the immobilization of antibodies antibenzodiazepine (Illicit
drugs) on porous silicon via isocyanate chemistry, producing an immunoaffinity
surface (Lowe et al. 2010). They have demonstrated that their interfaces are able to
selectively capture benzodiazepine from a mixture of two benzodiazepines and
cocaine detected by mass spectrometry.
Applications
In Tables 1 and 2, some of the main applications of porous silicon as inorganic
target for LDI-MS analysis, detection, and imaging of different classes of
compounds are summarized.
DIOS
Enzymatic
activities/
inhibitors
screening
NIMS
(Nimzyme)
DIOS
AP-DIOS
NIMS
Forensics
PSi in mass spectrometry

Applications
Ionization
Omics:
DIOS
proteomics,
AP-DIOS
cellulomics,
NIMS
metabolomics
DESI
MSI/
DESI
metabolite
DIOS
profiling
NIMS
AP-DIOS
On-plate
DIOS
enrichment
Inhibitor screening
Enzymatic Kinetics
Immobilized enzyme or
substrate on PSi
Co-deposition enzyme/
substrate/inhibitors
Immobilization of
substrate
Microfluidic
Hutchens and Yip (1993), Xu et al. (2004), Greis

(2007)
Huikko et al. (2003), Kebarle and Tang (1993),

Northen et al. (2007), Yanes et al. (2009),
75, Thomas et al. (2001b), Shen et al. (2004)
Patti et al. (2010), Meng et al. (2004), Lowe

et al. (2010)
Immobilized anti-cocaine
antibody
Fluoro-tagged compounds
and fluorinated PSi
Hydrophobic interaction (fluorotagged compounds and fluorinated

PSi)
Biotinavidin interaction
Suspect sexual assault investigation
Drug seizure
Drug abuse detection
Explosive
Enzymatic activities
Woo et al. (2008), Stoeckli et al. (2001), Go

et al. (2007), Liu et al. (2007)
Details see Table 2
Tissues imaging
Disease diagnosis
Biomarkers discovery
Pharmaceutical tissue distribution
Immuno-specific capture
References
Greving et al. (2011), Patti et al. (2010), Hutchens
and Yip (1993), Vaidyanathan et al. (2005), Fuchs
et al. (2010), Liu et al. (2007), Law and Larkin
(2011), Prenni et al. (2003), Miura et al. (2012)
Remarks
Details see Table 2
Principle
Small compounds detection
Table 1 Main applications of PSi in mass spectrometry
878
Lipidsfatty
acids
NIMS
DIOS
DESI
DIOS
NIMS
DESI
DIOS
Amino acids
Steroids
DIOS
AP-DIOS
NIMS
DESI
Ionization mode
DIOS
NIMS
Drugs,
xenobiotics,
pharmaceuticals
Class of
compounds
Carbohydrates
Molecules
Mannose
Borate complexed : xylose, arabinose, ribose, lyxose
Sucrose
Raffinose
Maltotriose
Glucose (Fluoro-tag)
Amphetamines, fentanyls, midazolam, diazepam,
tetrahydrocannabinol (THC), dobutamine,
benzodiazepines, cocaine, raclopride, nicotine, cotinine
(metabolite of nicotine), ketamine, norketamine, clozapine
(antipsychotic), propafenone, verapamil, Sutent, reserpine,
paracetamol, naphthoquinone, propranolol, dopamine,
VitB12, caffeine, etc.
Various (histidine, arginine, tryptophan, methionine,
phenylalanine, etc.)
Fluoro-tagged amino acids
Pregnenolone, Pregnenolone sulfate
Testosterone
Acetylcholine (ACh), choline (hydrolysis of Ach),
cholesterol, 1-palmitoyllysophosphatidylcholine,
phosphatidylethanolamine, lysophosphatidyl,
phosphocholine (DPPC)
Table 2 Main classes of compounds detected by LDI-MS on PSi
(continued)
Kebarle and Tang (1993), Woo et al. (2008), Thomas

et al. (2001a), Hutchens and Yip (1993), Fuchs et al. (2010),
Liu et al. (2007), Budimir et al. (2006), Reindl and Northen
(2010)
Kebarle and Tang (1993), Lewis et al. (2003)
Trauger et al. (2004), Woo et al. (2008) Patti et al. (2010),

Vaidyanathan et al. (2005), Lewis et al. (2003), Chen
et al. (2008), Vaidyanathan et al. (2007)
Huikko et al. (2003), Kebarle and Tang (1993), Northen

et al. (2007), Calavia et al. (2012), Yanes et al. (2009),
75, Liu et al. (2007), Law (2010), Ostman et al. (2006),
Nordstrom et al. (2006)
References
Trauger et al. (2004), Thomas et al. (2001a), Patti
et al. (2010), Compton and Siuzdak (2003), Li et al. (2005),
Law (2010)

879
DIOS
Polymers,
chemicals
Explosive
NIMS
Nucleotides
DIOS (Ion
Mobility S)
AP-DIOS
DIOS;
NIMS
Ionization mode
DIOS
AP-DIOS
NIMS
Proteins
Class of
compounds
Peptidesprotein
mass fingerprint
(digests)
Table 2 (continued)
Molecules
BSA, casein, cytochrome C,
Adenovirus penton protein
Flock house virus protein
Hemagglutinin (influenza virus type A)
B-Lactoglobulin
Numerous peptides (bradykinin, neurotensin,
fibrinopeptide, etc.)
Thymopoietin
Leucine-enkephalin, angiotensin
Phosphopeptides (fluoro-tag)
Beta lactoglobulin
Cytochrome C
Myoglobine
Bovine serum albumin (BSA)
Membrane protein bacteriorhodopsin
XDP (U, A, G)
XTP (U, A, G)
PEGs, spermicides (nonoxynol-9, octoxynol-9),
terephthalate (dye)
Dodecyltrimethylammonium chloride
Propidium iodide, brominated indoles
Pyrazole, fluorescein, naphthalene, etc.
Polystyrenes
Organic dyes (rhodamine B, methylene blue, etc.)
Putrescine, pyruvate, malate, etc.
TNT
Martynov et al. (2011)
Go et al. (2007), Vaidyanathan et al. (2005), Liu

et al. (2007), Thomas et al. (2001b), Shen et al. (2004),
Ostman et al. (2006), Ciolacu et al. (2006), Seino
et al. (2005), Okuno et al. (2004)
Amantonico et al. (2009)
Rousell et al. (2004), Bhattacharya et al. (2002), Woo

et al. (2008)
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Greving et al. (2011) Woo et al. (2008), Patti et al. (2010),
Hutchens and Yip (1993), Liu et al. (2007), Law and Larkin
(2011), Prenni et al. (2003), Lewis et al. (2003)
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Porous Silicon Immunoaffinity Microarrays

Belinda Adler, Hong Yan, Simon Ekstrom, and Thomas Laurell
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Surface Fabrication and Fluid Interaction Properties of Microarrays . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Antibody Microarrays for Prostate-Specific Antigen (PSA) . . . . . . . . . . . . . . . . . .
Immunoaffinity Extraction on Porous Silicon Microarrays and MALDI MS Readout . . . . . . .
Fluorescence Quenching Assay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon as Substrate for Sol-Gel Aptamer Microarrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
887
888
889
891
894
895
896
Abstract
Porous silicon with immobilized recognition biomolecules is an attractive platform for many microfluidic chip-based bioanalytical applications. We review
the progress in the field since its earliest developments in the 1990s. An
improved assay for early detection of prostate cancer has reached clinical
evaluation, but there are also exciting developments in both aptamer-based
biosensing and mass spectrometry-based biosensing.
Introduction
Protein microarray technology has emerged as excellent high-throughput method
(Kambhampati 2004; Schena 2004; Korf 2011). Porous silicon has gained attention
as an attractive substrate for immobilization of proteins on microchip surfaces in
microarray applications (Ressine et al. 2007). Its inherently large surface area
yields a high loading capacity of macromolecules when integrating microchip
B. Adler (*) H. Yan S. Ekstrom T. Laurell

Faculty of Engineering, Department of Biomedical Engineering, Lund University, Lund, Sweden
e-mail: belinda.adler@bme.lth.se; thomas.laurell@bme.lth.se
DOI 10.1007/978-3-319-05744-6_89
887
888
B. Adler et al.
Fig. 1 Example of an early

porous silicon enzyme
microreactor with surfaceenlarging parallel
microchannels,
anisotropically etched in
silicon followed by a porous
silicon anodization step
structures with biospecific proteins, e.g., enzymes or antibodies in microfluidic

systems. Early work in coupling enzymes to porous silicon for biospecific sensing
was reported by Laurell et al. (1996) (Fig. 1) where glucose oxidase was
immobilized covalently in porous silicon microchannels as part of a miniaturized
glucose monitoring system. In parallel Thust et al. (1996) reported physical adsorption of penicillinase on porous silicon where the chip served as a pH-sensitive
potentiometric structure that monitored the H+ ion generation as the enzyme
converted penicillin G. Simultaneously Lin et al. published the groundbreaking
paper on porous silicon as a Fabry-Perot-based sensor for biomolecule binding (Lin
et al. 1997), opening the route to a broad range of developments of optically based
biomolecular sensor applications. These are all examples of early developments
that have brought attention to porous silicon as a micro-/nanostructured material for
highly efficient and sensitive bioanalytical applications. The continued developments of biospecific sensing using immobilized recognition biomolecules and
optical detection techniques are covered elsewhere in this book (chapters Porous
Silicon Membranes and Porous Silicon Optical Waveguides). The use of
porous silicon, integrated in microfluidic structures in the format of flow-through
enzyme microreactors (Drott et al. 1997), has since been further developed in
numerous applications: sucrose analysis with FTIR detection (Lendl et al. 1997),
protein analysis linked to mass spectrometry (Ekstrom et al. 2000), atrazine
immunoassaying (Yakovleva et al. 2002), cellulose analysis (Melander
et al. 2005), and starch analysis (Melander et al. 2006) to mention a few.
Surface Fabrication and Fluid Interaction Properties

of Microarrays
To prepare porous silicon microarrays in the Laurell group, 380 m-thick <100>
silicon wafers were utilized. The p-type boron-doped wafer with a resistivity of
1015 cm was mounted in an in-house-made electrochemical etch cell. The
porosification was made in an electrolyte solution of HF/DMF 1:10, and the
889
wafer was illuminated by a 100 W halogen lamp at a distance of 10 cm. A current

density of 2 mA/cm2 was applied for 1 h. The macropores in the porous layer
produced for protein microarrays typically measured 0.51.5 m with a fine side
branching network of nanopores (Ressine et al. 2005).
Porous silicon offers attractive features in terms of solid/fluid interaction where
the macro-/nano-sponge silicon network, depending on the pore morphology, may
act as a hydrophobic surface in a Cassie-Baxter mode (Cassie and Baxter 1944).
This is in spite of the fact that oxidized silicon is hydrophilic. This effect was
specifically utilized by Ressine et al. (2003, 2005) in an early work of developing
antibody microarrays on porous silicon where the hydrophobic properties of the
pore morphology yielded a high surface area, providing an improved limit of
detection and a homogenous antibody coverage, on each micro spot in the microarray. The beneficial effects of the high fluid contact angle of the porous silicon
eliminated the well-known coffee ring effect. This is explained by the fact that the
evaporation rate from a droplet with a contact angle larger than 90 displays an
evaporation rate at the fluid/solid contact line that is lower than along the rest of the
fluid-air interface. Thereby, the enrichment of antibody molecules at the fluid/solid
interface is avoided which otherwise is the case for low-contact-angle antibody
droplets (Ressine et al. 2005). In addition, and most importantly, the porous silicon
displays excellent properties in immobilizing antibodies solely by physical adsorption without the need for extensive covalent coupling protocols.
The Cassie-Baxter mode also yielded a minimized footprint of the deposited
droplets, hence allowing the production of high-density noncontact printed arrays
(14,000 spots/cm2) (Ressine et al. 2007). The fact that the surface is hydrophilic on
a molecular scale is highly beneficial since the antibody has a lower risk of being
denatured and lose its biospecific activity in contrast to what would be the case for,
e.g., a highly hydrophobic fluoro-terminated surface. It should also be noted that the
macro-/nanoporous silicon used for antibody microarrays displays a very low
unspecific binding and hence a low background fluorescence.
Porous Silicon Antibody Microarrays for Prostate-Specific

Antigen (PSA)
Prostate cancer is the most common cancer form in males in the USA and Western
Europe. One of the methods to diagnose prostate cancer is to measure the prostatespecific antigen (PSA) which leaks into the bloodstream from the prostate. In cancer
patients the cells in the prostate are growing unrestrained and become more unstructured which leads to an increased leakage of PSA into the blood. But only 25 % of
men with elevated PSA levels have prostate cancer, while the remaining patients
have, for example, benign prostatic hyperplasia (BPH) or a temporary infection. This
makes it important to develop improved and more differentiated PSA assays to
enable discrimination of patients with malignant disease.
In this perspective Ressine et al. developed porous silicon as a solid support for
PSA antibody arrays (Ressine et al. 2005). The morphology of the porous silicon
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B. Adler et al.
was optimized for fluorescence microarray applications. The assay was initially
developed in a direct labeling format, i.e., PSA was fluorescently labeled with FITC
and captured by the anti-PSA antibody 2E9 that was microarrayed and immobilized
by physical adsorption on the porous silicon. The PSA-FITC was spiked into human
serum to investigate the assay performance in a complex and clinically relevant
sample. The detection limit for PSA was 0.7 ng/ml, which corresponded well to the
reference limit of 34 ng/ml where decisions on clinical actions may be taken. This
work was later followed up by Jaras et al. who demonstrated that a PSA sandwich
microarray assay had increased sensitivity compared to the assay performance of
reverse assay format (the antigen is spotted onto the surface and detected with an
antibody) (Jaras et al. 2007). The sandwich assay, consisting of one capture and one
detector antibody, displayed a five-orders-of-magnitude lower limit of detection,
0.7 ng/ml, as compared to 70,000 ng/ml (reverse assay) for PSA in buffer. The
better limit of detection was explained by the enrichment of PSA on the capture
antibody that was highly specific with a high affinity constant. To even further
increase the sensitivity, Jaras et al. used europium nanoparticles for signal enhancement (Jaras et al. 2008). The capture antibody was arrayed onto the porous silicon,
capturing biotin-labeled PSA in serum. The detection was done using polystyrene
nanoparticles loaded with europium for amplified detection and labeled with
streptavidin as the coupling functionality to the bound PSA. This signal enhancement protocol yielded a tenfold enhancement compared to europium-labeled
streptavidin; limit of detection 0.070.14 ng/ml for the nanoparticles and compared
favorably to 0.480.70 ng/ml for conventional europium-labeled streptavidin.
To further validate the PSA sandwich microarray assay, a study on patient
samples was performed. Jaras et al. (2012) successfully measured PSA quantitatively (dynamic range, 0.1444 ng/ml) in a cohort of 80 patients undergoing clinical
PSA testing (Fig. 2). To better discriminate prostate cancer from benign disease,
both total PSA and free PSA need to be quantitated. Therefore, Jaras et al. (2012)
also developed a sandwich duplex setup measuring total PSA and free PSA on the
same chip. The duplex was verified on 16 patient samples with the dynamic range
of total PSA 0.87295 ng/ml and free PSA 0.4074.9 ng/ml. Further developments
of this microarray format toward a multiplex diagnostic chip with the goal of a
triplex assay that measures total, free, and intact PSA on the same chip have also
been shown (Adler 2009). These experiments were carried out on a patient sample
diluted into four different concentrations and seemed to correspond well to the
clinically measured values.
The previously mentioned developments were all carried out on serum samples,
and in an effort to develop a diagnostic system with an outlook toward a point-ofcare application, it would be favorable to offer a diagnostic chip that operates with
whole blood as the input sample. In view of this Lenshof et al. (2009) and Tajudin
et al. (2013) coupled an acoustically driven plasmapheresis chip to the porous
silicon PSA sandwich microarray assay. The plasmapheresis chip eliminated erythrocytes and leukocytes from whole blood at a rate of 5080 l/min, by means of
acoustic forces in a continuous laminar flow system. The obtained plasma (1020
l/min) was subsequently routed to and assayed on the PSA microarray. Low
891
Fig. 2 Schematic of the assay sequence performed in the testing of the PSA assay on 80 patient
samples (Jaras et al. 2012) (Reprinted from Clinica Chimica Acta, 414, Jaras, Adler, Tojo, Malm,
Marko-Varga, Lilja, Laurell, Porous silicon antibody microarrays for quantitative analysis: Measurement of free and total PSA in clinical plasma samples, 7684. Copyright 2012, with permission from Elsevier)
abundant PSA with the concentration range of 0.19100 ng/ml was successfully
measured from whole blood in this integrated system.
Immunoaffinity Extraction on Porous Silicon Microarrays

and MALDI MS Readout
In addition to porous silicons use as an immobilization matrix for enzyme reactors
and optical biosensor material, it has been extensively used in the field of mass
spectrometry (see chapter Porous Silicon Phononic Crystals for a dedicated
review). The most widespread use of porous silicon in this field is as a medium for
matrix-less desorption/ionization on silicon (DIOS) (Wei et al. 1999). DIOS has
been applied for the analysis of many different analytes (Shen et al. 2001; Thomas
et al. 2001), although the technique is best suited for small molecular analysis (Kraj
et al. 2003; Arakawa et al. 2004; Pihlainen et al. 2005). One of the difficulties with
DIOS is the introduction of affinity elements without interfering with the ionization/desorption properties of the surface (Xu et al. 2004). In this respect the
application of unspecific affinity-modified porous silicon DIOS materials is more
convenient and has been demonstrated for, e.g., hydrophobic modification (Trauger
et al. 2004) and ion exchange (Luo et al. 2005; Shmigol et al. 2009). More specific
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B. Adler et al.
capture using DIOS has also been shown using biotinylation schemes (Mengistu
et al. 2005) and antibodies (Lowe et al. 2010; Chen et al. 2008). The application of
DIOS surfaces for pharmaceutical screening has been shown by using surfaces with
BSA or hemoglobin (Hu et al. 2007), where protein-bound drugs could be detected
by mass spectrometry (MS). A promising development of the DIOS is the
nanostructure-initiator mass spectrometry (NIMS) principle (Woo et al. 2008),
whereby addition of a fluoroorganic layer on the porous silicon material
fluorotagged substrates could be subjected to enzymatic screening on chip (Northen
et al. 2008). Due to the difficulties associated with retaining the ionization/desorption properties and achieving high reproducibility of the surface, no laser desorption/ionization (LDI)-based method to date has been able to consistently
outperform the standard matrix-assisted laser desorption/ionization (MALDI)
matrixes in affinity applications. An alternative approach to affinity porous silicon
microarrays for MS applications is therefore to focus on the surface enlargement
and low background binding characteristics of porous silicon and avoid use of the
porous silicon for the actual desorption/ionization step.
Porous silicon surfaces with various functional groups and biomolecules have
been developed to capture analytes for direct analysis by matrix-assisted laser
desorption/ionization mass spectrometry (MALDI) (Chen et al. 2009; Xu
et al. 2006; Zou et al. 2002). The combination of immunocapture and MALDI
(iMALDI MS) is highly desirable since the immunocapture reduces the complexity
of the sample to be analyzed at the same time as the target species is enriched,
thereby increasing the possibility of detecting the analyte of interest at lower
abundant levels (Sparbier et al. 2009). Compared with fluorescence readout, the
mass spectrometry analysis of an immunoassay can also serve to provide unequivocal identification of the captured antigens and be used to pinpoint different
structural variants of an antigen that may be linked to a disease state (Nedelkov
2008; Nedelkov et al. 2007). Along this line a chemical derivative-based
immunocapture strategy amenable for MALDI MS was developed in Xiaos
group (Chen et al. 2008), where N-hydroxysuccinimide (NHS)-ester-terminated
monolayers on porous silicon were used for covalent conjugation with antibodies
and then for the antigen capture. B-type natriuretic peptide (BNP) and BNP
derivatives with the concentration of 10 pg/mL were successfully detected by
MALDI with the matrix added onto the surface.
An earlier and analogous step along this line employed a porous silicon trypsinimmobilized enzyme reactor (IMER) that was operated in flow-through mode for
protein digestion prior to MALDI MS identification of the resulting peptide map
(Ekstrom et al. 2000; Bengtsson et al. 2002). Another example is the dual-readout
concept based on both fluorescence and MALDI MS presented by Finnskog
et al. (2004). Using this approach, antibody-captured FITC-labeled angiotensins
and IgG were first analyzed by fluorescence, and then the MALDI matrix was added
to the porous silicon chip for subsequent analysis by MALDI MS. A difficulty with
the dual-readout method was the confinement of the MALDI spot as the entire
surface was porous. In an effort to improve the spot confinement, porous silicon
nanovials (300 m in diameter and 25 m deep) were employed. The porous silicon
893
Fig. 3 Schematic workflow of porous silicon-ISET iMALDI: top (I), antibody-immobilized

porous silicon was used to capture the antigen angiotensin I; bottom (II), RP solid-phase extraction
sample preparation protocol on the ISET chip was used to purify and reconcentrate the elution
followed by MALDI MS detection (Yan et al. 2011) (Reprinted with permission from Analytical
Chemistry, 83, Yan, Ahmad-Tajudin, Bengtsson, Xiao, Laurell, Ekstrom, Noncovalent antibody
immobilization on porous silicon combined with miniaturized solid-phase extraction (SPE) for
array based immunoMALDI assays, 49424948. Copyright 2011 American Chemical Society)
nanovials were prefilled with trypsin solution, which was allowed to dry, after
which proteins and buffers were added by microdispensing. Porosified and
nonporosified nanovial arrays were compared for trypsin digestion and subsequent
MS identification of three model proteins: lysozyme, alcohol dehydrogenase, and
serum albumin at levels of 20 and 100 fmol. In an effort to assess the rapid digestion
platform in a context of putative clinical applications, two prostate cancer biomarkers, PSA and human glandular kallikrein 2 (hK2), were also digested at levels
of 100 fmol (PSA), 20 fmol (PSA), and 8 fmol (hK2). All biomarker digestions
were completed in less than 30 s, with resulting improvements in MS identification
using the porous nanovials (Finnskog et al. 2006).
In many immunoaffinity-capture assays, the analyte of interest is an intact
protein. When mass spectroscopy is to be used as final readout, the highest
sensitivity is obtained if the intact protein is digested into peptides. If this is done
on the antibody carrying surface, the drawback is that digested fragments of the
antibody also generate a large background. Therefore, a promising approach is to
elute the intact immunocaptured proteins by acid shock and transfer them to another
sample preparation platform for the digestion step. A key aspect in immunoaffinity
MALDI assays is the sample preparation step after the immunocapture, removing
buffer adducts, yet enabling reconcentration of the captured and displaced analytes
onto well-defined MALDI spots. In an earlier work, we have reported a chipintegrated microarray-based solid-phase extraction platform for MALDI MS sample preparation, the integrated selective enrichment target (ISET) (Ekstrom
et al. 2004, 2006, 2007), which allows multiple sample processing steps directly
on a MALDI target. Using reverse-phase (RP) ISET, sample preparation
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B. Adler et al.
Fig. 4 Schematic for the aptamer affinity-specific assay for adenosine based on the fluorescence
quenching properties of macroporous silicon as presented by Yoo et al. (Yoo et al. 2012)
(Reprinted from Biosensors and Bioelectronics, 41, Yoo, Ahn, Ahn, Laurell, Lee, Yoo, Lee, A
simple one-step assay platform based on fluorescence quenching of macroporous silicon, 477483.
Copyright 2012, with permission from Elsevier)
immunoaffinity-captured analytes can thus be reconcentrated after elution. If

needed, additional sample preparation steps such as digestion of immunocaptured
intact proteins can also be performed on-bead in the ISET microarray (Tajudin AA
et al. 2009). Recently Yan et al. reported a new strategy (Fig. 3) to combine the
power of antibody-based capturing of target molecules in complex samples on
porous silicon with the benefits of microfluidic sample preparation and the analysis
speed of MALDI MS (Yan et al. 2011). The performance of the immuno-MALDI
(porous silicon-ISET iMALDI) assay was evaluated by successful detection of
angiotensin I spiked in 10 L diluted plasma at 1 nM levels. Furthermore, using a
footprint conforming to the standard for 384-well microtiter plates, adaption of the
protocol to automated sample handling robots was also demonstrated.
Fluorescence Quenching Assay

Recently the group of J. Lee reported that a one-step aptamer-based affinity-specific
sensing assay can be performed on porous silicon utilizing the intrinsic fluorescence
quenching of porous silicon as the basis for detection (Yoo et al. 2012) (Fig. 4).
Macroporous silicon was initially streptavidin coated and subsequently activated
with a biotin-terminated capture aptamer directed against adenosine. The surfacebound capturing aptamer was conjugated with a secondary fluorescently labeled
895
detector aptamer. As long as the detector aptamer was bound to the surfaceimmobilized capture aptamer, the fluorescent label was quenched by the proximity
to the porous silicon surface (<30 nm). When adenosine was added to the sample
solution, competitive binding of adenosine to the capture aptamer released the
detector aptamer, which now became fluorescent as it diffused away from the
quenching porous silicon surface. When compared to the conventional fluorescence
quenching assay surfaces as polystyrene and ZnO nanorods, at least two orders of
improved limit of detection were obtained (from 10 M to 100 nM). The improved
assay sensitivity was attributed to both the excellent fluorescence quenching properties of porous silicon and the vast surface area for coupling the capture aptamer
complex.
Porous Silicon as Substrate for Sol-Gel Aptamer Microarrays

Macroporous silicon has also been used in applications for sol-gel encapsulated
affinity ligands where the porous silicon network served as a matrix for anchoring
ink-jet-spotted sol-gel droplet microarrays to the assay surface. Sol-gel microarrays
have proven to be an attractive means of immobilizing antibodies in a three-
Fig. 5 A sol-gel microarray on a macroporous silicon chip. Insert images show the morphology of
the sol-gel matrix and the actual anchoring of the sol-gel spot to the porous silicon surface (Ahn
et al. 2012) (Reprinted with permission from Analytical Chemistry, 84, Ahn, Lee, Jo, Kang, Kim,
Jeong, Laurell, Kim, Sol-gel derived nanoporous compositions for entrapping small molecules and
their outlook toward aptamer screening, 26472653. Copyright 2012 American Chemical Society)
896
B. Adler et al.
dimensional network that offers a very high sensitivity (LOD in the range of fg/ml)
in assaying antibodies against diseases such as hepatitis virus C (Kwon et al. 2008)
and HIV (Kim et al. 2006). Most importantly, aptamers can be immobilized in a
sol-gel matrix with retained binding specificity and activity (Lee et al. 2007). When
designing sol-gels for aptamers that are specific against small molecules, the assay
protocols commonly involve organic solvent-washing steps which cause the sol-gel
to detach from the assay surface. In order to alleviate this macroporous silicon
proven to be an inert substrate that retains the sol-gel spots independent of washing
conditions can be utilized (Ahn et al. 2012) (Fig. 5). Also, and most importantly, the
intrinsically low background signal obtained on porous silicon is of value in the
development of these assays.
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(SPE) for array based immunoMALDI assays. Anal Chem 83:49424948
Yoo L, Ahn KY, Ahn JY, Laurell T, Lee YM, Yoo PJ, Lee J (2012) A simple one-step assay
platform based on fluorescence quenching of macroporous silicon. Biosens Bioelectron
41:477483
Zou HF, Zhang QC, Guo Z, Guo BC, Zhang Q, Chen XM (2002) A mass spectrometry based
direct-binding assay for screening binding partners of proteins. Angew Chem Int Ed
41:646648
Porous Silicon in Brachytherapy

Leigh Canham and Drew Ferguson
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The Medical Isotope 32P and BrachySil TM Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
In Vitro Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preclinical Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Clinical Trials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ongoing Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
901
902
903
904
904
906
906
906
Abstract
Highly targeted radiotherapy (brachytherapy) was the first clinical application

of stain-etched silicon microparticles. We briefly review here the manufacture,
testing, and clinical use of the 32P:Si beta-emitting formulation for unresectable
hepatocellular and pancreatic carcinoma. Clinical data from a number of trials
suggests that the technology offers patients with inoperable solid tumors an
attractive alternative to external beam radiotherapy.
Introduction
Brachytherapy refers to forms of highly targeted radiotherapy where the radioactive
source is placed near or in the target tissue area. For interstitial therapy where the
source is placed within the tumor itself, high radiation doses can be applied with
L. Canham (*)
D. Ferguson
OncoSil Medical Ltd, Malvern Hills Science Park, Malvern, Worcestershire, UK
DOI 10.1007/978-3-319-05744-6_90
901
902
L. Canham and D. Ferguson
Fig. 1 Common brachytherapy sites
minimal radiation of surrounding healthy tissue and minimal side effects (Devlin
2007; Venselaar et al. 2012). It has been successfully used for treating cervical,
prostate, primary liver, pancreatic, and breast cancer but also has potential in many
other sites (Fig. 1). The first nanostructured porous silicon product chosen for
clinical assessment by pSiMedica Ltd UK was a brachytherapy product:
BrachySilTM. Targeted indications were unresectable hepatocellular and pancreatic
carcinomas. The prognosis for patients diagnosed with pancreatic cancer in particular, regardless of stage, is generally poor. The World Cancer Research Fund
estimated in 2010 that 280,000 people globally were diagnosed and that the relative
5-year survival rate for all stages combined was approximately 6 %. Patients
present late because most signs and symptoms of pancreatic cancer are nonspecific.
At diagnosis, more than 95 % of patients have excessive local invasion and/or
distant metastases, making their cancers unresectable. We briefly review here the
manufacturing process, in vitro testing, and preclinical and clinical data accumulated to date.
The Medical Isotope 32P and BrachySil TM Manufacture

BrachySilTM comprises 30 micron diameter partially porosified silicon particles
containing very high concentrations of the medical isotope 32P. It is delivered
intratumorally under local anesthetic with imaging guidance. Classified as an active
implantable medical device, it is provided to the surgeon in the form of a kit
containing a vial of microparticles suspended in a proprietary formulant.
Si: P alloy
PATIENT
903
Solid
particles
Formulation
&
packaging
Partial
etching
Neutron
transmutation
Fig. 2 BrachySilTM GMP manufacturing process
This isotope has been used in colloidal chromic form for brachytherapy for many
years (Order et al. 1996; Gao et al. 2010; Kickingereder et al. 2012; Zubilliaga
et al. 1996; Rosemurgy et al. 2008), but in some preclinical studies there were
issues with tumor retainment (Zubilliaga et al. 1996), and in a recent randomized
trial for pancreatic cancer, results were very disappointing (Rosemurgy et al. 2008).
During the period 20042006, the company developed the five-stage GMP
process for manufacture shown in Fig. 2. Extremely pure, highly phosphorus
doped (>1 at%) Si microparticles are engineered from ultrapure polycrystalline
Si using a foundry technique and water atomization. After size classification to a
D50 of 30 microns, these are then acid washed and stain etched (see Porous
Silicon Formation by Stain Etching). The powder then undergoes irradiation by
neutron bombardment to transmute the natural phosphorus isotope 31P to the
radioactive medical isotope 32P. This isotope is an excellent choice for brachytherapy due to its pure beta-emitting properties and moderate half-life. It has
high-energy emission with a maximum tissue range of about 8 mm and a half-life
of about 2 weeks (343.2 h).
In Vitro Testing
A critical technical, clinical, and regulatory challenge in the successful development of the product was to ensure that the product behaved in a similar manner to
approved brachytherapy sealed sources such as titanium seeds containing a
radioisotope. The phosphorus isotope in BrachySilTM distributed within the silicon
matrix has to be retained during its phase of activity, with minimal leakage into
surrounding tissue. The particles must also not migrate from their point of implantation while still radioactive. To confirm this key attribute, a series of in vitro tests
were undertaken in line with the ISO standards 2919 (Radiation protection-Sealed
radioactive sources-General requirements and classification) and 9978 (Radiation
protection-Sealed radioactive sources-Leakage test methods). These ISO standards
define that a sealed source is considered leak tight if the activity released in
immersion tests is below 0.2KBq (~5nCi). Tests confirmed that a series of full-scale
904
production batches met this demanding requirement. An optimized stain etch

process was utilized to deplete the outer microparticle surfaces of phosphorus, in
order to achieve such low radioisotope leakage.
Preclinical Studies
Preclinical studies also quantified the efficacy of intratumoral implantation on
human tumor xenografts in rodents and the safety of intrahepatic delivery using a
coaxial needle system in a large animal model. BrachySilTM suppressed the growth
of both human hepatocellular and pancreatic carcinoma xenografts and at higher
activities caused complete response (Zhang et al. 2006). Autoradiography and
histology demonstrated confinement of the microparticles to the implantation site,
effecting localized cytocidal radioactivity without measurable systemic response.
Clinical Trials
Following very encouraging preclinical studies (Zhang et al. 2006), the first-in-man
clinical safety trial of BrachySilTM was carried out in 2006 and published a year
later (Goh et al. 2007). Eight patients with unresectable hepatocellular carcinoma
received single percutaneous and transperitoneal implantations. BrachySilTM was
injected using ultrasound guidance and computed tomography (CT) directly into
liver tumors to an activity level of 4 MBq/cc of tumor (Fig. 3). Toxicity was
assessed by the nature, incidence, and severity of adverse events and by hematology
Fig. 3 BrachySilTM: first-in-man trial at Singapore General Hospital 2006
905
Fig. 4 BrachySilTM: human liver tumor regression after administration in a clinical safety trial
and clinical chemistry parameters. Target tumor response was assessed with CT
scans (Fig. 4) at 12 and 24 weeks postimplantation using WHO (World Health
Organization) criteria. Implantations were successfully carried out in all eight
conscious patients under local anesthesia (1374 MBq, mean 40 MBq per tumor).
Six of the 8 patients reported 19 adverse events, but no serious events were
attributable to the study device. Changes in hematology and clinical chemistry
were similarly minimal and reflected progressive underlying hepatic disease. All
targeted tumors were responding at 12 weeks, with complete response (100 %
regression) in three lesions. At the end of the study, there were two complete
responses, two partial responses, three stable diseases, and one progressive disease.
The overall conclusion was that percutaneous implantation of BrachySilTM into
hepatocellular tumors is a safe and well-tolerated procedure. The significant degree
of antitumor efficacy seen at this low dose warranted further investigation at
higher doses.
The results of a Phase IIa clinical trial of BrachySilTM for the treatment of
advanced inoperable pancreatic cancer were published in 2008 (Meenan et al. 2007;
Ross et al. 2008). Designed as a second safety study, BrachySilTM radiotherapy was
combined with standard chemotherapy (gemcitabine) with 17 patients at three
centers for cancer therapy: Guys and St Thomas NHS Foundation Trust,
London, UK; University of Birmingham NHS Foundation Trust, UK; and Singapore General Hospital, Singapore. BrachySilTM was found to be easily deliverable
to tumors in a minimally invasive manner using ultrasound-guided endoscopy (Yan
and Van Dam 2008). CT assessments of response were performed at weeks 8, 16,
and 24. The treatment was well tolerated with disease control in 82 % of patients.
The preliminary data therefore suggested efficacy, with (albeit in small numbers
of patients) a doubling of overall survival (OS) compared to standard of care at that
time (gemcitabine chemotherapy), with a median OS of greater than 10 months.
Approximately half of the patients were still alive at 18 months, whereas typically
80+ percent of patients are dead within 1 year.
906
Ongoing Studies
In 2012 the BrachySilTM technology was acquired from pSiMedica by Enigma
Therapeutics who subsequently changed their name to OncoSil Medical Limited
and replaced the BrachySilTM trademark with the OncoSilTM one. OncoSil Medical
plans to conduct a clinical study of OncoSil versus standard of care chemotherapy to provide data to regulators and clinicians to achieve regulatory approval of the
medical device. The trial aims to recruit 150 patients in a number of centers across
the world. The study design adopted will be a 2:1 randomization of 150 patients
with locally advanced pancreatic cancer to receive OncoSil in addition to standard chemotherapy (e.g., gemcitabine plus nab-paclitaxel) versus chemotherapy
alone. The primary outcome measure of success will be overall survival, and
secondary outcome measures will include progression-free survival, quality of
life, and pain scores. A clinically meaningful benefit as defined by the statistical
criteria in the trial protocol is to extend overall survival by at least 30 % or better
than the comparator arm in the study.
Concurrently a CE Mark application is being submitted for OncoSil and is
expected to be granted in 2014. This will allow for earlier commercialization of
OncoSil in the EU, Canadian, Singaporean, and Australian markets.
Conclusions
OncoSil is a localized radiation therapy for the treatment of inoperable solid
tumors administered using endoscopic-guided ultrasound. The device, given as a
single dose, is radioactive phosphorus (32P) which uses inert 30um diameter silicon
particles as the carrier, with the microparticles being delivered directly into the
center of the tumor. Radioactive phosphorus has a half-life of 14.3 days, meaning
that local radiation therapy (extending approximately one centimeter from the
radiation source) is produced over approximately a 3-month period. This radiation
therapy is synergistic with chemotherapy to control tumors and symptoms associated with them including pain and advancement of the disease.
As such, OncoSil offers an alternative to external beam radiation therapy, a
course of treatment requiring 30 treatments over a 6-week period, with substantial
collateral damage to healthy tissues, and a number of unpleasant treatment-related
side effects.
References
Devlin PM (ed) (2007) Brachytherapy: applications and techniques. Lippincott Williams &
Wilkins, Philadelphia, USA
Gao W et al (2010) Intratumoral injection of 32P chromic phosphate in the treatment of implanted
pancreatic carcinoma. Cancer Biother Radiopharm 25:215224
Goh AS, Chung AY, Lo RH, Lau TN, Yu SW, Chng M, Satchithanantham S, Loong SL, Ng DC,
Lim BC, Connor S, Chow PK et al (2007) A novel approach to brachytherapy in hepatocellular
907
carcinoma using a phosphorus 32 brachytherapy delivery device a first in man study. Int J
Radiat Oncol Biol Phys 67(3):786792
Kickingereder P et al (2012) Intracavity brachytherapy using sterotactically applied phosphorus32 colloid for treatment of cystic craniopharyngiomas in 53 patients. J Neurooncol
109:365374. doi:10.1007/s11060-012-0902-8
Meenan J, Mesenas S, Douglas N et al (2007) EUS-delivered therapy for pancreatic cancer: initial
experience with targeted injection of 32P Biosilicon Gastrointest Endosc 65, Abstract AB208
Order SE et al (1996) Preliminary experience of infusional brachytherapy using colloidal 32P. Ann
Acad Med Singapore 25:347351
Ross PJ, Meenan J, ODoherty M, Calara J, Palmer DH, Heatley S, Chow PH et al (2008) Novel
delivery via endoscopic ultrasound of a 32P brachytherapy device in addition to gemcitabine in
advanced pancreatic cancer. Abstract No. 205. ASCO Gastrointestinal Cancers Symposium
Rosemurgy A et al (2008) 32P as an adjunct to standard therapy for locally advanced unresectable
pancreatic cancer : a randomized trial. J Gastrointest Surg 12:682688
Venselaar J et al (eds) (2012) Comprehensive brachytherapy: physical and clinical aspects. CRC
Press, Boca Raton, USA
Yan BM, Van Dam J (2008) Endoscopic ultrasound-guided intratumoural therapy for pancreatic
cancer. Can J Gastroenterol 22(4):405410
Zhang K, Loong SLE, Connor S, Yu SWK, Tan SY, Ng RTH, Lee KM, Canham L, Chow PKH
et al (2006) Complete tumor response following intratumoral 32P BioSilicon on human
hepatocellular and pancreatic xenografts in nude mice. Clin Cancer Res 11(20):75327537
Zubilliaga MB et al (1996) Use of colloids of chromic (32P) phosphate in treatment of solid tumors.
Nucl Med Biol 23:907910
Drug Delivery with Porous Silicon

Jarno Salonen
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oral Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Subcutaneous Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Intravenous Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Intravitreal Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Additional Functionalities of Porous Silicon Delivery System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
909
910
911
912
913
914
914
916
Abstract
Biodegradable porous silicon is under preclinical assessment for a range of drug

delivery applications. Studies to date on oral, subcutaneous, intravenous, and
intravitreal modes of delivery are reviewed. Both the merits of this nanostructured carrier technology and some existing challenges are briefly discussed.
Introduction
Any chemical substance used for medical therapy can be considered a drug. Today
many thousands of synthetic drugs are available and drug delivery is a multibillion
euro market with hundreds of companies developing formulations that improve
efficacy and safety (Ranade and Cannon 2011). The use of nanotechnology and
nanostructured materials is also being increasingly investigated in this field (Kumar
et al. 2013).
J. Salonen (*)
Turku, Finland
DOI 10.1007/978-3-319-05744-6_91
909
910
J. Salonen
Fig. 1 Illustration of the

most commonly used drug
administration routes. Bold
text entries represent the
routes where PSi has been
utilized to date
The first report about bioactivity in 1995 (Canham 1995) made PSi an attractive
choice when considering the utilization of it in biomedical applications. In the
following 2 years, several reports related to biocompatibility of PSi (see chapter
Biocompatibility of Porous Silicon) were published, e.g., the paper describing
bioresorbable property of PSi (Canham et al. 1996a, b, 1997; Canham 1997;
Canham and Reeves 1996). The tunable biocompatibility of PSi makes it a very
fascinating material. While the medium porosity Si (p < 60 %) is bioactive, high
porosity Si is bioresorbable and its dissolution rate in body fluids, excluding gastric
fluid, is dependent on the porosity, varying from hours to days. That is an important
advantage considering drug delivery applications, where the dissolution of a carrier
material is an essential factor and strongly dependent on the administration route.
The tunable pore size and volume together with a number of methods to modify the
surface chemistry are also important factors for drug delivery applications. These
factors enable high drug loads and tunable release properties. In addition, the possibility to produce all kinds of particle sizes from large microparticles to nanoparticles
below 100 nm makes PSi applicable to all the drug administration routes from enteral
to parenteral (Fig. 1). This is very promising because of the increasing number of new
challenges the pharmaceutical industry is currently facing, in order to increase
bioavailability of new drug candidates (Ranade and Cannon 2011; Lehto et al. 2013).
Oral Delivery
Although there were biomedical studies of PSi published in the late 1990s and early
2000s (Bayliss et al. 1999; Desai et al. 1999), the first paper about PSi in oral drug
delivery was published in 2003 (Foraker et al. 2003). In the paper, Foraker
et al. used microfabricated porous silicon particles to enhance insulin permeability
across Caco-2 cell monolayer, which is commonly used in vitro model of the human
small intestinal mucosa to predict the absorption of orally administrated drugs.
They observed that the flux of insulin across the cell monolayer was approximately
911
50-fold compared with liquid formulations and nearly 10-fold higher compared
with liquid formulations with permeation enhancer, if insulin was loaded in PSi.
In 1994, Anglin et al. showed for the first time that the surface chemistry has a clear
effect on the release rate of drug loaded in PSi (Anglin et al. 2004). They used a steroid
dexamethasone as a model drug. The mechanism of drug release is thought to involve
a combination of leaching and matrix dissolution. A year later, Salonen et al. published
a paper in which they studied the effect of PSi on oral delivery of five different model
drugs (Salonen et al. 2005). They found that the release rate of a loaded drug was
dependent on the characteristic dissolution behavior of the drug. When the dissolution
rate of the unloaded drug was high, the loading of the drug in the PSi microparticles
caused slightly delayed release. However, with clearly poorly soluble drugs, the
loading remarkably improved dissolution. They also found that pH dependency of
the dissolution was reduced when the drug was loaded into the PSi. In addition, it was
possible to load a relatively high amount of drugs, up to 45 wt%, into PSi.
These observations were interesting because many potential drug candidates
cannot be delivered orally due to their poor pharmacokinetics. This includes the
poor solubility and dissolution of the drug in the intestinal lumen, poor permeation
properties in the gastrointestinal (GI) tract, as well as high intestinal or hepatic firstpass metabolism. It is estimated that more than 95 % of new drug molecules suffer
from these kinds of problems in bioavailability (Brayden 2003).
The improved solubility and dissolution behavior is based on the fact that the
formation of crystalline material is restricted by the confined space of the pores. It is
well known that in their amorphous state, many drugs exhibit higher dissolution
rates than their crystalline counterparts, especially when solubility is limited by
high lattice energies (Yu 2001). The dissolution rates from the porous materials will
also be improved by their very high surface areas.
Despite the improved solubility behavior of loaded drugs observed in vitro, it is
not obvious to gain an improved bioavailability also in vivo. There are also other
obstacles to overcome before a drug reaches the systemic circulation than solubility
issues, such as permeation across a gut wall and first-pass metabolism. In 2010,
Wang et al. reported important results about in vitroin vivo correlation (IVIVC)
(Wang et al. 2010a). They observed that all the pharmacokinetic parameters of
indomethacin were significantly improved when PSi was used as a drug carrier.
Using a fasted rat model, they found out that the maximum plasma concentration
was 2.6-fold when PSi was used and the time to reach it reduced from 2.75 h down
to 0.56 h. In addition, the bioavailability of indomethacin increased from 53.54 %
up to 100 %. All the parameters were better compared to commercially available
formulation (Indocid) and the IVIVC was found to be high (level A).
Subcutaneous Delivery
There are a number of different peptides with promising therapeutic effects, but
which cannot be used practically. Peptide and protein delivery is a rather challenging
task and typically conventional drug delivery systems are not useful. In general,
912
J. Salonen
Fig. 2 PYY3-36 plasma

concentrations up to 96 h after
subcutaneous delivery in
mice with three different PSi
nanocarriers: thermally
oxidized (TOPSi), thermally
hydrocarbonized (THCPSi),
and undecylenic acid treated
THCPSi (UnTHCPSi)
(Kovalainen et al. 2013)
(Reprinted with permission
from American Chemical
Society)
bioavailability of orally administered peptides is very poor, and because peptides

have a short duration of action in vivo due to their rapid degradation and elimination from the blood circulation, the treatment may require several daily injections to
keep the plasma concentration at an effective therapeutic level. Although there are
several different systems developed for subcutaneous delivery, the main problem,
in the case of peptides, is that they are very fragile biomolecules and cannot stand
strong solvents, high temperatures, or harsh environments at all.
Drug loading in PSi is a relatively gentle process which can be done at room
temperature using mild solvents, with achievement of high payloads. In 2007,
Prestidge et al. showed that a protein can be loaded and released from PSi
(Prestidge et al. 2007), and in 2009, Kilpelainen et al. showed in vivo that the
loaded peptide was pharmacologically active after the loading (Kilpelainen
et al. 2009). In the following years, more results about subcutaneous administration
of different peptides were published (Kilpelainen et al. 2011; Kovalainen
et al. 2012, 2013). In addition to the remaining pharmacological activity, some
other important findings were published recently. For example, a prolonged release
of a peptide YY (PYY) up to several days from PSi nanoparticles and clearly
enhanced bioavailability are both promising results for future development of PSi
based peptide delivery systems (Fig. 2) (Kovalainen et al. 2013).
Intravenous Delivery
The highly sophisticated immune system of the human body makes intravenous
delivery of inorganic particles problematic. Despite the challenges related to the
intravenous route, the high hopes for rapidly developing nanotechnology have
initiated an intensive research of targeted drug delivery. One of the main aims of
this research is focused on the development of novel cancer therapies and this has
been the major research field of PSi nanoparticles too.
913
Due to the versatile properties of PSi, it can be used as a simple drug carrier but
also as a multifunctional material for therapeutic and imaging purposes. Tasciotti
et al. introduced this kind of multifunctional multistage delivery system in 2008
(Tasciotti et al. 2008). They used PSi as a first-stage carrier in which the secondstage nanoparticles, quantum dots or single-walled carbon nanotubes, were loaded.
In 2009, Park et al. reported the first in vivo results of PSi nanoparticles (Park
et al. 2009). They used PSi intrinsic photoluminescence properties for near-infrared
monitoring the nanoparticles in vivo. With a dextran coating, the particles manage
to avoid rapid clearance and the blood circulation time of nanoparticles increased
significantly. Even more importantly, they observed a passive accumulation of
nanoparticles in the tumor tissue (enhanced permeability and retention effect,
EPR). In 2012, also Godin et al. observed enhanced accumulation in the tumor
tissue, although they used large discoidal particles instead of nanoparticles (Godin
et al. 2012). In addition to passive accumulation, PSi can be used in active targeting
also. Several other groups have published their work on actively targeted delivery
recently (Secret et al. 2013; Mann et al. 2011; Shen et al. 2013; Rytkonen
et al. 2012).
Unfortunately, in the other in vivo studies only rapid clearance of the PSi
nanoparticles in the spleen or liver has been observed without any controlled
accumulation or homing, although many different surface chemistries have been
tested (Kovalainen et al. 2013; Tanaka et al. 2010a; Bimbo et al. 2010; Sarparanta
et al. 2012; Rytkonen et al. 2012). However, a promising release of siRNA from
particles cleared to spleen and liver for at least 3 weeks has been reported (Tanaka
et al. 2010b). The results indicate that particles may be able to release their payload
even after they have been captured in the spleen or liver. This may be used as a new
potential delivery system for compounds which suffer from fast renal clearance or
need to be delivered to metabolic tissues (e.g., type IB prodrugs).
Intravitreal Delivery
Continuously increasing life expectancy and prevalence of diabetes in developed
countries have increased an incidence of retinal diseases like age-related macular
degeneration and diabetic retinopathy rapidly. Unfortunately, intravitreal delivery
is a challenging task. There are obstacles like the bloodretina barrier and the tight
junctions of the retinal pigment epithelium which lower the effectiveness of dosed
drugs and complicate the administration (Cheng et al. 2008). Since the introduction
of anti-VEGF medications, the need of intravitreal injections has significantly
increased. Due to the short half-life of most injectable intravitreal drugs, frequent
administrations are necessary. To overcome these problems, new delivery systems
are continuously studied to obtain prolonged sustained release of drugs and reduce
the frequency of injections.
Despite having promising relevant properties, the use of PSi in intravitreal drug
delivery has not been extensively studied. Low et al. implanted PSi membranes into
rat eye at superior, temporal, and inferior locations and the rats were observed over
914
J. Salonen
a period of 9 weeks until the pieces were no longer visible with a microscope
(Low et al. 2009). Implanted PSi did not erode the underlying or overlying tissue,
did not cause a marked accumulation of inflammatory cells, and did not become
vascularized. The results indicated that PSi is nontoxic, noninflammatory, and
biodegradable material and suitable for intravitreal drug delivery.
Chhablani et al. showed that in oxidized PSi covalently loaded daunorubicin
demonstrated sustained intravitreal release for 3 months without any evidence of
toxicity, while physisorbed daunorubicin was released within 2 weeks and localized
retinal toxicity were observed due to high daunorubicin concentration. Wu
et al. added a new functionality to PSi drug delivery system (Wu et al. 2011).
They used 1-dimensional porous silicon photonic crystal in intravitreal delivery.
The reflectance spectrum of the crystal (i.e., color) changed from red to green as
daunorubicin was releasing enabling real-time monitoring of the drug release
process. These types of multifunctional delivery systems based on versatile properties of PSi are expected to be published much more in future.
Additional Functionalities of Porous Silicon Delivery System

In the previous chapter, two examples of multifunctional drug delivery systems
applying PSi luminescent and photonic properties were described, but there are
many other possibilities to include additional functionalities to the delivery
systems. One of the most studied applications is PSi-polymer composite structures
in which PSi have a dual role as a hydroxyapatite growth activator and drug carrier
(Mukherjee et al. 2006; Fan et al. 2009, 2011). The composite structures are
described in detail in chapter Polymer - Porous Silicon Composites.
Due to the easily modified surface chemistry, PSi enables attachment of all kind of
active species on its surface. However, in certain case, simple capping of PSi may
lead to desired functionality. This approach has been used to obtain pH-triggered
delivery systems, in which pH-sensitive protein or polymer is used to trigger the
release of loaded drug (Perelman et al. 2008; McInnes et al. 2012). Another approach
to the triggered drug release is to use thermoresponsive polymers. Vasani
et al. grafted poly-N-isopropylacrylamide on PSi and demonstrated that modulation
of temperature significantly alters the release of anticancer drug camptothecin
(Vasani et al. 2011). There are some other strategies also to obtain triggered release,
like oxidation triggered release and electrically enhanced erosion of PSi. The latter is
relatively rarely studied applications, but promising results considering, e.g.,
chronotherapeutic applications have been reported (Leong et al. 2007).
Summary
There are a number of potential drug administration routes in which PSi can be used
(Table 1). Some of the routes are not even explored yet. In biomedical applications,
in addition to the nontoxic behavior of the carrier material and bioresorbability, it is
Subcutaneous
Oral
Oral
Oral
Parenteral
Intravitreal
Intravenous
Intravenous
Several
Griseofulvin
Indomethacin
Ethionamide
Triclosan
Daunorubicin
siRNA
Mitoxantrone
Ketoconazole
X
In
vivo
Subcutaneous
Oral
Oral
Oral
Parenteral
Administration
route
Oral
Ghrelin antagonist,
melanotan II
Peptide YY
Compound
Furosemide, griseofulvin,
ibuprofen
Ranitidine, antipyrine
Ibuprofen
Furosemide
Doxorubicin
Gramicidin A, papain
Permeability
Bioavailability
Dissolution,
permeability
Release, antibacterial
activity
Dissolution
Gene silencing
Release
Release, antifungal
activity
Pharmacological
activity
Bioavailability
Dissolution
Dissolution
Permeability
Release
Loading, release
Study type
Dissolution
Table 1 Examples of drug delivery studies using PSi as a drug carrier material
Sustained release, monitoring

Sustained release
Sustained release
Sustained release
Enhanced permeation
Enhanced bioavailability
Enhanced permeation and metabolic
activity
Sustained release
Sustained release
Sustained release
Sustained release, no effect

Effect of surface chemistry
Enhanced permeation
Sustained release
Sustained release
Effect
Improved dissolution rate
(Wu et al. 2011)

(Tanaka et al. 2010b)
(Tzur-Balter et al. 2013)
(Tang et al. 2013)
(Wang et al. 2010b)
(Salonen et al. 2005)

(Limnell et al. 2006)
(Kaukonen et al. 2007)
(Vaccari et al. 2006)
(Prestidge et al. 2007,
2008)
(Kilpelainen et al. 2009,
2011)
(Kovalainen et al. 2012,
2013)
(Bimbo et al. 2011)
(Wang et al. 2010a)
(Vale et al. 2012)
References
(Salonen et al. 2005)

915
916
J. Salonen
important that the degradation products are also nontoxic. PSi degradates into
monomeric silicic acid, which is the most natural form of silicon and an important
nutrient for humans (Jugdaohsingh et al. 2004).
Despite the very positive results published about PSi, there still exists one big
stumbling block which hinders the commercialization. This is the cost of PSi
production for drug delivery applications. The cost of silicon wafers used in
microelectronics is high because of the strict demands for high purity. These
demands are well beyond that what would be needed for biomedical applications,
and although it is possible to produce low-cost PSi from metallurgical grade silicon
(Loni et al. 2011; Chadwick et al. 2012), it is not yet clear if this type of PSi can be
used for biomedical purposes. Quite recently, a new promising approach to produce
low-cost PSi has been started to explore, namely, magnesium-induced reduction of
silicon dioxide to silicon (Bao et al. 2007 and chapter Porous Silicon Formation
by Porous Silica Reduction), which may open a way to produce low-cost PSi with
an environmentally friendly process (Batchelor et al. 2012).
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Porous Silicon and Tissue Engineering

Scaffolds
Jeffery L. Coffer
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Representative Porous Silicon Scaffolds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Milestones for Use of Porous Silicon in Tissue Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon/Polymer Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
921
922
922
923
926
Abstract
Porous silicon possesses a number of favorable properties that make it relevant

to the field of regenerative medicine / tissue engineering (i.e. the idea that the
human body can heal itself with the assistance of a temporary scaffold). These
properties include tunable scaffold dissolution based on Si nanostructure thickness/porosity and surface chemistry; in vitro and in vivo compatibility; and facile
formation of easily processible porous silicon / biocompatible polymer constructs. In this review, selected formulations of porous Si relevant to scaffold
evaluation are described, followed by key tissue engineering milestones for
porous silicon, and brief summaries of studies of porous silicon-containing
materials with relevance to specific therapies.
Introduction
The field of regenerative medicine centers on the concept that the human body can
heal itself, beginning at the cellular level with the assistance of a temporary
synthetic three-dimensional scaffold (Lanza et al. 2007). In order to (re)create a
J.L. Coffer (*)
Department of Chemistry, Texas Christian University, Fort Worth, TX, USA
e-mail: j.coffer@tcu.edu
DOI 10.1007/978-3-319-05744-6_92
921
922
J.L. Coffer
healthy tissue, several key requirements must be met: eventual scaffold dissolution with appropriate kinetics under physiological conditions, along with
cellular attachment, proliferation, and differentiation onto the scaffold. The
scaffold also needs to possess a three-dimensional macrostructure that ensures
proper vasculature and neural ingrowth to the extent of the native tissue. The
ability to easily process such materials also provides strong motivation for
widespread adaptation.
The genesis of the idea that porous silicon (pSi) could be exploited as a
biomaterial for such applications is attributed to the 1995 publication that exposure
of a mesoporous silicon layer to a solution of simulated body fluid at physiological
temperature results in calcification, an early signature of bioactivity (Canham
1995). Subsequent in vivo experiments using a guinea pig model demonstrated
another crucial result that mesoporous Si will resorb in a living system with a
negligible inflammatory response (Bowditch et al. 1999). Such results triggered
subsequent investigations of additional fundamental properties of relevance to its
ultimate function as a tissue engineering scaffold.
Pure silicon-containing scaffolds have been fabricated by a number of techniques, including anodization (Canham 1995), metal-assisted chemical etching
(Yang et al. 2010), dry etching (Hajj-Hassan et al. 2011), localized irradiation
(Punzon-Quijorna et al. 2012), and micromachining (Aston and Canham 2001).
Illustrations of selected formulations of porous Si relevant to scaffold evaluation
are shown in Fig. 1. Studies that demonstrate completion of many of the above
requirements by porous silicon are listed in Table 1. An overview of pSi/polymer
constructs that have been investigated in vitro and, in some cases, in vivo is listed in
Table 2, along with selected images of these composites (Fig. 2). Finally, brief
comments regarding studies of porous silicon-containing materials with relevance
to specific therapies are provided.
Representative Porous Silicon Scaffolds

The pSi-containing scaffolds shown (Fig. 1) span a diverse range: (a) porous
machined cubes (Aston and Canham 2001), (b) thin macroporous films (Sun
et al. 2007), and (c) free-standing microparticles. The motivation for a specific
scaffold is driven by porosity and mechanical requirements.
Milestones for Use of Porous Silicon in Tissue Engineering

Table 1 lists the various requirements that porous silicon has met for tissue
engineering applications, along with published reports associated with these
particular benchmarks.
Porous Silicon and Tissue Engineering Scaffolds
923
Fig. 1 Representative pSi scaffolds: (a) micromachined Si cube (Aston and Canham 2001),
(b) macroporous Si film (Sun et al. 2007), and (c) free-standing mesoporous Si microparticles
Porous Silicon/Polymer Composites

To facilitate the ultrahigh three-dimensional porosity values necessary in these
scaffolds (as noted above) and to provide the ability to easily manipulate pSi
materials in a biological environment, pSi can be blended with known
FDA-approved polymers such as poly(caprolactone) (PCL). Representative types
of such composites are illustrated in Fig. 2. Handbook chapter Polymer - Porous
Silicon Composites reviews the different fabrication strategies available.
Classes of pSi/polymer composites for tissue engineering can be readily sorted
into three categories, primarily classified on the basis of morphology and associated
surface area. These are listed in Table 2. The relevant associated target tissue is also
identified within this table as well. Compositionally, the polymer constituent has
principally focused on PCL, but scaffolds incorporating poly (L-lactide) (PLLA)
and poly(lactide-co-glycolide) (PLGA) have also been evaluated.
924
J.L. Coffer
Table 1 Key tissue engineering milestones for PSi

Milestone
Resorption/
bioactivity
Cytocompatibility
Cell attachment
Cell
differentiation
Property evaluated
Bioactivity
In vivo resorption
Quantitation of pSi dissolution as a function of
porosity
Neuronal B50 and CHO cell proliferation in
the presence of pSi
HEK 293 cell proliferation in the presence of
pSi
Neuronal B50 attachment on anodized and
stain etch pSi
Primary hepatocyte attachment on oxidized
pSi
Effect of thermal treatment and surface carbon
layers on attachment of HREC cells, MAEC
cells, murine melanoma cells on pSi surface
attachment
Aplysia (primary) neurons
PC12 and human lens epithelial cell
attachment on as prepared and surfacemodified pSi
Osteoblast attachment as a function of pSi
porosity
Vascular endothelial cell attachment to porous
nanocrystalline Si membranes
CHO cell attachment to Si nanosponges/
nanowires formed by metal chemical etching,
including effects of surface treatment with
different organosilanes
Murine bone marrow-derived mesenchymal
stem cell attachment to pSi formed by dry
etching
Neuroblastoma (N2A) and cortical neuronal
cells (HCN1A) attachment on two different
mesoporous Si types
3 T3 fibroblast attachment on pSi prepared by
laser ablation
Human mesenchymal stem cell (hMSC)
attachment onto pSi patterns formed by
localized irradiation
Mesenchymal stem cell (MSC) differentiation
(osteogenic) on pSi/polymer composites
Mesenchymal stem cell differentiation
(osteogenic) and in vitro calcification on
pSi/PCL composites
MSC differentiation on pSi gradients
Reference
Canham (1995)
Bowditch et al. (1999)
Anderson et al. (2003)
Bayliss et al. (1997,
1999)
Coffer et al. (2005)
Mayne et al. (2000);
Sapelkin et al. (2006)
Chin, 2001 (Chin
et al. 2001)
Angelescu et al. (2003)
Ben-Tabou de Leon
et al. (2004)
Low et al. (2006)
Sun et al. (2007)

Agrawal et al. (2010)
Yang et al. (2010)
Hajj-Hassan
et al. (2011)
Gentile et al. (2012)
Premnath et al. (2012)

Punzon-Quijorna
et al. (2012)
Whitehead et al. (2008)
Fan et al. (2011)
Wang et al. (2012)
925
Table 2 Selected examples of pSi/biocompatible polymer composites for tissue engineering

Composite
pSi/PCL solid fixative
Target
tissue
Bone
pSi/PCL porous PCL sponge
Bone
pSi/PCL PCL electrospun microfibers
Bone;
eye
Bone
Bone
pSi/PLGA microspheres
pSi/PCL composites containing platelet-rich plasma,
peptide amphiphiles, bone morphogenetic protein-2,
and mesenchymal stem cells
Reference
Aston and Canham (2001);
Mukherjee et al. (2006)
Coffer et al. (2005);
Whitehead et al. (2008)
Fan et al. (2011); Kashanian
et al. (2010)
Fan et al. (2012)
Murphy et al. (2011)
Fig. 2 Selected pSi/polymer scaffolds. (a) Solid PCL cube (3 mm) with mesoporous Si (67 %
porosity) on opposite faces (Mukherjee et al. 2006), (b) pSi/porous PCL sponge (Whitehead
et al. 2008), (c) pSi/PCL microfibers (Fan et al. 2011), and (d) pSi/PLGA microspheres (Fan
et al. 2012)
926
J.L. Coffer
In terms of long-term clinical targets, it is clear that much of the effort directed in
the use of porous Si for tissue engineering has been with respect to the bone. This is
likely a consequence of the observation that the pSi dissolution product silicic acid,
Si(OH)4, stimulates calcification in the form of spherulite deposit formation
(Canham et al. 1996a, b), as well as osteogenic differentiation (Reffitt
et al. 2003). The second therapeutic target identified for several studies has been
the eye, where human lens epithelial cell attachment (Low et al. 2006), along with a
negligible inflammatory response in a rat-eye model (Kashanian et al. 2010), has
been secured for pSi and pSi/PCL fiber composites. Other candidates will likely
emerge in due course.
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Porous Silicon in Photodynamic and

Photothermal Therapy
Victor Yu Timoshenko
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photosensitization Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
In Vitro Testing of PSi for PDT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
PSi as Photothermal Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
929
931
933
935
935
Abstract
Porous silicon has been under evaluation as both a photosensitizer and a

photothermal agent against cancer. Photodynamic therapy approaches exploit
the ability of mesoporous silicon to generate reactive oxygen species under
illumination; photothermal therapy exploits its ability to absorb near-infrared
light and the low thermal conductivity. Both the in vitro and in vivo data
acquired to date are reviewed.
Introduction
Photodynamic therapy (PDT) is a kind of phototherapy which is used for minimally
invasive treatment of malignant tumors and other tissue pathology (Moser 1998).
Usually PDT combines three steps (see Fig. 1a) such as a drug (photosensitizer)
injection (step I), the drug accumulation (step II), and its activation by illumination
(step III) in order to photosensitize molecular oxygen in the tissue. The photosensitization results in formation of singlet oxygen (SO) and/or other reactive oxygen
species (ROS) as superoxide and peroxide (Moser 1998). SO is the most reactive
V.Y. Timoshenko (*)
Physics Department, M.V. Lomonosov Moscow State University, Moscow, Russia
e-mail: timoshen@physics.msu.ru
DOI 10.1007/978-3-319-05744-6_93
929
930
V.Y. Timoshenko
II
III
Fig. 1 (a) Scheme of PDT, which indicates three main steps (I, II, III), and (b) the energy level
diagram of molecular oxygen (electron spins in the upper singlet, lower singlet, and ground triplet
states are schematically marked by blue, red, and black arrows, respectively
form of molecular oxygen, which reacts with many organic compounds (Arnold
et al. 1968). The relaxation of SO back to the ground (triplet) state is not allowed by
the spin-selection rule, and thus, SO is characterized by rather long radiative
lifetimes (see Fig. 1b) which are favorable for transferring the excess energy to
other molecules (Turro 1991).
PDT is used clinically for over a decade now, but there are some important
limitations with the all-organic systems (Moser 1998). Luminescent porous silicon
(PSi) was found to be a photosensitizer of the SO generation in gases (Kovalev
et al. 2002; Gross et al. 2003; Fujii et al. 2005) and liquids (Fujii et al. 2004a, b,
2005). While the low-temperature (LT) experiments on the SO generation revealed
the basic mechanism of photosensitization properties of PSi (Kovalev et al. 2002;
Gross et al. 2003; Fujii et al. 2005), the room temperature (RT) studies demonstrated practically important features of PSi as photosensitizer for PDT applications
(Fujii et al. 2004a, b; Ryabchikov et al. 2007; Kovalev et al. 2004; Gongalsky
et al. 2010, 2011; Konstantinova et al. 2006, 2007, 2008; Xiao et al. 2011;
Timoshenko et al. 2006, 2007; Low et al. 2010; Osminkina et al. 2011, 2012).
Besides the numerous investigations of bare PSi for the ROS generation, a couple of
the studies were devoted to composites of PSi with another photosensitizer
(porphyrins, fullerenes) where PSi particles are considered as a carrier for
molecular photosensitizer (Parkhutik et al. 2007; Chirvony et al. 2007;
Pikulev et al. 2007; Kuznetsov et al. 2009; Secret et al. 2013).
Photothermal therapy (PTT) is another kind of phototherapy, which is based on
the light-induced overheating (hyperthermia) of tumors above 4041 C. The
treatment with tissue temperature above 46 C is particularly termed
thermoablation, and it is characterized by direct cytotoxic effects. Photoexcited
PSi nanoparticles were explored as a therapeutic agent, which generated sufficient
heat to kill cancer cells without chemical toxicity (Lee et al. 2007). PSi
nanoparticles under irradiation with NIR light were used to destroy cancer cells
selectively without damaging the surrounding healthy cells (Lee et al. 2008). Both
Porous Silicon in Photodynamic and Photothermal Therapy
931
in vitro and in vivo studies confirmed the required photothermal properties of PSi
for PTT application (Lee et al. 2012; Hong et al. 2011; Hong and Lee 2013).
Photosensitization Properties
The photosensitization of SO generation by PSi is explained by considering the
energy transfer from excitons confined in silicon nanocrystals (nc-Si) to oxygen
molecules (O2) adsorbed on nc-Si surface (Gross et al. 2003). This process is
favorable in mesoporous and (meso-PSi) and microporous PSi (micro-PSi) because
of large specific surface area (102 103 m2/g) and rather long radiative lifetimes
(ex 105 103 s) of the excitons (see chapter Photoluminescence of
Porous Silicon). The strong quenching of the exciton photoluminescence (PL) of
PSi with adsorbed O2 molecules was used to clarify the energy transfer mechanism,
and the following value was evaluated: Q IPLvac/IPLox, where IPLvac and IPLox are
the PL intensities of PSi in vacuum and in oxygen ambient, respectively (Kovalev
et al. 2002). The PL quenching by O2 is accompanied by a significant decrease of
the PL decay time, PL, because the adsorbed O2 molecules on the nc-Si surface
represent a channel for the nonradiative recombination of the excitons. The spectral
dependence of PL follows the spectrum of Q (Gross et al. 2003). The average time
of the energy transfer from excitons in nc-Si assembly to O2 molecules can be
calculated from the following expression: ET1 PL1 ex1 (Fujii
et al. 2004b). The values of ET for the energy transfer to the 1 and 1 states of
O2 (see Fig. 1b) are about of 50100 s and <3 s, respectively (Gross et al. 2003;
Fujii et al. 2005). The spectra of Q and PL for PSi at LT demonstrate the main
maximum at photon energy of 1.63 eV (13 transition between the upper singlet
and ground triplet states in O2), additional maximum at ~57 meV below the main
maximum, and numerous maxima separated by energy of ~63 meV. These additional maxima correspond to the energy transfer from nc-Si with bandgaps, which
do not match resonantly the excitation energies of the singlet states of O2, and then
the momentum conserving TO phonon with energy of 57 meV, and TO/LO
phonons near the center of the Brillouin zone with energy of 63 eV are required
to maintain the energy balance (Gross et al. 2003).
The efficiency of energy transfer from excitons in nc-Si to O2 molecules can be
defined as ET 1 Q1 (Ryabchikov et al. 2007). The quantum yield of SO
generation can be expressed as SO ETPL, where PL is the quantum efficiency
of the exciton PL of nc-Si without interaction with O2 molecules. It is worth to note
that the interaction of photosensitized SO with nc-Si surface can result in
photodegradation of the exciton PL efficiency (Kovalev et al. 2004) and then the
SO efficiency decreases (Gongalsky et al. 2010, 2011).
Simultaneous measurements of the exciton PL and infrared emission from the
1
-state of O2 molecules at 1,270 nm (0.98 eV) were used to estimate SO ~ 1 %
and SO lifetime, SO 5 ms, in microporous PSi at RT and normal atmospheric
pressure of O2 (Gongalsky et al. 2010, 2011). The interaction of photosensitized SO
with internal surface of PSi was recognized to be the main limiting factor for the SO
932
V.Y. Timoshenko
generation efficiency and lifetime. PSi can be more efficient photosensitizer if the
spatial separation between individual nc-Si is large enough to minimize the exciton
PL photodegradation and SO quenching due to the interaction with PSi surface
(Gongalsky et al. 2011).
X-band electron paramagnetic resonance (EPR) spectroscopy of Si dangling
bonds in photoexcited micro-PSi revealed the concentration of photosensitized SO
of the order of 1019 cm3 at RT and normal pressure of gaseous O2 (Konstantinova
et al. 2006, 2007). Results of the Q-band EPR spectroscopy demonstrated that ~30 %
of O2 molecules could be converted into SO under photoexcitation of micro-PSi
powder in O2 atmosphere at RT (Konstantinova et al. 2008).
Meso-PSi nanoparticles, prepared from electrochemically etched c-Si wafers,
were tested as photosensitizers of the SO generation in ethanol or in aqueous media
by using the DPBF decomposition analysis (Xiao et al. 2011). The optimal formulation was consisted of PSi nanoparticles 146 nm in diameter, with nominal pore sizes
of 12 nm. The quantum yield for SO production was reported to be 10 % in ethanol
and 17 % in water, while the possibility of such highly efficient SO photosensitization
by meso-PSi in liquids was not explained (Xiao et al. 2011; Table 1).
Table 1 Summary of the experimental evidences for PSi as a photosensitizer
Sensitization
efficiency and SO
concentration
Q > 103(T 5 K)
Q < 1.5 (RT)
Photoexcitation
and ambient
conditions
488 nm, 514.5 nm;
adsorbed and
gaseous O2
514.5 nm,
632.8 nm;
40 mW, 1060
min, organic
liquids with
dissolved O2, RT
488 nm, 514.5 nm;
organic liquids,
water, RT
High-pressure
Hg-lamp with
infrared filtering,
100 W; gaseous
O2, RT
532 nm, 20 mW;
gaseous O2, RT
Type of PSi
Microporous
films
Diagnostic
methods
Quenching of the
exciton PL
Microporous
particles
DPBF
decomposition
Relative change of
the optical
absorbance ~1.5
Microporous
particles
ET ~ 0.8
Microporous
powder
Quenching of the
exciton PL; PL at
1.27 m of SO
EPR of Si
dangling bonds
Microporous Si
powder
SO luminescence
at 1.27 m
SO ~ 1 %
Mesoporous
Si nanoparticles
DPBF
decomposition
SO ~ 10 % in
ethanol,
SO ~ 17 % in
water
SO concentration
~1019 cm3
White light
(infrared filtered),
100 mW/cm2,
10 min; liquids
with dissolved O2,
RT
References
Kovalev et al.
2002
Gross et al.
2003
Fujii
et al. 2004a
Fujii et al.
2004, 2005
Konstantinova
et al. 2006
Gongalsky
et al. 2010,
2011
Xiao
et al. 2011
933
In Vitro Testing of PSi for PDT

In vitro testing of PSi for PDT has utilized cell culture (see chapter Cell Culture
on Porous Silicon).
The first observation of suppression of cancer cell proliferation by photoexcited
PSi microparticles in vitro was reported in Ref. (Timoshenko et al. 2006) where the
number of mouse fibroblasts relative to the control decreased after illumination
in the presence of PSi with concentration above 0.5 g/L. The death of ~80 %
of cells was detected for the concentration of 2 g/L. These facts were
explained by the effect of photosensitized generation of SO because of PSi
microparticles. At the same time, the effect of PSi in darkness was almost
negligible over the PSi concentration range of 0.52.5 g/L. Further experiments revealed that photoexcited PSi microparticles resulted in an increase of
the apoptosis rate for cancer cells (Timoshenko et al. 2007). The death of
cancer cells was related mostly to the oxidizing action of photosensitized SO,
while other reactive oxygen species (ROS), e.g., superoxide ions O2, could
also contribute to the PDT effect. The ROS generation by non-oxidized PSi
microparticles in solution was revealed by means of the fluorescent probe and
by detection the ROS-induced formation of cytotoxic species in vitro (Low
et al. 2010).
Cancer cell cultures (HeLa and NIH-3 T3) impregnated with 0.1 g/L meso-PSi
nanoparticles and exposed to 60 J/cm2 white light exhibited ~45 % cell death, while
controls containing no nanoparticles showed ~10 % and ~25 % cell death for HeLa
and NIH-3 T3 lines, respectively. The dark control experiment yields <10 %
cytotoxicity for either cell type (Xiao et al. 2011). Micro-PSi nanoparticles were
found to penetrate into cancer cells, resulting in ~70 % cell death after illumination
(Osminkina et al. 2011). Micro-PSi nanoparticles were also examined as SO
photosensitizers and photoluminescent labels in bioimaging in vitro, and then
they were proposed for application in cancer theranostics (therapy and diagnostics)
(Osminkina et al. 2012).
Different combinations of PSi particles and molecular photosensitizers were
tested to explore possibilities of both increasing the ROS generation and targeted
drug delivery for PDT (Parkhutik et al. 2007; Chirvony et al. 2007; Pikulev
et al. 2007; Kuznetsov et al. 2009; Secret et al. 2013). The hybrid porphyrin/
oxidized PSi structures were stable in aqueous media toward outwashing of porphyrins and degradation of its photosensitizing properties (Parkhutik et al. 2007;
Chirvony et al. 2007). C60 fullerenes incorporated in ultrathin PSi layer resulted in
both the quenching of the exciton PL of PSi and the SO generation via the energy
transfer from photoexcited nc-Si (Pikulev et al. 2007). A comparative study in vitro
of the PDT efficiency of PSi powder and its composite with C60 molecules revealed
that the composite outperforms the bare PSi due to higher rate dynamics of cells
death (Kuznetsov et al. 2009).
Meso-PSi nanoparticles have been used for the delivery of porphyrin drugs (see
chapter Drug Delivery with Porous Silicon) into breast cancer cells in vitro.
The porphyrin was covalently immobilized onto the surface of PSi via a new
934
V.Y. Timoshenko
Table 2 Summary of in vitro and in vivo testing of PSi for PDT and PTT
Si nanomaterial
Microporous Si
flakes, 0.52.5 g/L
BioSiliconTM
microparticles and
membranes
Microporous Si
nanoparticles,
0.52.5 g/L
Mesoporous Si
nanoparticles,
0.1 g/L
Microporous Si
nanoparticles,
0.05 g/L
Mesoporous Si
nanoparticles with
porphyrin, 0.02 g/L
Microporous Si
with cylindrical
macropores; PSi
suspension filtered
with 200 nm
membrane
Mesoporous SiEtOH-PEG
suspension with
nanoparticles
~140 nm, 0.7 g/L
DMSO: porous Si
colloid with
particles ~67 nm
Bio-object
Mouse
fibroblasts
(NIH-3 T3
cells)
Human
lens
epithelial
cells (SRA
01/04)
NIH-3 T3
cells
HeLa and
NIH-3 T3
cells
NIH-3 T3
cells
MCF-7
breast
cancer
cells
Breast
cancer
SK-BR-3
cells
Murine
colon
carcinoma
CT-26
cells and
tumors of
mice
Pancreatic
cancer
BXPC-3
cells
Photoexcitation
360600 nm,
1 mW/cm2 for
1h
PDT/PTT effect
PDT effect: 80 % cell
death due to apoptosis
Study
examples
Timoshenko
et al. 2006,
2007
Native
illumination,
24 h
PDT effect:
cytotoxicity
Low
et al. 2010
360600 nm,
1 mW/cm2 for
20 min
White (infrared
filtered) light
100 mW/cm2
for 10 min
360600 nm,
1 mW/cm2 for
1.5 h
650 nm,
14 J/cm2,
40 min
PDT effect:
>80 % cell death
Osminkina
et al. 2011
PDT effect:
~45 % cell death
Xiao
et al. 2011
PDT effect:
70 % cell death
Osminkina
et al. 2012
PDT effect:
42 % cell death
Secret
et al. 2013
0.3 W/cm2 for

20 min
PTT effect:
cell viability of 2.6 %
Lee
et al. 2008
Laser 808 nm,

1.5 W/cm2,
4 times of for
2 min
PTT effect:
cell viability of
2.6 %;
tumors were
completely resorbed
Hong
et al. 2011
Laser 808 nm,

1.25 W/cm2,
for 20 min
PTT effect:
cell viability of 5.7 %
Hong and
Lee 2013
chemical modification scheme, which retains the porphyrin photoactivity. The

functionalized nanoparticles were better internalized by cancer cells compared to
the plain photosensitizer, and a more efficient cell death was observed (Secret
et al. 2013).
935
PSi as Photothermal Agent

PSi was also utilized as a therapeutic agent for PTT application upon exposure to
NIR light with wavelength of 0.781.4 m (Lee et al. 2007). In vitro studies showed
a strong destruction of cancer cells after interaction with PSi particles excited by the
NIR light at 0.3 W/cm2, while the separate action of NIR or PSi did not lead to any
significant changes in the cell viability (Lee et al. 2008). Annexin V-FITC apoptosis
assay results demonstrated that the cell death is mostly due to necrosis rather than
apoptosis, and the former could be also initiated by NIR illumination of both bare
and oxidized PSi (Lee et al. 2012). In vivo animal test results showed that murine
colon carcinoma tumors could be completely resorbed without nearly giving
damage to the surrounding healthy tissue after 5 days of the PSi and NIR laser
treatment (Hong et al. 2011). Stable colloidal solution of DMSO-modified PSi
nanoparticles under NIR laser irradiation was successfully used to destroy almost
completely pancreatic cancer cells in vitro (Hong and Lee 2013). Both the in vitro
cell tests and in vivo experiments suggest that the PSi-based PTT is rather efficient
to selectively destroy cancer cells without damaging the surrounding healthy cells.
Both the thermal capacity and thermal conductivity of meso-PSi are important
properties here (see chapter Thermal Properties of Porous Silicon) (Table 2).
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Porous Silicon in Immunoisolation and

Bio-filtration
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Materials for Immunoisolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microfabricated Porous Silicon as Immunoisolation Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microfabricated Porous Silicon for Bio-filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
937
938
940
941
942
Abstract
This chapter focuses on cell immunoisolation and bio-filtration applications of

porous silicon membranes. After an introduction on immunoisolation for the
treatment of diabetes, the different materials used for that function are reviewed
and compared. Applications involving porous silicon are then presented in more
detail. Other uses of microfabricated porous silicon membranes in hemofiltration
and protein sorting are also discussed.
Introduction
Transplantation of healthy pancreatic islet cells represents a potential cure for type
1 diabetes. However, dangerous immunosuppressive drugs have to be used to
prevent rejection of these cells. An alternative method consists in encapsulating
J. Schweicher (*)
Department of Chemistry, Universite Libre de Bruxelles, Bruxelles, Belgium
e-mail: julien.schweicher@gmail.com; julien.schweicher@ulb.ac.be
T.A. Desai
Department of Bioengineering and Therapeutic Sciences, University of California,
San Francisco, CA, USA
e-mail: tejal.desai@ucsf.edu
DOI 10.1007/978-3-319-05744-6_94
937
938
Fig. 1 Size of different biomolecules and biological entities versus pore size classification
the cells with protective membranes before transplantation. The semipermeable

membranes serve as immunoisolation barriers (they have to impede contact with
immune cells, antibodies, etc.) but should also allow rapid transport of oxygen,
glucose, insulin (Stokes radius: 2.75 nm) (Oliva et al. 2000), and waste products, all
of these molecules being smaller than immune components (Stokes radius of
immunoglobulin G (IgG): 5.9 nm) (Leoni and Desai 2004; Kang et al. 2007).
Figure 1 compares the size of different biomolecules and biological entities with
the general pore size classification.
Two configurations of cell encapsulation are currently being studied:
macroencapsulation where a large number of transplanted cells are confined in an
implantable device and microencapsulation where only 1 to 3 cells are encapsulated in each microbead (a large number of these beads are transplanted). Advantages and disadvantages of these approaches have already been discussed in the
literature (Scharp et al. 1984; Lysaght et al. 1994; Colton 1995; Lanza et al. 1995;
de Vos and Marchetti 2002; Beck et al. 2007; Wilson and Chaikof 2008;
Mendelsohn and Desai 2010; Basta and Calafiore 2011; Nafea et al. 2011;
OSullivan et al. 2011; Schweicher et al. 2014).
Besides immunoisolation, semipermeable membranes can also be used in
bio-filtration applications such as hemofiltration, blockage of viruses, etc.
Materials for Immunoisolation

Polymers were the first type of materials to be studied for cell immunoisolation
purposes. They can be separated in two classes: hydrogels (Nafea et al. 2011)
(alginates, agarose, polyvinyl alcohol, polyethylene glycol, etc.) and thermoplastics
Porous Silicon in Immunoisolation and Bio-filtration
939
Table 1 Comparison of different materials for immunoisolation membranes

Membrane
material
Biocompatibility
Tight pore size
distribution
High pore
density
Choice of pore
geometry
Thin membrane
Robustness
Affordability
References
Micromachined
Si
++
+++
Anodized Al2O3
+/
++
Anodized
TiO2
+++
++
Polymers
+++
+/
+/
+++
+++
+++
+++
+
Leoni and Desai
(2004), Desai
et al. (1998,
2000a, b, 2004)
+++
++
+++
+++
Gong et al. (2003),
Popat et al. (2004),
Swan et al. (2005),
La Flamme et al.
(2005, 2007),
Cho et al. (2013)
++
+
+++
Albu et al.
(2007,
2010),
Paulose et al.
(2007,
2008),
Schweicher
and Desai
(2014)
+
+++
++
Wilson and
Chaikof
(2008), Basta
and Calafiore
(2011), Nafea
et al. (2011),
Li (1998),
Dunleavy
(1996), de Vos
et al. (2006)
(Li 1998) (polyurethane, polysulfone, polytetrafluoroethylene, etc.). Despite excellent biocompatibility, polymeric membranes cannot be produced with very tight
pore size distributions (Dunleavy 1996). This parameter is obviously of utmost
importance for immunoisolation applications since it is estimated that rejection will
occur if only 1 % of the pores are larger than the size cutoff goal (Colton 1995).
This explains the more recent development of inorganic membranes with very
controlled pore sizes and distributions (Mendelsohn and Desai 2010; Schweicher
et al. 2014): micromachined porous silicon (Si), anodized porous alumina (Al2O3),
and anodized nanotubular titania (TiO2). These membrane materials are compared
with polymers in Table 1. The inorganic membranes that are presented display
straight pores, which is ideal for diffusion of nutrients and therapeutic products. On
the other hand, fabrication techniques such as powder sintering or solgel methods
produce tortuous pores (Adiga et al. 2009). Solgel procedures have nonetheless
been investigated to encapsulate islets: Pope et al. used silica gel to protect mouse
islet cells (Pope et al. 1997; Peterson et al. 1998); Carturan et al. deposited a solgel
silica layer on rat islet cells using silica precursors in the gas phase (Carturan
et al. 1997) and later used the same technique over alginate microencapsulated
cells (Boninsegna et al. 2003; Carturan et al. 2004); Sakai et al. developed another
silicate coating procedure for alginate microbeads containing mouse insulinoma
cells (Sakai et al. 2003, 2004).
940
Microfabricated Porous Silicon as Immunoisolation Membrane

The handbook chapter Porous Silicon Membranes reviews the different fabrication routes and applications of mesoporous and macroporous silicon membranes.
Among inorganic membrane materials, porous silicon has been the most studied for
immunoisolation (macroencapsulation). Desai and Ferrari developed a microfabrication technique to produce controlled slit pores in 0.55 m-thick Si membranes
(see Fig. 2) (Leoni and Desai 2004; Desai et al. 1998, 2000a, b, 2004). The width of
these pores (constant length of 45 m) can be varied from 7 to 100 nm with less than
5 % of variation. The pores are produced by dissolution of a thermally grown
sacrificial silicon oxide layer. These membranes present a porosity of ~1 % (Leoni
and Desai 2004; Desai et al. 2000b).
Desai et al. showed that rat islets encapsulated in 18, 66, and 78 nm slit pore Si
membranes present similar insulin release profiles as those of unencapsulated islets,
while the smallest pores significantly hindered the passage of IgG (Desai
et al. 1998, 1999a), thereby proving the potential of this immunoisolation technology. In vivo tests were also carried out with encapsulated rat and mouse insulinoma
cells implanted intraperitoneally in mice (Desai et al. 1999b). After 8 days,
biocapsules were surgically removed to assess the cell viability and functionality.
The cells encapsulated with 18 nm membranes showed higher functionality than
those in 66 nm porous capsules, highlighting the correlation between small pores
and immunoisolation. However, glucose diffusion is constrained for pores below
13 nm (Leoni and Desai 2004; Leoni et al. 2002), meaning that too small pores are
not adapted for this application. Surprisingly, a small leakage of IgG was observed
for 7 nm slit pores. This may be due to the flexibility of IgG that can adopt different
conformational structures or to the unfolding of its 3D structure, easing its diffusion
through the slit pores (Leoni and Desai 2004). The use of square or circular pores
would certainly help to completely block such flexible proteins, although a tiny leak
of IgG may not be so detrimental to the encapsulated cells: Iwata et al. showed
that complement components are rapidly inactivated (Iwata et al. 1994, 1995;
Fig. 2 Picture of a Si mesoporous membrane with support (left), SEM micrograph showing
mesopores in a membrane cross section (right) (Leoni et al. 2002)
941
Lanza et al. 1996), and therefore, it may be good enough to hinder IgG diffusion in
the first days after implantation rather than totally block it.
One interesting feature of porous Si membranes is the possibility to easily
modify their surface chemistry (Stewart and Buriak 2000). The handbook chapter
Silicon-Carbon Bond Formation on Porous Silicon reviews the techniques and
surface chemistries available. In order to prevent undesired adsorption of proteins
on the membranes (ultimately clogging the pores), it is also possible to coat them
with a thin layer of polyethylene glycol (PEG) (Zhang et al. 1998; Sharma
et al. 2003). PEG chains covalently linked to Si decrease the adsorption of albumin,
IgG, and fibrinogen by 76, 82, and 64 %, respectively, as compared to untreated Si.
Microfabricated Porous Silicon for Bio-filtration

Fissell and Roy currently study a modified version of the microfabricated Si
membranes with slit pores (with less than 1 % of width variation over the entire
Si wafer) for use in renal replacement devices (artificial kidney) (Fissell
et al. 2009). The latter would be a far better alternative to dialysis for people
suffering from chronic kidney failure. This group already showed that porous Si
membranes retain hydraulic permeability and molecular selectivity during a 90 h
hemofiltration experiment with anticoagulated bovine whole blood. They also
highlighted the beneficial effects of PEG coating over the membranes: significant
inhibition of protein adsorption, fouling, and thrombosis. Moreover, another recent
article from the same group showed very encouraging results for the blood compatibility of silicon materials (Muthusubramaniam et al. 2011).
Fauchet et al. developed a totally different strategy to produce ultrathin (1050
nm) porous nanocrystalline silicon membranes with round pores that can be varied
from 3 to 80 nm (Striemer et al. 2007; Agrawal et al. 2010; Gaborski et al. 2010;
Fang et al. 2010a, b; Snyder et al. 2011). These pores are created by inducing Si
crystal growth in a sputtered amorphous Si layer, and the temperature applied to
induce crystallization (annealing) determines the pore size distribution. These
membranes have been labeled nanocrystalline as the Si crystal grain sizes are
smaller than 100 nm. Finer control over pore size (subnanometer precision) can
be obtained by rapid thermal carbonization after production of the porous
membranes (Fang et al. 2010b). This type of membranes exhibits exceptional
properties: very high permeability due to the ultrathin thicknesses, pore distribution
sharp cutoff that can be tuned from 5 to 80 nm, porosity as high as 15 %, and
robustness (the membranes can support 1 atm of differential pressure without
plastic deformation or fracture). This group showed that the Si membranes have
the capability to significantly hinder IgG diffusion relative to bovine serum albumin
(BSA) while their diffusion coefficients are only within 25 % of each other
(Striemer et al. 2007). They also developed a technique to measure the
ion-selective permeability of Si membranes (Ishimatsu et al. 2010). However,
these membranes are still far from being the ideal candidate for immunoisolation
because of their fast degradation profile under physiological conditions
942
(Agrawal et al. 2010). Indeed, these Si membranes dissolve in cell culture media
over only 1 day. A postproduction annealing procedure has been developed to
extend their stability to 4 days, but this is still extremely short as compared to the
requirements for immunoisolation (desired stability of at least several months or
years). However, a special coating procedure may be able to resolve that longevity
issue in the future. The handbook chapter Functional Coatings of Porous
Silicon reviews the wide range of surface modifications studied to date.
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Porous Silicon and Solar Cells

Tayyar Dzhafarov
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reflectance of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon in Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Transfer of the Thin Silicon Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
946
946
949
952
953
Abstract
Today over 90 % of all photovoltaic solar cells produced worldwide are composed of the silicon (single crystal, multicrystalline, amorphous, etc.). Despite
this, the relatively high cost of silicon solar cells remains the main obstacle for
their even wider applications. Physical principles of working of photovoltaic
solar cell and action of antireflecting coating have been briefly presented. This
chapter reviews investigations carried out over the last 1015 years concerning
the use of porous silicon layers in silicon solar cells. Data on photovoltaic
parameters of silicon solar cells with thin porous silicon layer as antireflecting
coating and also reflectance data of PS layers have been summarized. Advantages of nanostructured PS use in silicon solar cells, concerning increase of the
cell effective surface area, lowering of the reflectance, broadening of the effective band gap of near-surface region of cell, etc., which finally promote
improved silicon cell efficiency and simplify the technology, have been
presented.
T. Dzhafarov (*)
Department of Solar and Hydrogen Energy Converters, Institute of Physics,
Azerbaijan National Academy of Sciences, Baku, Azerbaijan
e-mail: caferov@physics.ab.az
DOI 10.1007/978-3-319-05744-6_95
945
946
T. Dzhafarov
Introduction
The first observation of visible photoluminescence in nanostructured porous silicon
(PS) at room temperature opened the possibilities of a wide range photovoltaic and
photonic applications due to tunable refractive index and band gap, large surface/
volume ratio, simplicity of fabrication technology, etc. (Canham 1997). Today
porous silicon has become a very interesting and versatile material for future silicon
solar cell technology.
Photovoltaic solar cells convert sunlight energy into electricity directly. Most of
the cells are based on homojunction and heterojunction semiconductor structures
(Wurfel 2009; Nelson 2003). Homojunction presents a contact of two different type
regions (p-type and n-type) in same semiconducting material. When the materials of
n-type and p-type are different, the cell is called heterojunction. Both types of
junctions are characterized by presence of strong electric field (about 103107
V/cm) in thin junction region (about thickness of 104106 cm). Solar cell operation
consists in (a) absorption of sunlight and creating of carriers of charges (electronhole
pairs), (b) diffusion of carriers to junction, (c) separation of electrons and holes in the
electric field of junction, and (d) their moving in opposite directions, i.e., creation of
electricity on load connected to solar cell. Solar cells are characterized with an opencircuit voltage (Voc), short-circuit current density (Jsc), maximum power point
voltage and current density (Vm and Jm, respectively), conversion efficiency
or performance (), fill factor (FF), and series and parallel (shunt) resistance
(Rs and Rp). The conversion efficiency of solar cell is defined as the percentage of
incident of sunlight power which can convert in electric power. The fill factor defines
a portion of electric power produced in load connected with cell.
The main requirements for ideal solar cell material are (a) high absorption coefficient
with direct band gap of 1.21.5 eV, (b) high conversion efficiency, (c) long diffusion
length and low recombination velocity of carriers, (d) abundant, cheap, and eco-friendly
material, (e) high stability and long life (more than 25 years), and (f) integrated
processing and manufacturability, etc. Si, GaAs, CdTe, CuInGaSe (CIGS), etc., semiconducting materials meet most of the abovementioned demands. Over 95 % of all
solar cells produced worldwide are composed of silicon, and domination of siliconbased cell market probably will continue in the immediate future. Conversion efficiency
as high as 2224 % was reached today with monocrystalline silicon cells and 1821 %
with multicrystalline silicon cells. The limited conversion efficiency and cost of silicon
and other solar cells reached today are main problems which must be solved.
The reduction of different energy losses related with high reflectance, narrow band
gap, etc., is very important for the increase of silicon solar cell efficiency.
Reflectance of Porous Silicon

Minimization of surface reflection losses in solar cells is required for highefficiency silicon solar cells. Usually, the reflectance is normally reduced in crystalline silicon by using pyramidal texturing and antireflection coating (ARC) layer
947
deposition. However, the average reflectance (more than 12 %) in the wavelength

range of 4001,100 nm after current pyramid texture formation is still high. A
standard single-layer ARC works only in narrow spectral region and under a limited
range of angles of incident. Moreover, standard antireflection coating fabrication is
expensive due to use of vacuum equipment compared to chemical techniques.
Formation of porous silicon (PS) on the surface of silicon solar cells provides a
promising approach to minimize reflection (Fig. 1) and replace conventional ARC
layers on cells (Prasad et al. 1982; Menna et al. 1995; Yerokhov and Melnyk 1999;
Dzhafarov 2013).
Porous silicon consists of silicon and air. The refractive index of PS can be
changed between refractive index of silicon (nSi 3.84) and air (no 1) depending
on porosity. Reflectance of PS can be controlled by change of porosity during
electrochemical fabrication by change of etching conditions (Perez 2007). For a
dedicated review, see handbook chapter Refractive Index of Porous Silicon. It
facilitates the application of PS layers on silicon as an ARC in solar cells.
Three types of porous silicon layer as ARC are usually applied for silicon solar
cell fabrication: (1) single-layer PS of constant refractive index (of constant porosity), (2) single-layer PS of graded refractive index (of graded porosity), and
(3) double-layer PS with different refractive index (of different porosity). The
theoretical requirements for the design of single- and double-layer PS as
antireflection coating on silicon solar cell are given (Strehlke et al. 1999, 2000).
For single-layer PS on silicon substrate, the optimal ARC effect (zero net
reflection) is fulfilled under two conditions. First, refractive index of the ARC
layer (narc) is equal to the square root of the refractive index of silicon (nSi
3.84), i.e., narc (n0nSi)1/2 1.96 (no 1 is the refractive index of air). Second,
the optical thickness of the ARC to be equal to a quarter of the wavelength (min),
i.e., (narcdarc) min/4. Calculated thickness of ARC layer is 83 nm at
Fig. 1 Schematic illustration of the light reflection decrease in PS/(n-p)Si solar cell
948
T. Dzhafarov
Table 1 Effective reflectance for silicon surface with different treatments

Silicon surface treatment
PS(60 %), 105 nm)/(n+-p)
Si (100)
PS (graded)/PS
PS (78 %)/PS (38 %)/(n+-p)Si
PS (macro)/PS(micro)/mc-Si
mc-Si (acid textured)
mc-Si (KOH textured)
SiNx/mc-Si
Si (polished)
SnO2/mc-Si
PS (stain etching)/mc-Si
Cz-Si (alkaline textured)
PS (electrochemical)/Cz-Si
(alkaline textured)
PS (stain etching)/Cz-Si
(alkaline textured)
PS (electrochemical)/Cz-Si
(polished)
PS/(n+-p)Si (100) (textured)
PS/SiOx (105 nm)/(n+-p)Si
(100)
PS/Si (100)
PS/SiNx/(n+-p) Si (100)
Al2O3/PS/Si
SiNx/PS/mc-Si
Multilayer PS/Si (in air)
Multilayer PS/Si (under
glass)
PS/(n+-p) Si
PSNW/Si
Reflectance (%)
7.3
(nm)
4001,000
References
Strehlke et al. (1999)
3.7
2.4
5.8
11.4
23.4
5.3
33.9
9.4
6.6
12.6
3.4
4001,000
5001,000
500900
5001,000
5001,000
500800
5001,100
550900
5001,000
6001,000
500900
Striemer and Fauchet (2002)

Strehlke et al. (2000)
Lipinski et al. (2003a)
Lipinski et al. (2000)
3.1
500900
9.7
500900
5
3.8
500900
6001,000
Lee and Lee (2007)

Remache et al. (2010)
9.0
5
7
6
3
1.4
5001,000
4001,000
4001,100
4501,100
4001,100
4001,100
Remache et al. (2010)

Weiying et al. (2011)
Ben Rabna et al. (2013)
Rabna et al. (2012)
Selj et al. (2010)
Selj et al. (2010)
4
0.1
4001,000
Dzhafarov et al. (2012)

Najar et al. (2012)
min 650 nm. Experimental realization of single-layer ARC on silicon of 60 %

porosity and 105 nm thickness reduces the effective reflectance up to 7.3 % in the
range 400100 nm (Strehlke et al. 1999; Table 1).
PS layer with gradient refractive index was fabricated in only one technological
process and therefore permits to avoid the interface problems meeting in the
fabrication of classical multilayer ARC. Formation of thin PS layer (thickness of
100 nm) with gradient in porosity by decreasing the current density from
100 mA/cm2 to 0 mA/cm2 during electrochemical etching for 10 s leads to low
average reflectance of 3.7 % across the terrestrial solar spectrum (Table 1; Striemer
and Fauchet 2002).
For double-layer antireflection coating with refractive index of top and bottom
layers n1 and n2, respectively, on silicon (air/ARC(top)/ARC(bottom)/Si system)
the zero reflectance at normal incident light is realized at conditions n1 (non2)
949
and n2 (n1nSi) (Jayakrishnan 2009). For air/layer 1/layer 2/Si system, the ideal
values n for top layer are n1 1.57 and d1 102 nm, whereas the bottom layer
parameters are n2 2.46 and d2 65 nm. Experimental investigation of doublelayer PS ARC on silicon substrate showed that minimal effective reflectance about
2.4 % at wavelength 600 nm is achieved when PS layers of 78 % porosity
(n 1.404) and 38 % porosity (n 2.793) were used as top and bottom ARC
(Strehlke et al. 2000).
Data on reflectance of single-layer PS, double-layer PS, and combined layers
used in silicon solar cell fabrication are given in Table 1.
Layer of porous silicon nano-wires (PSNW) with pore size of 1050 nm is the
best ARC with record reflectance (R 0.1 %) (Najar et al. 2012). Good ARC effect
showed the PS layer with graded porosity (3.7 %), PS layer on textured surface of
silicon (about 3 %), double-layer PS (about 2.4 %), and combined double-layer
ARCs (SiNx, SiO2, or Al2O3/PS) with R 47 %.
Porous Silicon in Solar Cells

Standard screen-printed technology of silicon solar cells consists of six main
stages (chemical etching, p-n junction formation, parasitic junction removal,
passivation, ARC deposition, screen-printing contacts) including passivation of
surface and ARC deposition using SiNx, TiOx, or SiOx (Lipinski et al. 2003b).
These processes are usually carried out at moderate or high temperatures
(300800 C). Porous silicon layer as ARC on silicon solar cell is fabricated by
etching in HF/HNO3 solution (stain etching) or electrochemical anode etching
that is suitable for a standard silicon solar cell processing. PS layers with a wide
range of porosity, pore size (from a few nanometer to a few tens micrometers),
thickness, surface areas (up to 103 m2/cm3), morphology, and band gap for
nanoporous silicon in the range of 1.11.9 eV due to quantum size effect
(Dzhafarov and Aydin Yuksel 2009; Pickering et al. 1984) can be formed
depending on the doping level of the substrate and the etching conditions. The
room temperature fabrication of porous silicon layer on frontal surface of ready
silicon solar cell (instead of multistep process texturization, antireflection layer
deposition and passivation performed at high temperatures on standard technology) can essentially improve the photovoltaic parameters and decrease the cost
of silicon solar cells.
The potential advantages of using of porous silicon in silicon solar cells consist
of (Fig. 2; Dzhafarov 2013):
1. An increase of effective surface area of the cell exposed to illumination
2. A lowering of the effective reflectance of silicon solar cell and possibility of
formation of PS layer with smooth-changing refractive index
3. Broadening of the effective band gap of nanoporous layer playing role of a wideband optical window and formation of PS layer with a variable band gap which
can result in increase of photocurrent
950
T. Dzhafarov
Fig. 2 Energy band diagram

of nPS/(n+-p)Si solar cell
4. Possibility of the conversion of high-energy ultraviolet and blue part of the solar
spectrum into long-wavelength radiations due to photoluminescence in nanocrystalline porous silicon (Svrcek et al. 2004)
5. Surface passivation and gettering role of porous silicon (Weiying et al. 2011;
Ben Rabna et al. 2013; Solanki et al. 2004; Khedher et al. 2005)
6. Simplicity and lower cost of fabrication technology of nanoporous silicon due to
electrochemical modification of silicon
There are two types of technology of formation of porous silicon layer on silicon
solar cells: (1) the thin porous silicon is formed in the final step on the surface of
ready Si solar cell with metal contacts and (2) the relatively thick porous silicon
layer is formed prior to emitter diffusion and metal contact deposition. In the first
case, which is more applied, the thickness of porous layer (70150 nm) must be less
than the depth of n+-p (or p+-n)-junction (300800 nm), and the duration of
electrochemical etching is short (about 515 s).
Data of photovoltaic parameters of silicon solar cells (under AM1.5) with and
without porous silicon is presented in Table 2.
The review of investigations of use of the porous silicon in silicon solar cells
showed that the increase in the conversion efficiency (about of 2530 %) is
achieved for PS/Si solar cell compared to a cell without a PS layer. At the same
time, the performance of silicon solar cells with PS layer is more than that of silicon
solar cells with conventional ARC. Ag-induced chemical etching of
multicrystalline silicon solar cells producing nanoporous black silicon (see handbook chapter Color of Porous Silicon) with low surface reflectance (<5 %)
results in significant efficiency enhancement of 26 % (Shi et al. 2013). Fabrication
of nanoporous structure on screen-printed silicon solar cells using wet chemical
etching by size-controlled silver nanoparticles demonstrates reflectance less than
5 % and 15.7 % efficiency (Dan et al. 2013). The low value of effective reflectance
951
Table 2 Photovoltaic parameters of silicon solar cells with and without porous silicon layer
Jsc (mA/cm2)
or I (mA)
23.1
34.2
21.5
28.4
95 mA
137 mA
17.2
20.1
23.3
25.5
Voc
(mV)
500
520
580
585
580
570
598
606
592
595
FF
0.74
0.75
0.55
0.74
0.74
0.75
0.70
0.74
Eff.
(%)
12.1
14.5
7.5
12.5
10.3
13.5
7.6
9.5
9.6
11.2
R(%) (
650 nm)
28
4
12
3
7
12
3
18.5
27.2
580
601
0.73
0.77
7.85
12.54

7
PS/(n+-p) Si
SiOx/(n+-p) Si
(p+-n)PS/Si (100)
(p+-n)PS/Si (111)
(n+-p)PS/Si (111)
SiO2/(n+-p)
Si (111)
(ZnO-TiO2)/
(n+-p)Si
(p+-n)PS/Si
PS on one side
(p+-n)PS/Si/PS
PS on both sides
(n+-p)PS/Si
33.4
34.8
15.9 mA
12.4 mA
12.4 mA
5.1 mA
460
530
480
440
440
340
0.81
0.82
0.82
0.77
15.4
11.2
11.2
3.3
9
3.8
7
16
15
6.0 mA
370
0.79
4.4
8.8 mA
430
0.78
7.4
16
12.4 mA
490
0.84
12.75
28.9
627
0.76
13.8
PS/(n+-p) Si
SiN/(n+-p) Si
(n+-p) mc-Si
PS/(n+-p) mc-Si
(n+-p) mc-Si
(n+-p)PS/mc-Si
(n+-p) Si
PS/(n +-p) Si
PS/(n+-p) mc-Si
(n+-p) mc-Si
PS/(n+-p)Si (100)
(n+-p) Si (100)
26.3
28.4
26.6
28.9
29.8
30.2
12.5 mA
21.2 mA
27.2
22.4
30.1
23.8
602
606
572
582
577
587
480
530
592
588
571
573
0.76
0.75
0.75
0.76
0.75
0.76
0.61
0.65
0.75
0.69
0.70
0.69
12
13
11.3
12.7
12.9
13.5
12.1
9.0
12.1
9.4
10
15
5
8
12
6
3.1
12.6
Solar cell
(n+- p) Si
PS/(n+- p) Si
(n+-p) Si
PS/(n +-p) Si
(n+-p) Si
PS/(n +-p) Si
(n+-p) Si
PS/(n +-p) Si
Textured (n+-p) Si
PS/textured (n+-p)
Si
(n+-p) Si
PS/(n +-p) Si
References
Dzhafarov
et al. (2012)
Saadoun
et al. (1999)
Yerokhov
et al. (2000)
Panek
et al. (2000)
Chaoui and
Messaoud
(2007)
Remache
et al. (2010)
Aziz
et al. (2009)
Aziz
et al. (2011)
Ramizy
et al. (2001)
Ludemann
et al. (2000)
Hilali
et al. (2010)
Panek (2004)
Lipinski
et al. (2003)
Vitanov
et al. (1997)
Bilyalov
et al. (1999)
Lipinski
et al. (2000)
(continued)
952
T. Dzhafarov
Table 2 (continued)
Solar cell
(n+-p) Si (100)
textured
PS/(n+-p) Si (100)
PS/(n+-p) Si (100)
textured
PS/(n+-p) mc-Si
PS/(n+-p)Si
(n+-p) Si
M/SnO2/nSi
M/SnO2/PS/nSi
M/TiO2/nSi
M/TiO2/nSi
PS/(n+-p) pc-Si
(n+-p) pc-Si
PS/Si thin film
(30 m, 79.2 cm2)
ZnO/PS/(n+-p)Si
PS/(n+-p)Si
(n+-p)Si
Jsc (mA/cm2)
or I (mA)
130 mA
Voc
(mV)
560
FF
0.55
Eff.
(%)
9.55
R(%) (
650 nm)
14
150 mA
160 mA
560
570
0.64
0.66
10.52
11.28
5
4
720 mA
560
0.69
10.6
8.2
26.3
20.9
29
31.5
29
31.5
27
22
28.7
580
578
550
580
590
670
550
540
633
0.74
0.74
0.57
0.67
0.61
0.71
0.78
0.68
0.74
11.3
9.1
9.1
12.1
10.4
14.8
11.5
8
13.5
68
35
35.5
33.9
14.5
627
595
367
0.82
0.76
0.69
18.2
15.5
3.6
4
8
36
References
Kwon
et al. (2007)
Drabczyk
et al. (2003)
Chakravarty
et al. (2007)
Badawy (2008)
Ben Rabha
et al. (2009)
Hasse
et al. (2009)
Salman
et al. (2012)
(about 13 %) for nanoporous silicon layer that significantly reduces the optical
losses is one of the main reasons for improving the performance of PS/Si solar cell.
A wide-band gap nanoporous silicon (up to 1.9 eV) results in widening of the
spectral region of photosensitivity of the cell to the ultraviolet part of solar spectrum
and promotes the increase in the efficiency of silicon solar cells with PS layer.
Moreover, the PS layer serves as luminescence down converter (see handbook
chapter Photoluminescence of Porous Silicon) transforming the blue solar
light to red-orange light which generates additional electronhole pairs (Svrcek
et al. 2004). Application of porous silicon Bragg mirrors on backside of silicon solar
cells can improve the efficiency (Ivanov et al. 2013). It is also important to consider
the passivation and gettering properties of SiH and SiO bonds on pore surfaces
(see handbook chapter Porous Silicon Gettering) which can increase the
lifetime of minority carriers (Remache et al. 2010; Weiying et al. 2011).
Porous Silicon Transfer of the Thin Silicon Films

The reduction in the amount of high-quality expensive silicon material per solar cell
is one of the ways of lowering the cell cost. At present one of the technologies
developed to fulfill the aim of reducing the cost of silicon solar cell is porous silicon
transfer process (PSTP) (Solanki et al. 2004). The thickness of monocrystalline
953
silicon solar cell prepared by PSTP (about 550 m) is significantly lower than that
of crystalline silicon cell fabricated by standard technology (250300 m). The
PSTP process consists of four steps. First, double layers of porous silicon are
fabricated by electrochemical etching on surface of monocrystalline silicon: the
12 m-thickness low-porosity layer (20 %) at the top and 350 nm-thickness highporosity layer (5060 %) beneath. Second, the thin monocrystalline epitaxial silicon
layer (about 550 m thickness) is growing on the top (low-porosity) layer. The
low-porosity layer is of monocrystalline quality which allows the growth of a highquality epitaxial layer of silicon (see handbook chapter Homoepitaxy on Porous
Silicon). At the third step, the epitaxial silicon layer is detached from the silicon
substrate through a high-porosity layer by liftoff technique and then it is transferred
onto a foreign substrate. At the final step, the thin-film silicon solar cell is fabricated
by a standard technology. Shortly after using PSTP, cell efficiency gradually
increased from 12.5 % (in 1997) to 16.9 (in 2009). Today the record value of
efficiency of 19.1 % (S 4 cm2, Voc 650 mV, Jsc 37.8 mA/cm2, FF 77.6) for
monocrystalline silicon solar cell of 43 m thickness prepared by porous silicon
transfer technique was demonstrated (Petermann et al. 2012). It should be noted that
this porous silicon transfer process is certainly complex for industrial application;
nevertheless it still shows high-efficiency potential.
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Yerokhov V, Melnik I, Tsisaruk A, Semochko I (2000) Porous silicon in solar cell structures. Opto
Electron Rev 8:414417
Porous Silicon and Micro-Fuel Cells

Gael Gautier
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon as Gas Diffusion Layers and Catalyst Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silicon Electrochemical Etching to Achieve Flow Fields in FC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Other Applications of Porous Silicon in FC Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
957
962
962
962
962
962
Abstract
Miniaturization of fuel cells (FC) can offer a possibility in the field of small
energy sources. Many silicon-based technologies can be used to perform microfuel cells and, in particular, porous silicon. In this chapter, after general consideration on fuel cells, we describe the state of the art of porous silicon integration
in micro-fuel cells. In particular, we show how porous silicon has arisen as a
promising material to perform many functions necessary to the core fuel cell
such as proton exchange membrane, gas diffusion layer and catalyst support or
flow fields. The performances of the several final devices reported in the
literature are discussed.
Introduction
The last decade has seen an explosion of the number of portable devices integrating
more complex and energy-consuming functions. These functions require more
electrical power even if a tremendous effort is done to lower application power
G. Gautier (*)
Universite de Tours, GREMAN, Tours, France
e-mail: gael.gautier@univ-tours.fr
DOI 10.1007/978-3-319-05744-6_96
957
958
G. Gautier
needs. Therefore, miniaturization of fuel cells (FC) can offer a possibility for more
long-lasting small energy sources, as it can reach up to 530 Wh/kg (Dyer 2002), for
replacement of the current battery technologies: NiMH (3080 Wh/kg) or Li-ion/
LiPo (100200 Wh/kg). For a more extensive review focused on miniaturized fuel
cells, one can see (Sundarrajan et al. 2012; Stolten and Emonts 2012; Zhao 2009;
Nguyen and Chan 2006; Morse 2007; Kundu et al. 2007).
When dealing with miniaturization of systems, MEMS (microelectromechanical
systems) technology has permitted many silicon-based microsystems production
and, in particular, micro-fuel cells. Some authors report silicon etching using
reactive ion etching (RIE) technique (see, for instance, (Yen et al. 2003; Kundu
et al. 2006) or RIE combined with silicon wet etching techniques (Lee et al. 2009;
Zhu et al. 2008). Porous silicon (PS) has already been used to realize successful
MEMS devices (see handbook chapter Porous Silicon for Microdevices and
Microsystems). Moreover, considering PS properties, this material has been therefore a natural candidate for miniaturization of fuel cells when starting from a silicon
substrate. Reported works in this chapter will concern PEMFC (proton exchange
membrane fuel cells) with direct hydrogen fuel cells (DHFC) and other direct fuel
sources like methanol fuel cells (DMFC) or direct ethanol fuel cells (DEFC).
In the case of a DHFC, when hydrogen is delivered at the anode side, the gas has
to reach the catalyst site, generally Pt. There, the gas is adsorbed on the catalyst
surface in contact with a proton-exchanging membrane. When this condition is
fulfilled, hydrogen is protonated to form an ion that can diffuse through the
membrane. This protonation involves a loss of electron. If a conducting material
is placed at the reaction site, all the released electrons can be collected with the
conductor and driven through an external circuit to a load. The protons go through
Fig. 1 Schematic of a typical micro-fuel cell structure with a solid electrolyte membrane,
catalysts, and gas diffusion layers on both sides. The structure is sandwiched by the two current
collector bipolar plates acting also as the flow fields (After Morse 2007)
959
Table 1 PEM micro-fuel cell prototypes, incorporating mesoporous silicon as the proton
exchange membrane in the core system, are reported in the literature. The performance of the
membranes (proton conductivity) and the FC, i.e., the open circuit voltage (OCV) and the power
density peak during the test, is reported
Fuel cell type

DHFC
PEMFC
DHFC
DHFC
DHFC
PEMFC
DMFC
PEMFC
Membrane
technology
Filling by
Nafion
Sulfuric acid
(8 M)-loaded
membrane
Filling by
Nafion
Sulfuric acid
(20 %) loaded
membrane
Pore surface
grafting by
silane
molecules
Acid-loaded
membrane
Filling by
Nafion
Filling by
Nafion
Sulfonated
pore surface
Membrane
proton
conductivity
(mS/cm)
40
Fuel cell
performance: OCV
(V)/power density
(mW/cm2)
0.8/20 (H2,
ambient air)
7330
References
(Pichonat and
Gauthier-Manuel
2006a, b)
(Gold et al. 2004)
0.89/1.27 (H2,
ambient air)
0.97/12.75 (H2,
ambient air)
(Nagayama
et al. 2005)
(Nagayama
et al. 2005)
0.47/17 (H2/
ambient air)
(Pichonat and
Gauthier-Manuel
2006c)
44
0.65/94 (formic acid +

sulfuric acid/air)
2030
110
1/332 (H2,
ambient air)
(Chu et al. 2006,

2007)
(Torres-Herrero
et al. 2010)
(Wang
et al. 2011)
(Moghaddam
et al. 2010)
the membrane to the cathode side where they are consumed in a catalyzed reaction
with oxygen if electrons coming through the external circuit can reach the anode.
A schematic view of a typical micro-fuel cell structure is given on Fig. 1
illustrating the different parts of the system. This figure points out the necessary
parts to carry out a fuel cell stack. Flow fields are necessary for fuel delivery to the
reaction sites and current collection. The gas diffusion layer (GDL) allows a good
distribution of the fuel on the catalyst layers. The membrane conducts the ions
(protons) from the anode to the cathode when generated during the fuel cell
operation. This membrane must also be impermeable to fuel and electrically
isolating. Considering its intrinsic properties, PS can act as the membrane of the
fuel cell (see handbook chapter Porous Silicon Membranes for a review of
fabrication routes). This function can be achieved only if the porous membrane is
functionalized by molecule grafting or by Nafion filling, for example. PS can be
also integrated in the core system (i.e., the MEA, membrane electrode assembly).
There, it can act as the membrane support of the fuel cell performing the gas

0.16
0.6
Au/PS structure
Au/PS structure
MEA support (GDL)

MEA support
Borohydride FC
Direct hydrogen
sulfide FC
DMFC
DMFC
0.64
MEA support (GDL)
DMFC
1
1
0.63
0.75
0.25
0.25
Aactive (cm2)
MEA support (GDL)
MEA support (GDL)
FC PART
MEA support
(CC/GDL/FF)
MEA support (GDL)
MEA support (GDL)
MEA support(GDL)
DHFC and RHFC

SOFC
DMFC
DHFC
DHFC/DMFC
DHFC
DMFC
Fuel cell type

DHFC
0.7
0.55
0.4
0.45
0.9
1
0.15
0.7
0.8
0.30.45
OCV (V)
0.9
13
13
28
37
145
0.016
0.009
1.5
0.045
PP (mW/cm2)
60
H2 and O2
H2 and air
MeOH 1 M
and air
MeOH 1 M
and air
MeOH 2 M
and air
NaBH4 and air
H2S 80 M
and air
MeOH 2 M
and air
Fuel (A and K)
H2 and O2
RT
RT
RT
RT
40
600
80
T ( C)
RT
(Dzhafarov et al. 2010)

(Dzhafarov and Yuksel
2011)
(Miu et al. 2009)
(Zhou et al. 2011)
(Liu et al. 2006)
(Onoe et al. 2005)
(Yamazaki 2004)
Reference
(Meyers and Maynard
2002)
(Min et al. 2003; 2006)
(Darrigo et al. 2003)
(Hayase et al. 2004)
Table 2 Micro-FC prototypes, incorporating mesoporous silicon in the core system, reported in the literature for DHFC (direct hydrogen fuel cell), DMFC
(direct methanol fuel cell), and RHFC (reformed hydrogen fuel cell). Aactive is the active surface, OCV the open circuit voltage of the cell, PP the power peak
during the test, fuel A and K are the fuels provided at anode (A) and cathode (K), T is the temperature during the test, RT is the room temperature, MeOH is
methanol and EtOH is ethanol
960
G. Gautier
PS type
Localized electropolishing
CPS
CPS
CPS
CPS
Macropores
Macropores
Fuel cell
type
DHFC
DEFC
DMFC
DHFC
PEMFC
DHFC
DHFC (3D)
1.82
Aactive (cm2)
0.9
0.85
0.9
OCV (V)
0.9
0.26
90
9.5
250
100200
PP (mW)
60
8
H2 and air
GAS A & K
H2 and O2
EtOH 8.5 M
and O2
MeOH and
HNO3
H2 and air
H2 and air
RT
RT
RT
RT-60
T ( C)
RT
RT
(Ohlsen et al. 2003; Mallari

et al. 2004; Paulson 2003)
(Lee et al. 2007)
(Starkov 2007)
(Desplobain et al. 2009; Gautier
et al. 2012)
(Deplobain and Gautier 2008; Kouassi
et al. 2012)
References
(Meyers and Maynard 2002)
(Aravamudhan et al. 2005)
Table 3 Micro-FC prototypes, incorporating macroporous silicon in the core system, reviewed from the literature. See Table 2 for abbreviations. CPS
designates coherent macroporous silicon

961
962
G. Gautier
diffusion layer and catalyst support function. Macroporous silicon can be also used
to perform the cell flow fields.

Table 1 lists the performances of functionalized mesoporous silicon PEM.
Porous Silicon as Gas Diffusion Layers and Catalyst Support

Table 2 provides performances of fuel cells based on a PS GDL.
Silicon Electrochemical Etching to Achieve Flow Fields in FC

Table 3 provides performances of fuel cells based on electrochemically etched flow
fields.
Other Applications of Porous Silicon in FC Systems

Presting et al. performed a microsized reformer unit using porous silicon (Presting
et al. 2004). Porous silicon can be also integrated as hydrogen source in the gas feed
system (Lysenko et al. 2005). A maximal hydrogen concentration of 66 mmol/g
was detected in high-porosity nanoporous layers. This value is comparable with
other substances containing hydrogen such as hybrid materials or methanol. One
can see also the work of Moghaddam et al. on the integration of the PS fuel
reservoir (Moghaddam et al. 2008). Recent development on enzymatic biofuel
cells has been also reported (Wang et al. 2009).
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Chu K, Shannon M, Masel R (2006) An improved miniature direct formic acid fuel cell
based on nanoporous silicon for portable power generation. J Electrochem Soc 153:
A1562A1567
Chu K, Shannon M, Masel R (2007) Porous silicon fuel cells for micro power generation.
J Micromech Microeng 17:S243S249
Darrigo G, Spinella C, Arena G, Lorenti S (2003) Fabrication of miniaturised Si-based
electrocatalytic membranes. Mater Sci Eng C 23:1318
Deplobain S, Gautier G (2008) Cell holder for fuel cell. US Patent 12/679,266
Desplobain S, Gautier G, Ventura L, Bouillon P (2009) Macroporous silicon hydrogen diffusion
layers for micro-fuel cells. Phys Stat Solidi (a) 206:12821285
963
Dyer CK (2002) Fuel cells for portable applications. J Power Sources 106:3134
Dzhafarov T, Yuksel SA (2011) Nano-porous silicon-bases mini hydrogen fuel cells. Intech, Rejka
Croatia
Dzhafarov T, Oruc Lus C, Aydin Yuksel S, Caliskan M, Yesilkaya S (2010) Au/porous siliconbased sodium borohydride fuel cells. Int J Energy Res 34:13861392
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layers for micro-fuel cells: from planar to 3D structures. Microelectr Eng 90:7982
Gold S, Chu K, Lu C, Shannon M, Masel R (2004) Acid loaded porous silicon as a proton
exchange membrane for micro-fuel cells. J Power Sources 135:198203
Hayase M, Kawase T, Hatsuzawa T (2004) Miniature 250 m thick fuel cell with monolithically
fabricated silicon electrodes. Electrochem Solid-State Lett 7:A231A234
Kouassi S, Gautier G, Thery J, Desplobain S, Borella M, Ventura L, Laurent J (2012) Proton
exchange membrane micro fuel cells on 3D porous silicon gas diffusion layers. J Power
Sources 216:1521
Kundu A, Jang JH, Lee HR, Kim SH, Gil JH, Jung CR, Oh YS (2006) MEMS-based micro-fuel
processor for application in a cell phone. J Power Sources 162:572578
Kundu A, Jang JH, Gil JH, Jung CR, Lee HR, Kim SH, Ku B, Oh YS (2007) Micro-fuel cells:
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Lee C, Lee S, Huang R, Chuang C (2007) Integration of the micro thermal sensor and porous
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Lee CY, Lee SJ, Hu YC, Shih WP, Fan WY, Chuang CW (2009) Integration of silicon micro-hole
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Liu X, Suo C, Zhang Y, Zhang H, Dhum C, Chen W, Lu X (2006) Application of MEMS
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Lysenko V, Bidault F, Alekseev S, Zaitsev V, Barbier D, Turpin C, Geobaldo F, Rivolo P, Garrone
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109:1971119718
Mallari JC, Snyder SM, Chung V, Petrovic S (2004) Fuel cell electrode pair assemblies and related
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Meyers J, Maynard H (2002) Design considerations for miniaturized PEM fuel cells. J Power
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Min K, Tanaka S, Esashi M (2003) Silicon-based micro-polymer electrolyte fuel cells. In: IEEE
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Min K, Tanaka S, Esashi M (2006) Fabrication of novel MEMS-based polymer electrolyte fuel
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Porous Silicon and Li-Ion Batteries

Nae-Lih Wu
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Si Anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
965
966
971
972
Abstract
Research for advanced Li-ion batteries (LIBs) has been following the direction
toward higher energy and power densities. As an anode active material for LIBs, Si
has a maximum theoretical capacity far greater than that of the currently commercial graphite anode. However, Si lithiation/de-lithiation is accompanied by large
volume expansion/contraction, leading to mechanical instability and hence fast
capacity fading. Significant advancement in overcoming this problem has been
demonstrated by adopting nanostructured porous Si anode materials, which contain
preset voids to accommodate volume expansion of the Si particles so that the
dimensional variations of the entire electrode layer can be mitigated. This chapter
reviews reports of porous Si anode materials synthesized by different methods,
including etching, magnesiothermic reaction, templating, and electro-spraying, and
the electrochemical performance of the resulting Si anode materials.
Introduction
Lithium-ion batteries (LIBs) (Wakihara and Yamamoto 1998) continue to be the
predominant energy storage devices in the foreseeable future in meeting the need of
mobile communication devices and electric vehicle (EV) and renewable energy
N.-L. Wu (*)
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
e-mail: nlw001@ntu.edu.tw
DOI 10.1007/978-3-319-05744-6_98
965
966
N.-L. Wu
Fig. 1 Schematics of two methods to introduce preset voids into the electrode structure for
accommodating volume expansion of the Si component in the electrode during lithiation
applications. As an anode active material for LIBs, Si has a maximum theoretical

capacity of ca. 4,200 mAh/g (Li4.4Si) (Wen and Huggins 1981; Obrovac and
Christensen 2004), which is far greater than that of the currently commercial graphite
anode (370 mAh/g). However, the lithiation process is accompanied by reduction in
density, and this will lead to large volume expansion and contraction of the Si electrode
upon electrochemical lithiation/de-lithiation, respectively. The consequences of the
cyclic volumetric variations of the electrode active material during the operation of a
battery cell include, among others, destruction of the integrity of the electrode active
layer, causing the layer to crumble, and detachment of the entire active layer from the
underlying current collector. Both lead to escalated increase in cell resistance and fast
fading in capacity. It has lately been a research trend to utilize porous Si-containing
materials for the LIB anode applications in order to enhance the dimensional stability of
the high-capacity anode active layer. The idea behind this enhancement is to incorporate preset voids into the electrode active layer in order to accommodate the volume
expansion of the Si particles so that the dimensional variations of the active layer
during the charge/discharge cycle can be mitigated. As schematically shown in Fig. 1,
there are basically two approaches that have been adopted to introduce the preset voids.
In the first approach (Fig. 1a), Si particles, mostly nanoparticles, are embedded within a
porous supporting matrix (mostly C) that provides the open space to accommodate the
volume expansion of the Si particles. The use of nanoscaled Si facilitates stress relief,
minimizing particle fracturing. In the second approach, the Si particles themselves are
made porous so that the open space created within individual particles can accommodate the volume expansion of the solid skeleton.
Porous Si Anodes
Table 1 summarizes some microstructural and electrochemical properties of porous
Si anode materials, as pertaining to the second approach mentioned above,
collected from the literature published since 2005. Several synthesis methods
Reference
Li et al. (2012)
Lee et al. (2012)
Zhao et al. (2012)
Ge et al. (2012)
Lin et al. (2012)
Bang et al. (2012)
Liu et al. (2012)
Bang et al. (2011)
Thakur et al. (2012b)
Chen et al. (2012b)
Shen et al. (2012)
Tao et al. (2012b)
Xin et al. (2012)
Tao et al. (2012a)
Yu et al. (2010)
Chen et al. (2011)
Methoda
E
E
E
E
E
E
E
E
E
M
M
M
M
M
M
M
Morphologyb
P
P
P
NW
P
P
P
P
P
P
P
P
P
P
P
P
1st-cycle: de-lithiation
capacity (mAh/g)/
Coulombic efficiency (%)c/
Currentd
770/55/0.1C
1600/83/0.1C
1215/81/
3038/91/0.1C
800/80/0.05C
2050/94/0.2C
2278/80/0.2C
2420/91/0.1C
1000//f
3160/84/0.03C
1818/73/
913/51/0.06C
850/50/0.04C
850/61/0.07C
2903/81/0.2C
3000/61/0.01C
Table 1 Synthesis and electrochemical and microstructural properties of porous Si anode

Capacity
retentione (%)/
cycle #
86/100
91/100
123/50f
65/200
125/50f
87/50
28/50
95/70
1000/600f
70/100
35/30
97/60
118/30
45/220
70/100
21/50
Rate performance
(mAh/g)/Current
530/1.5C
1500/3C
1300/2.4C
2500/3C
2234/3C
2000/0.1C
504/0.6C
530/3C
400/2C
1500/2C
(continued)
Surface area (m2/g)/

Pore volume (cm3/g)
256.4/1.13
46/
298/0.84
(24 %)g
14/
4.5/
46.85/
103/
96/
124/0.13
181.5/0.54
437/0.26
162/

967
Method
M
M
M
T
T
T
T
AE
AE
AE
AE
ES
Morphology
P
P
P
P
P
F
P
F
F
W
W
P
1st-cycle: de-lithiation
capacity (mAh/g)/
Coulombic efficiency (%)c/
Currentd
1155/67/0.2C
2790/93/0.02C
2462/72/0.03C
2353/64/0.1C
2729/77/0.1C
1689/78/0.1C
2760/88/0.2 C
1280/79/0.05C
980/70/1.5C
(40 mC/cm2)
1134/81/0.03C
1615/65/0.02C
Capacity
retentione (%)/
cycle #
86/200
55/300
50/100
69/100
40/700
88/145
99/100
198/35
122/20
35.7/19
62/50
AE anodic etching, E etching, M magnesiothermic reaction, T template, ES electro-spray

F film, P particle, NW nanowire (NW), W wafer
c
Coulombic efficiency (%) de-lithiation capacity/lithiation capacity
d
Current is expressed in terms of C-rate
e
Capacity retention (%) de-lithiation capacity at selected cycle number/de-lithiation of 1st cycle
f
Lithiation/de-lithiation cycling test is performed with fixed lithiation capacity
g
Porosity
Reference
Gao et al. (2011)
Liu et al. (2013)
Xing et al. (2013)
Chen et al. (2012a)
Yao et al. (2011)
Esmanski & Ozin (2009)
Kim et al. (2008)
Thakur et al. (2012a)
Nishio et al. (2012)
Kang et al. (2008)
Sun et al. (2012)
Yin et al. (2011)
Table 1 (continued)
Rate performance
(mAh/g)/Current
680/2C
644/2C
1150/0.3C
900/2.5C
2060/2C
866/1C
2471/2C
800/0.1C
Surface area (m2/g)/

Pore volume (cm3/g)
141/
234/
150/0.62
158/
(70 %)g
57/
968
N.-L. Wu
969
Fig. 2 Porous Si particle

synthesized by the metalassisted chemical etching
(MACE) method
have been identified for preparing the porous Si anode materials (column
1, Table 1). One of the two most adopted methods is known as the metal-assisted
chemical etching (MACE; denoted as E in Table 1). The fundamental principle of
this method can be found in the handbook chapter Porous Silicon Formation by
Metal Nanoparticle-Assisted Etching. Figure 2 shows an example of the MACEderived porous Si particle. The other most adopted method is magnesiothermic
reduction (denoted as M in Table 1). In this method (see handbook chapter
Porous Silicon Formation by Porous Silica Reduction), porous Si oxide materials are reduced by magnesium vapor under high-temperature thermal treatment.
The porous Si oxide precursors may be synthesized via the conventional solgel
processes. Porous Si particles with unique pore structures, such as hollow interior
and ordered mesoporosity, may be obtained from Si oxides having the same pore
structures which are achieved by using proper templates.
The third method is the template process (T), where Si is deposited, by either
chemical vapor deposition or solution chemistry, on SiO2 or other template materials, and the templates are subsequently removed to produce porous Si (see
handbook chapter Routes of Formation for Porous Silicon). Anodic etching
method (AE) has been adopted to produce porous Si surface layers/film on Si wafer
(chapter Porous Silicon Formation by Anodization). Finally, electro-spraying
(ES) is used for making SiC porous composite particles.
To form the LIB anode from Si or Si-containing particles, the particles along
with conductive additives, typically acetylene black and graphite flakes, and
polymer binder are dispersed in an solvent to make slurry mixture. The slurry is
then casted on to a metal (Cu for anode) foil, which serves as current collector, and
finally dried to form the active layer. The charge storage capacity, expressed in
terms of mAh/g, of the electrochemical active material, is measured in a half-cell
configuration, where the Si-containing electrode is subjected to electrochemical
970
N.-L. Wu
Fig. 3 Voltage versus a

Li/Li+ of Si anode upon
lithiation and de-lithiation
Potential vs. Li+ /Li (V)
1.2
1.0
0.8
0.6
de-lithiation
0.4
lithiation
0.2
0.0
200
400
600
800
Capacity (mAh/g)
1000
lithiation and de-lithiation cycles against a Li foil counter electrode in an organic

electrolyte that contains Li ions. Li ions in the electrolyte might be consumed
during cycling by irreversible side electrochemical reactions, such as electrolyte
decomposition at electrode surface, and incomplete de-lithiation from the active
materials. The use of Li foil as the counter electrode in the half-cell configuration is
to ensure unlimited supply of Li ions in the electrolyte. In the practical full-cell
operation, the Li ions are supplied by the cathode electrode, and, unlike in the halfcell, the cathode provides limited amount of the Li ions. Therefore, any irreversible
consumption of Li ions by the anode (as well as cathode itself) during cycling will
result in capacity fading of the entire cell.
Figure 3 shows an example of the potential curves of a Si electrode acquired
during a lithiation/de-lithiation cycle in the half-cell configuration (against a Li-foil
counter-electrode). Here the potential of the Si working electrode is plotted versus
accumulative charge per gram of the anode electrode. Upon lithiation (in the
direction of increasing accumulative charge), the potential of the Si-containing
working electrode is reduced with increasing capacity. Lithiation of Si typically
commences at ca. 0.3 V (vs. Li/Li+ reference), as indicated by the occurrence of a
sloped plateau. The capacity above 0.3 V originates mainly from irreversible
electrolyte decomposition at the anode surface to form the so-called solid-electrolyte
interphase (SEI) layer and possible lithiation of the other components, such as the
skeletal support materials (Fig. 1a), in the electrode. These side electrochemical
reactions may proceed concurrently with lithiation of Si below 0.3 V. Upon
de-lithiation (in the direction of decreasing accumulative charge), there is a
corresponding sloped plateau toward higher potential. The potential difference
between the lithiation and de-lithiation plateaus is caused by polarization. One
notices in Fig. 3 that the de-lithiation capacity is less than the lithiation capacity so
that the accumulative capacity does not become zero upon the completion of one
cycle. The difference between the lithiation and de-lithiation capacities is referred
to as irreversible capacity. The ratio of de-lithiation capacity to lithiation capacity is
called the coulombic efficiency of a cycle. Other than the abovementioned SEI
971
formation, several other irreversible electrochemical events may contribute to the

irreversible capacity, such as formation of Li2O via reaction between Li and
O-containing contaminants and trapping of Li ions within the amorphous C support
materials and native silicate surface layers. The irreversible capacity is typically the
largest during the first cycle and rapidly reduces during the subsequent cycles. It is
worth mentioning that the irreversible consumption of Li ions by anode may in
particular lead to escalated capacity fading in the operation of a practical full cell,
where only limited amount of Li ions is provided by the cathode.
The third column in Table 1 lists the first-cycle de-lithiation capacity, coulombic
efficiency, and the current density at which the data have been acquired. Up to now,
the state-of-the-art Si-based LIB anodes typically exhibits considerable first-cycle
irreversible capacities. As a result, the first-cycle de-lithiation, rather than lithiation,
capacity reflects more closely the practical capacity that can be utilized in subsequent cycles of a Si anode. The lithiation capacity can be calculated by taking into
account of the coulombic efficiency. The current for battery test is in general
expressed in terms of C-rate, which corresponds to the fraction of the total capacity
that can be drawn in an hour. For example, 0.1 C-rate corresponds to a discharge
current that draws one-tenth of the total capacity of the electrode in an hour.
To reflect the cycling stability of the Si electrodes, column 4 in Table 1 lists the
fraction of the de-lithiation capacity remaining after a certain number of lithiation/
de-lithiation cycles. Two types of testing protocols can be found in the literature.
The most popular protocol is to fully lithiated and de-lithiated the Si-containing
electrode during every cycle. In this case, the capacity retention will be no greater
than 1.0, as the capacity of the electrode gradually decreases with cycling. The
other test protocol, referred to as the fixed-capacity lithiation, is to lithiate the
electrode only to a fixed capacity below the maximum capacity and then
de-lithiated. This testing protocol is meant to mimic the situation where the
capacity of Si anode is not to be fully utilized (in order to reduce the extent of
volume expansion) by introducing excess anode capacity in the full cell. Under this
protocol, the de-lithiation capacity may in some cases increase during early cycles,
leading to capacity retention values being greater than unity within limited cycles,
as shown in Table 1.
Finally, column 5, Table 1 lists the capacities at higher current rates. They
indicate the capability of the Si-containing electrode to be operated under highpower conditions, as demanded for electric vehicle and power-tool applications.
Conclusions
Significant advancement in overcoming the volume expansion problem of Si anode
has been demonstrated in recent years by adopting nanostructured porous Si
materials. Porous Si particulate materials can easily be incorporated into existing
slurry-based coating process for making thick (a few tens m) electrodes for
practical applications. This is an important advantage over the Si nanotube/
wire-type electrodes (Cui et al. 2009), where the Si nanotube/wires are grown
972
N.-L. Wu
through a time-consuming deposition reaction on metal substrates. Other than

dimensional stability, there are other important facts to consider when operating
and designing a porous Si anode material. Firstly, although the reported porous Si
anodes have unanimously shown remarkable increase in specific capacity, attention
should be paid to capacity/energy density (based on volume), which determines the
size of a battery and is of primary concern for most practical applications. Commercial graphite electrodes have a typical press density of ca. 1.5 g/cm3, while such
information is usually missing in the literature of porous Si electrodes. As an
example, a press density of merely 0.5 g/cm3 is obtained in authors laboratory
for the MACE-derived porous Si electrode that contains carbon conductive additives of 20 wt% and prepared via a pilot assembly line. The presence of excessive
porosity in the porous Si materials, although benefiting the dimensional stability of
the electrode upon cycling, may run the risk of lower capacity (energy) per unit
volume of the electrode as compared with graphite electrode. Secondly, the porous
Si electrodes commonly exhibits very large first-cycle irreversible capacity
(column 4 in Table 1), as well as appreciable capacity loss (>0.5 %) in subsequent
cycles. These capacity losses originate mainly from irreversible electrolyte decomposition (SEI formation) resulting from interaction between the electrolyte and
electrode surface at low potentials. The use of porous Si materials increases the
electrolyte/Si interfacial area and hence may amplify the SEI formation problem.
These additional issues also need to be coped with for porous Si materials to
become viable LIB anodes.
References
Bang BM, Kim H, Song HK, Cho J, Park S (2011) Scalable approach to multi-dimensional bulk Si
anodes via metal-assisted chemical etching. Energy Environ Sci 4:50135019
Bang BM, Lee JI, Kim H, Cho J, Park S (2012) High-performance macroporous bulk silicon
anodes synthesized by template-free chemical etching. Adv Energy Mat 2:878883
Chen W, Fan Z, Dhanabalan A, Chen C, Wang C (2011) Mesoporous silicon anodes prepared by
magnesiothermic reduction for lithium ion batteries. J. Electrochem Soc 158:A1055A1059
Chen S, Gordin ML, Yi R, Howlett G, Sohn H, Wang D (2012a) Silicon corehollow carbon shell
nanocomposites with tunable buffer voids for high capacity anodes of lithium-ion batteries.
Phys Chem Chem Phys 14:1274112745
Chen D, Mei X, Ji G, Lu M, Xie J, Lu J, Lee JY (2012b) Reversible lithium-ion storage in silvertreated nanoscale hollow porous silicon particles. Angew Chem Int Ed 51:24092413
Cui LF, Ruffo R, Chan CK, Peng H, Cui Y (2009) Crystalline-amorphous core-shell silicon
nanowires for high capacity and high current battery electrodes. Nano Lett 9:491495
Esmanski A, Ozin GA (2009) Silicon inverse-opal-based macroporous materials as negative
electrodes for lithium ion batteries. Adv Funct Mater 19:19992010
Gao P, Jia H, Yang J, Nuli Y, Wang J, Chen J (2011) Three-dimensional porous silicon-MWNT
heterostructure with superior lithium storage performance. Phys Chem Chem Phys
13:2010820111
anode with long cycle life. Nano Lett 12:23182323
Kang DK, Gole JL, Shin HC (2008) Microstructured nanopore-walled porous silicon as an anode
material for rechargeable lithium batteries. J Electrochem Soc 155:A276A281
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Kim H, Han B, Choo J, Cho J (2008) Three-dimensional porous silicon particles for use in highperformance lithium secondary batteries. Angew Chem Int Ed 47:1015110154
Lee JI, Lee KT, Cho J, Kim J, Choi NS, Park S (2012) Chemical-assisted thermal disproportionation of porous silicon monoxide into silicon-based multicomponent systems. Angew Chem Int
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Li X, Meduri P, Chen X, Qi W, Engelhard MH, Xu W, Ding F, Xiao J, Wang W, Wang C, Zhang
JG, Liu J (2012) Hollow core-shell structured porous Si-C nanocomposites for Li-ion battery
anodes. J Mater Chem 22:1101411017
Lin CC, Yen YC, Wu HC, Wu NL (2012) Synthesis of porous Si particles by metal-assisted
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Liu Y, Chen B, Cao F, Chan HLW, Zhao X, Yuan J (2012) One-pot synthesis of three-dimensional
silver-embedded porous silicon micronparticle for lithium-ion batteries. J Mater Chem
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Liu N, Huo K, McDowell MT, Zhao J, Cui Y (2013) Rice husks as a sustainable source of
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Nishio K, Tagawa S, Fukushima T, Masuda H (2012) Highly ordered nanoporous Si for negative
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Sun X, Huang H, Chu KL, Zhuang Y (2012) Anodized macroporous silicon anode for integration
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Tao HC, Fan LZ, Qu X (2012a) Facile synthesis of ordered porous Si@C nanorods as anode
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Thakur M, Isaacson M, Sinsabaugh SL, Wong MS, Biswal SL (2012a) Gold-coated porous silicon
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Energetics with Porous Silicon

Monuko duPlessis
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Porous Silicon Layers for Explosive Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Types of Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Long-Term Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
New Developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
976
976
978
979
981
981
981
982
982
Abstract
The room-temperature energetic properties of porous silicon filled with an

oxidant was accidentally discovered in 2002. Since then, this new branch of
the porous silicon technology has made some progress, and several possible
applications of this technology have been proposed. Of importance in the
technology development are aspects like the type of oxidizer to be used,
stabilization of the oxidizer in the pores, the effect of surface hydrogen on
the long-term stability and energetic properties, the initiation of the reaction
via electrical hot wires or laser illumination, the energy released from the
reaction, as well as the reaction velocity. In this chapter, the above criteria are
discussed, but emphasis is also placed on the porous silicon growth conditions,
the effect of porous layer thickness, porosity, and the pore dimensions. The
method to deposit the solid-state oxidizer in the pores via solvents is investigated, as well as the gas being generated during the energetic reaction. Some
M. duPlessis (*)
Carl and Emily Fuchs Institute for Microelectronics, Department of Electrical, Electronic and
Computer Engineering, University of Pretoria, Pretoria, South Africa
e-mail: monuko@up.ac.za
DOI 10.1007/978-3-319-05744-6_99
975
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M. duPlessis
applications of this relatively new technology are proposed and discussed. As

an interesting new development, the correlation between the nano-explosions
of porous silicon and the appearance and development of the natural phenomenon of ball lightning, caused by small silicon particles covered with hydrogen
atoms, is discussed.
Introduction
With the scaling down of silicon technology feature sizes, more functionality can be
integrated onto a silicon chip, leading to the More than Moore concept. The
porous silicon technology opened the door to a number of new novel applications,
one of which is porous silicon being used as an energetic material. The importance
of particle technology as an integral part of energetic materials design is well
documented (Teipel and Mikonsaari 2004), as well as the influence of particle
size on reactions of energetic materials. Using porous silicon significantly increases
the oxidation reaction rates which are crucial for explosive reactions, since the
spacing between silicon and oxidizing atoms is at the atomic scale (Clement
et al. 2005). Nanoporous silicon filled with an oxidizer is a promising energetic
material which is compatible with silicon process technology, especially for incorporation into semiconductor circuitry. The first reference to porous silicon explosive behavior was in 1992 when it was reported (McCord et al. 1992) that a flash of
light and an audible pop could be observed when concentrated HNO3 was dropped
on the surface of dry porous silicon. Microscale silicon dimensions were studied in
1998 as an integral part of pyrotechnic compositions which burn mainly via solidsolid reactions (Brown et al. 1998). It was found that for silicon particles ranging
from 1 to 2.6 m radius, the maximum burning rate scales inversely with the silicon
particle radius in the Si/Pb3O4 system, reaching a value of 260 mm/s at 1 m silicon
particle radius. It was shown that at the smaller particle sizes, there are more contact
points between the silicon and the oxidant, thus increasing the burning rates. In
2001, nano-explosions were accomplished at cryogenic temperatures after filling
the pores of hydrogen-terminated porous silicon with condensed or liquid oxygen
(Kovalev et al. 2001). A major breakthrough was reported in 2002 of a nanoexplosion in porous silicon filled with a solid-state oxidant at room temperature
(Mikulec et al. 2002). Applying heat to the device resulted in a strong exothermic
reaction.
Porous Silicon Layers for Explosive Applications

Porous silicon is most often prepared using an electrochemical etch technique
(anodization), usually using a HF/ethanol electrolyte. Chapter Porous Silicon
Formation by Anodization of this handbook reviews this fabrication method.
Tables 1 and 2 list porous silicon parameters of layers prepared for explosive
977
Table 1 The electrochemical etch parameters of selected explosive devices

Reference
Kovalev et al. 2001
du Plessis 2007
Churaman et al. 2008
Plummer et al. 2008
Becker et al. 2010, 2011
Type
p-type
p-type
p-type
p-type
p-type
Resistivity
(-cm)
10 310
0.20.3
110
36
120
Current density
2070 mA/cm2
76.5 mA/cm2
20 mA/cm2
22.5 mA/cm2
Galvanic
Electrolyte HF/ethanol
1:1 (50 % HF)
1.5:1 (50 % HF)
1:1 (25 % HF)
1:1 (40 % HF)
3:1 (49 % HF) and
2.4 % vol 30 % H2O2
Table 2 The porous silicon properties of selected explosive devices

Reference
Kovalev et al. 2001
du Plessis 2007
Plummer et al. 2008
Becker et al. 2010, 2011
Porosity (%)
4070
65
55.9
6269
Pore size (nm)

210
3.4
4
9.714.7
2.653.05
Thickness (m)
57
40
15
6595
applications. It is evident that a wide range of etch parameters can be used, with
silicon resistivities ranging from 1 m-cm to 20 -cm and current densities
ranging from 20 to 76.5 mA/cm2. The porosities are generally higher than 60 %,
and the pore sizes vary for most applications between 2 and 15 nm. It was reported
(Clement et al. 2005) that the highest energy yield of the explosive reaction was
assured when a stoichiometric ratio of SiX2, where X is oxygen or sulfur, for
example, could be realized. This was only possible for porous layer porosities in
the range of 70 % for most oxidizers.
In Table 1, mention is made of a very interesting development of late, namely,
fabricating porous silicon layers using a galvanic etching approach that does not
require an external power supply (Becker et al. 2010). In the presence of a chemical
oxidant such as hydrogen peroxide (H2O2) in the HF/ethanol electrolyte, a noble
metal such as platinum or gold directly deposited on silicon can serve as a cathode,
while the silicon itself acts as the anode to form a galvanic cell that enables Si
etching without the need for an external current source. Chapter Porous Silicon
Formation by Galvanic Etching of this handbook reviews this approach. In an
effort to produce low-cost nanostructured porous silicon, a process has also been
developed where porous silicon can be formed from metallurgical grade silicon
powders through a chemical stain etching process (Subramanian et al. 2008). The
etching of the silicon powder, with silicon particles ranging in size from 4 to 11 m,
in a nitric acid-hydrofluoric acid mixture creates a network of nanocrystals only
45 nm in size. Chapter Porous Silicon Formation by Stain Etching of this
handbook covers this fabrication route.
978
M. duPlessis
Types of Oxidants
Several types of oxidants have been utilized in nano-explosive devices. Detailed
investigation into the properties of a range of oxidants (Clement et al. 2005)
showed that the perchlorates were much more efficient for energetic explosions
than the nitrates. Most of the oxidizers in use are available in a powder format,
and the simplest technique to impregnate the pores is to fill the pores from a
solution containing the oxidizer. Due to the organophilic surface nature of the
porous silicon, water does not penetrate the pores, and another solvent has to be
used. Methanol and ethanol are good solvents, and acetone can also be used in
some instances. A problem to overcome is the fact that oxidizers solvable in
organic liquids are always hygroscopic. Some of the oxidizers investigated are
summarized in Table 3, and the most promising for explosive interaction are
marked in bold.
A typical procedure to fill the pores with an oxidant was described (Becker
et al. 2010) as follows: The oxidizer (preferably NaClO4) was dissolved in either
methanol or anhydrous ethanol. The oxidizers were applied by dropping a few
Table 3 Properties of some common oxidizers (Clement et al. 2005)

Oxidizer
Perchlorates
Ca(ClO4)24H2O
NH4ClO4
LiClO43H2O
NaClO41H2O
KClO4
Nitrates
Ca(NO3)24H2O
NH4NO3
KNO3
Others
Sulfur
Solvent
(solubility)
Me (237 g/100 g)
Et (166 g/100 g)
Me (6 g/100 g)
Ac (>6 g/100 g)
Me (182 g/100 g)
Et (152 g/100 g)
Ac (137 g/100 g)
Me (~181 g/100 g)
Et (<181 g/100 g)
Me (<1.7 g/100 g)
Et (<1.7 g/100 g)
Ac (<1.7 g/100 g)
Me (>54 g/100 g)
Et (54 g/100 g)
Me (17 g/100 g)
Et (4 g/100 g)
Remarks
Strongly hygroscopic, but very efficient
Does not stay in pores; weaker reaction, lesser
oxygen yield due to water production
Does not stay in the pores, takes a while to come to
the surface
Less hygroscopic and stays inside the pores
Not solvable in any common solvent
Strongly hygroscopic
Does not stay inside the pores
Bad solubility, therefore no reaction
CS2 (good)
Me methanol, Et ethanol, Ac acetone
The only nonhygroscopic material which stays

inside the pores
979
drops of the oxidizer solution with a pipette directly on the porous silicon surface.
The solution was dried in a humidity-controlled box flooded with N2 gas.
Explosive Properties
The explosive responses shown in Fig. 1 are indicative of the relative energies
released by three different oxidants, with the sodium perchlorate explosion significantly more energetic than the oxidants gadolinium nitrate and sulfur (du Plessis
2007). It was demonstrated that a pore size in the region of 34 nm was optimal for
devices using sodium perchlorate as oxidant (du Plessis and Conradie 2006).
Another study concluded that a pore size of 11.8 nm was optimal for the oxidant
aluminum nitrate (Plummer et al. 2008).
Oxidants can be ignited thermally, electrically, or optically. In Table 4, the
experimentally determined initiation temperatures for some common oxidizers
are given.
Electrical ignition utilizes a hot wire or heating bridge element in close contact
with the oxidizer. Hot wires deposited directly on the porous silicon make use of the
much lower thermal conductance of the porous silicon. The first monolithically
integrated electronic initiator was reported in 2009 (Currano and Churaman 2009).
NaCLO4
Gd(NO3)3
10 cm
Sulphur
Fig. 1 Optical emissions from different oxidant nano-explosions

Table 4 Initiation temperatures of some common oxidizers
Reference
Clement et al. 2004
du Plessis and Conradie
2006
Ca(ClO4)2 ( C)
185210
NaClO4 ( C)
308337
313
Sulfur ( C)
239267
261
Gd
(NO3)3 ( C)
243
225
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M. duPlessis
Ti/Pt/Au and had a typical width of 25 m

The hot-wire stack was 200/1000/3800 A
and a length of 500 m. A porous silicon device with NaClO4 as oxidant could be
ignited within 475 s with a current of 840 mA from a 2.8 V supply, representing an
initiation energy of 0.83 mJ, a value very similar to the 1 mJ initiation energy
reported earlier (du Plessis 2008) for an aluminum thin film hot wire. Further
development and optimization of hot-wire stacks led to ignition times of less than
100 s for NaClO4 and initiation energies less than 0.1 mJ (Churaman et al. 2010b).
Aluminum thin film hot-wire ignition times for different oxidants were also determined, with values of 90 s for NaClO4, 560 s for sulfur, and 1 ms for Gd(NO3)3
(du Plessis 2008). The use of Cr microbridges as reliable hot-wire heating elements
was also demonstrated (Wang et al. 2012), and initiation energies varied from 0.15
to 0.29 mJ to ignite porous silicon devices with NaClO4 as oxidant, with ignition
delay times varying from 80 to 110 s. Laser ignition could be achieved using a
514 nm laser at 37.7 mW and a power density of 2.7 kW/cm2 at a standoff distance
of 23 cm (Churaman et al. 2010a).
The energy yield of porous silicon explosive devices was measured using a
calorimetric bomb test, resulting in a value of 7.3 kJ/g with calcium perchlorate as
oxidizer (Clement et al. 2005). Differential scanning calorimetry techniques were
also used to measure the energy output for sodium perchlorate at almost 9 kJ/g
(Plummer et al. 2008). The extent of the NaClO4 reaction was observed with bomb
calorimetry in N2 and O2 atmospheres. Without the supplementary O2 environment,
the heat of reaction was measured to be 9.9 1.8 kJ/g, but with supplementary O2,
the reaction yielded 27.3 3.2 kJ/g and approached the theoretical value of 33.0
kJ/g for complete Si oxidation (Becker et al. 2010).
An important parameter of nano-explosive devices is the reaction propagation
velocity. It was shown that the reaction velocity of porous silicon with NaClO4 as
oxidant and 34 nm pores increased with thicker porous layers, reaching a plateau
of about 400 m/s for layers thicker than 30 m (Plummer et al. 2011). Lowerporosity samples exhibited faster propagation speeds (Churaman et al. 2010b).
The increased reaction velocity of the lower-porosity samples is attributed to a
combination of the nearly ideal oxidizer/fuel ratio (Becker et al. 2011) and an
increased speed of sound in the lower-porosity porous silicon relative to the
higher-porosity counterpart. An interesting development recently demonstrated
that the propagation velocity can actually be controlled by structural modifications, for example, manufacturing pillars of porous silicon on the surface (Parimi
et al. 2012). The propagation speed for porous silicon in this case with Mg(ClO4)2
as oxidant could be varied from 1 to 500 m/s, depending on the structural surface
profiling used.
The temperature of the flame and the amount of gas generated during the
nano-explosion were also experimentally investigated (Mason et al. 2009).
The nominal maximum flame temperature for most porous silicon oxidizer systems is about 3,000 K, with the oxidant sulfur an exception where the
flame temperature is only 1,600 K. The maximum gas production of the porous
silicon explosives ranged from 650 cm3/g of reactant for sulfur to 4,800 cm3/g of
reactant for NaClO4.
981
Long-Term Stability
A relationship has been demonstrated between the decrease in the energy intensity
of the explosion of porous silicon layers after storage and the loss of hydrogen in the
course of storage (Lazaruk et al. 2007). To achieve long-term stability, the porous
silicon surfaces must be stabilized. This can be achieved by thermal annealing of
the porous silicon sample in an oxygen atmosphere below 250 C (Clement
et al. 2005), when the oxygen is mainly back bonded to surface silicon atoms,
while the hydrogen atoms covering the surface silicon atoms remain unaffected. A
process step to ensure a complete coverage of hydrogen atoms at the silicon surface
was proposed (Koch and Clement 2007), namely, that the freshly electrochemically
etched porous silicon be dipped in a solution of HF and ethanol. This will remove
the thin oxygen layer formed after exposure to air and re-saturate the dangling
bonds at the surface with hydrogen. The closed hydrogen cover was stable and the
oxygen back bonded during the low-temperature oxygen anneal.
In recent studies on the combustion performance of silicon-based nanoenergetic
composites (Thiruvengadathan et al. 2012) and the explosive composite of porous
silicon and sodium perchlorate (Becker et al. 2010), the need to passivate the silicon
surface with hydrogen was clearly demonstrated.
New Developments
In an effort to analyze the explosion and combustion of nanostructured silicon in the
presence and absence of hydrogen on its surface, special attention was paid to the
behavior of spherical plasma structures formed during these processes (Lazarouk
et al. 2006). The explosion and combustion of porous silicon were observed to be
accompanied by the formation of a luminous ball with a diameter up to several tens
of centimeters. The size of the luminous flash was maximal for samples with a high
content of hydrogen on the surface of the porous silicon. This study led to a
hypothesis to explain the appearance and development of the natural phenomenon
of ball lightning caused by small silicon particles covered with hydrogen atoms. A
subsequent study (Ito and Cappelli 2012) confirmed the presence of a silicon
nanoparticle network of high porosity within the fireballs. Since the mechanism
responsible for the creation of ball lightning during atmospheric lightning strikes in
nature is still the subject of ongoing debate, the effects observed during the
combustion of porous silicon devices may lead to new insights.
Applications
The emerging technology of porous silicon explosives may find a number of
applications. An initial application proposed was using gadolinium nitrate porous
silicon devices as the excitation source, but also as the matrix for the analyte, in
atomic emission spectroscopy analysis (Mikulec et al. 2002). An airbag initiator for
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M. duPlessis
the automotive industry was also developed (Clement et al. 2005), and nanoexplosive devices as fully integrated electronic detonators to be used as a primer
for secondary explosives in the mining industry were also envisaged (du Plessis and
Conradie 2006). Nano-explosive devices can also be used as a source of energy for
silicon micro actuators (Lazaruk et al. 2007). The integration of nano-explosive
porous silicon devices with a MEMS sensor has been demonstrated (Currano and
Churaman 2009), and the first report of nano-explosive devices propelling miniature mechanical devices, for example, microrobots, was reported in 2012
(Churaman et al. 2012).
Conclusion
Since the 2002 discovery of nano-explosive devices using solid-state oxidants in
porous silicon at room temperature, the technology has reached the stage where
several applications are considered. Issues of interest are the cost-effectiveness of
fabrication, future integration with CMOS technology, the long-term stability, and
the sensitivity to electrostatic discharge.
References
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reaction between galvanic porous silicon and sodium perchlorate. Appl Mater Interfaces 2
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Brown ME, Taylor SJ, Tribelhorn MJ (1998) Fuel-oxidant particle contact in binary pyrotechnic
reactions. Propell Explos Pyrotech 23:320327
Churaman W, Currano L, Singh AK, Rai US, Dubey M, Amirtharaj P, Ray PC (2008) Understanding the high energetic behavior of nano-energetic porous silicon. Chem Phys Lett
464:198201
Churaman WA, Becker CR, Metcalfe GD, Hanrahan BM, Currano LJ, Stoldt CR (2010a) Optical
initiation of nanoporous energetic silicon for safing and arming technologies. Proc SPIE
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Churaman W, Currano L, Becker C (2010b) Initiation and reaction tuning of nanoporous energetic
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Churaman WA, Currano LJ, Morris CJ, Rajkowski JE, Bergbreiter S (2012) The first launch of an
autonomous thrust-driven microrobot using nanoporous energetic silicon. IEEE J
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Porous Silicon and Functional Foods

Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silicon in the Environment and as a Trace Human Nutrient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silicon Levels in Food, Common Dietary Intake, and Excretion . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silicon Compounds as Food Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silicic Acid and Osteoporosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Development of Porous Silicon as a Food Additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nutrient Protection and Controlled Release . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abstract
Functional foods are often described as those that can have a positive effect on
health beyond basic nutrition. Examples include cholesterol-lowering oatmeal,
bacteria-loaded yogurt for gut health, and iodine-fortified bread for prevention of
thyroid disease. There is growing evidence that orthosilicic acid, the biodegradation product of porous silicon, can have a positive contribution to optimizing
bone health. The relevant nutritional literature on silicic acid and trials related to
osteoporosis are collated and discussed. Silica microparticles (and inadvertently
nanoparticles) have been used for decades as an approved food additive.
Preliminary studies have shown that porous silicon has high chemical stability
in many stored foodstuffs and dissolves in intestinal fluid faster than in gastric
fluid and that the taste and mouthfeel of oxidized porous silicon microparticles
can be acceptable. The potential uses of mesoporous silicon or silica particles in
both protecting and raising bioavailability of ingested high-value nutrients are
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_101
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analyzed. Despite its technical potential, inexpensive and very scalable fabrication routes are required if porous silicon is to have significant uptake by the food
industry.
Introduction
Let food be thy medicine and let medicine be thy food (Hippocrates 431 BC).
Some 2,500 years later, many would agree with this tenet, provided that the food
remains tasty. It is established that a varied and healthy diet can considerably
reduce the risk of disease, and the 1970s saw the upsurge of natural and organic
produce (examples in Fig. 1). From the 1980s onwards, we have had low and
light foods with less calories, salt, sugar, or fat. However, many consumers today
struggle to meet dietary guidelines with regard vegetable, fruit, fish, and unrefined
grains. Instead they have opted for healthier versions of their favorite products to
help prevent specific nutrient deficiency or lower cholesterol, for example. This is
why there are also a growing range of new products called functional foods
(Salminen et al. 1998; Katan and de Roos 2004; Siro et al. 2008), nutraceuticals,
or novel foods (examples in Fig. 1). This review attempts to justify why, and in
what ways, porous silicon could play a role in this area. It starts by discussing how
much silicon is in the human body, in what form, and its potential roles as a trace
element. The long-term use of silica by the food industry is then highlighted,
commenting on relevant chronic oral toxicity studies. Preliminary studies on the
viability of porous silicon to become a novel food additive are then reviewed.
Finally, the role of both mesoporous silica and silicon in protecting key nutrients
during food processing and storage is compared and contrasted. Both carrier
matrices could also improve the oral bioavailability of hydrophobic nutrients, in
Fig. 1 Natural organic food and synthetic functional food. According to many definitions, some
unmodified fruit and vegetables represent the simplest form of functional foods as they are already
rich in physiologically active components
987
analogy with their demonstrated effects on hydrophobic pharmaceutical actives

(See handbook chapter Drug Delivery with Porous Silicon).
Silicon in the Environment and as a Trace Human Nutrient

Silicon is the second most abundant element in the Earths crust, and although there
has been interest in the biological role of silicon for over a century, it is only in the
last four decades that it has been suggested as an essential trace element for
mammals. Both chickens and rats were shown to have bone abnormalities when
completely deprived of silicon (Carlisle 1972; Schwartz and Milne 1972).
Silicon may also have a role in a number of areas of human physiology and
metabolism, especially bone and connective tissue formation (Jugdaosingh
et al. 2004) but possibly also bone related gene expression and cardiovascular
health (Carlisle 1970; Schwarz 1977; Carlisle 1981; Seaborn 1993; Kim
et al. 2010). However, its essentiality for man has not yet been established, nor
have clear functional roles (EFSA 2004; Agostini et al. 2011).
Silicon is not found naturally in its elemental form as it readily reacts with
atmospheric oxygen and water to produce silicates which vary in composition from
simple soluble orthosilicic acid Si(OH)4 and oligomers and polymers to less soluble
colloids and gels and insoluble solid phase silicates (Iler 1979). The latter constitute
the vast majority of environmental silicates (e.g., soil minerals), although natural
waters contain soluble silicate (mostly orthosilicic acid) generally at 120 mg/l.
Given its environmental abundance, it is perhaps not too surprising that humans
contain significant levels of silicon compared to many other trace elements that are
already established as essential. Total silicon content of human adults can be as
high as 12 g, so it is the third most abundant trace element after iron and zinc
(Jugdaosingh 2007).
It is most concentrated in connective tissues, including aorta, trachea, tendon,
bone, and skin. Adult fasting serum levels of orthosilicic acid are typically about
100 ug/l (Van Dyck et al. 2000; Bisse et al. 2005, Jugdaosingh et al. 2013b).
Silicon Levels in Food, Common Dietary Intake, and Excretion

There are now a few studies of the silicon content of foods (Bowen and Peggs 1984;
Pennington 1991; Dejneka 2003; Mojsiewicz-Pienkowska 2003; Powell et al. 2005;
Robberecht 2008; Prescha et al. 2012). There are however difficulties associated
with the analytical procedures required for silicon analysis (Van Dyck et al. 2000)
and often problems with environmental contamination. In a comprehensive study
(Powell et al 2005), almost half of the UK foods analyzed had low levels of silicon
(<1 mg/100 g). Those with the highest levels (>5 mg/100 g) were from breads and
cereals with oat bran having the highest content of all. The silicon content of
vegetables and fruits was highly variable. Meat, poultry, fish, and seafood normally
contain very little silicon (Pennington 1981), and likewise dairy products had low
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levels. Of the beverages studied, beer, a macerated whole-grain cereal product, had
the highest levels, while drinking water was a variable source with some mineral
waters relatively high in silicon.
Orthosilicic acid is the most readily absorbed form of silicon/silicate in humans
(Jugdaosingh et al. 2002). Plants take up orthosilicic acid from the soil, which is
transported through the plant in this form and is then mostly deposited in cell
lumina and walls as solid amorphous silica deposits often known as phytoliths.
Therefore, in plants and plant-based foods, silicon is present as fairly insoluble
phytolithic silica, but intestinal uptake proceeds following luminal hydrolysis to
orthosilicic acid.
There is also a paucity of data on the dietary silicon intake of humans, but
estimates typically lie in the 2050 mg/day range for Western populations
(Bowen and Peggs 1984; Pennington 1991) and 140204 mg/day in China and
India where plant-based foods predominate in the diet (Jugdaosingh 2007).
Bioavailability of this dietary silicon will depend on its chemical form and
probably also the food matrix (Van Dyck et al. 1999; Sripanyakorn et al. 2009).
The main route of excretion for silicon is in urine via the kidneys, but feces also
contribute (Pruksa et al. 2014). Silicic acid removal is very efficient: with surplus
blood levels falling back to equilibrium within a few hours (Popplewell
et al. 1998). Only for dialysis patients is there evidence of systemic accumulation
(Gitelman et al. 1992).
Silicon Compounds as Food Additives

When considering using elemental solid silicon in food (Canham 2007), it is
important to note that humans have been ingesting significant quantities of silica
via food additives for decades, since food-grade amorphous silicas (e.g., Syloid
244, Britesorb C935) have GRAS (generally recognized as safe) FDA status. There
are relatively high levels of silica in common brands of instant coffee powder and
soup powders, for example (Prescha et al. 2012).
Table 1 lists the approved food additives containing silicon, together with their E
numbers and primary functions. Food-grade amorphous silicas (E551) have found a
wide variety of uses (Villota and Hawkes 1986) over decades including:
Bulking agent
Clarifying agent in beverages
Anticaking agent in powders
Antifoaming agent
Enzyme substrate
Volatile retention
Flavor microencapsulate
Barrier layer for packaging
Viscosity control
989
Table 1 Approved silicon-based compounds in food

Silicon compound
Silicon dioxide
Calcium silicate
Magnesium silicate/
magnesium trisilicate
Magnesium hydrogen
metasilicate (talc)
Sodium aluminum silicate
Calcium aluminum silicate
Aluminum silicate
Dimethylpolysiloxane
Formula
a-SiO2
CaSiO3
MgSiO3
Mg2Si3O8.2H2O
Mg3(Si2O5)2(OH)2
E number
551
552
553a
Function(s)
Numerous
Optical scattering
Stabilizing
553b
Clarifying
NaAlSi2O8
CaAl2Si2O8
Al2SiO5
(CH3)3-Si-(OSi(CH3)2-)n- CH3
554
556
559
900
Glossing
Fluffing
Filtration
Antifoaming
Of particular relevance is the GRAS (generally recognized as safe) status of

synthetic amorphous silica (SAS) in the form of pyrogenic (fumed), precipitated,
gel, or colloidal silicas. Many of these are highly porous, and it has recently been
demonstrated that numerous food products containing such E551 additives have
been shown to contain nanoscale silica at significant levels (Dekkers et al. 2011).
Since the very long (93 weeks in mice, 103 weeks in rats) oral in vivo study of the
1980s (Takizawa et al. 1988), there has been little chronic toxicology data reported.
This has prompted further reviews of the health risks of pyrogenic, precipitated, and
colloidal silica (Fruijtier-Polloth 2012) and oral toxicity studies of such nanostructured silica (Van der Zande et al. 2014). Such a recent review of the literature
concluded despite the new nomenclature designating SAS a nanomaterial, none of
the recent available data gives any evidence for a novel, hitherto unknown mechanism of toxicity that may raise concern with regard to human health (FruijtierPolloth 2012).
Silicic Acid and Osteoporosis

This complex field has received multiple reviews from different perspectives
recently (Jugdaosingh 2007; Price et al. 2013; Jurkic et al. 2013) and so is only
discussed briefly here.
Orthosilicic acid at physiological concentrations has been shown in vitro to
stimulate collagen synthesis in human osteoblast cells (Refitt et al. 2003;
Arumugam et al. 2006). In vivo evidence for silicon essentiality started in the
1970s (Carlisle 1972; Schwartz and Milne 1972) showing dramatic effects of
silicon deprivation. More recent studies have only found moderate beneficial
effects of silicon supplementation, and only in some cases (Jugdaosingh 2007). In
an epidemiological study, an important association between dietary silicon and hip
bone mineral density was found in premenopausal women, which was less strong in
men (Jugdaosingh et al. 2004).
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The 2007 comprehensive review concluded that both the mechanisms of action
and essentiality for humans remain to be established (Jugdaosingh 2007). Both
2013 reviews concluded that more attention to this important nutrient by the
medical community was warranted (Price et al. 2013; Jurkic et al. 2013). Certainly,
if stronger evidence and understanding for essentiality does appear in the coming
years, it will provide a large impetus for a wide range of soluble silicon supplements
to be developed, including mesoporous silicon, optimized to deliver orthosilicic
acid at high bioavailability via the GI tract (Anderson et al. 2003).
Development of Porous Silicon as a Food Additive

This section of the review summarizes some of the published and previously
unpublished R&D carried out by pSiMedica Ltd, UK, and Intrinsiq Materials Ltd,
UK, over the period 20062011 Canham 2007b. It covers six general issues of
particular relevance to food products.
The biodegradability of mesoporous silicon in body fluids underpins its medical
uses. There is a strong pH dependence of biodegradability kinetics (Anderson
et al. 2003) which explains why it dissolves faster in the intestine than the stomach.
However, corrosion, when within food and beverages, could limit its usage as a
protectant matrix (see next section). For this reason, the first studies in this area
included an assessment of corrosion rates in a variety of foodstuffs of high water
content and common drinks (Canham 2007). Much higher chemical stability was
observed than in physiological environments and attributed to primarily the more
acidic nature of food and drinks. The corrosion of mesoporous silicon in Coca-Cola,
for example (pH 2.54.2), was more than 50 times lower than in supermarket
mineral water (pH 7.9). In refrigerated pineapple juice (pH 3.5) at 5 C, it was
more than 1,500 times lower than in the mineral water at 18 C (Canham 2007).
This implies that mesoporous silicon could have acceptable shelf life in various
beverages, in addition to dry foods.
Unlike synthetic amorphous silica (SAS), synthetic elemental silicon (SES)
does not currently have GRAS status for use in food (cf. Table 1). Although
preclinical toxicology and human safety data exists for certain medical uses (see
handbook chapter Porous Silicon in Brachytherapy), additional peerreviewed published testing data is needed for food applications. A subchronic
toxicity study in rats of an appropriate form of SES (e.g., mesoporous silicon)
should be conducted to determine any potential adverse effects, when fed over
at least a 90-day period. A well-designed dose response study would
provide critical information for the determination of acceptable daily intake
(ADI) and be required as part of the process for achieving GRAS status for
mesoporous silicon.
In addition to primary concerns regarding toxicological safety, the organoleptic
properties of a potential food additive need assessment. The taste and mouthfeel of
oxidized porous silicon particles have been compared to those of solid silicon,
porous silica, and a trace metal salt (copper sulfate). Trained taste panels were
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Fig. 2 Silicon incorporation of foodstuffs for taste and mouthfeel trials: chocolate and chewing
gum. Milk chocolate impregnated with micronized metallurgical silicon using an industrial
process. The two darker brown slabs, with a hue similar to dark chocolate, contained 12 wt%
silicon. Chewing gum pellets blended with 10 wt% silica and 10 wt% silicon
employed to determine the taste threshold and taste descriptors in both water and
chewing gum base (Shabir et al. 2012). A variety of different food matrices can
generally be used for such testing (see Fig. 2). The gum-based experiments, for
example, found acceptable mouthfeel with d90 value of <12 um at 10 wt% loading.
Triangle testing (where the task is to identify (blind) one sample that is different
from the other two) of taste in water found that porous silicon particles were
detectable by 85 % of the panel at 1 mg/ml concentrations. In comparison, almost
98 % could detect copper at 0.2 mg/ml (Shabir et al. 2012). High concentrations of
porous silica gave a chalky taste; copper salt had a very strong metallic taste.
Solid silicon was also perceived as metallic by the supertasters of the panel but
not oxidized porous silicon. These preliminary findings are encouraging with regard
likely consumer acceptability of silicon supplemented foods and beverages.
Aside from shelf life issues, oral toxicology, taste, and mouthfeel, a further topic
to consider for porous silicon usage in food is its brown powder color (see handbook
chapter Color of Porous Silicon). Silicon incorporation in a foodstuff should
ideally not change its color significantly. One can choose foodstuffs that are already
brown (e.g., chocolate, bread, coffee, cereals, soup powder, pasta, etc.) but often,
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the color of the porous silicon may have to be modified. This has been achieved
using impregnation of a variety of nutrient pigments (Canham et al 2010). An
example is beta-carotene for color matching in orange juice suspensions.
A final key issue for the food industry is the cost of any new additive (Canham
2007; Batchelor et al. 2012). Although metallurgical grade silicon is available at
99 % purity and the ton level at a few $/kg, stain etching it to 80 % porosity can still
be too expensive a process for many food uses. In this regard, biogenic silica
reduction looks a much more viable process here. Conceptually, the ability to
convert a food waste product such as rice husk, into a functional food additive,
appears very attractive (see handbook chapter Porous Silicon Formation by
Porous Silica Reduction). If the desired powder hue can then also be achieved
with vegetable or fruit extract impregnation, then a near natural additive is
achieved.
The next topic addressed here is the current prime food manufacturer motivation
for exploring the use of mesoporous silicon in food: protection of established
nutrients. This remains a prevailing issue for functional foods, irrespective of
whether or not the degradation product of porous silicon becomes accepted as an
essential nutrient in its own right.
Nutrient Protection and Controlled Release

Protection via microencapsulation of food ingredients is not a new concept; flavors
were being encapsulated by acacia gum spray dried coatings in the 1930s. Nutrient
protection issues have received much attention and yet still remain. However, the
ever-increasing complexity of food products, the massive growth in functional
foods, and the interest in efficient delivery of nutrients are opening up many new
opportunities.
The main reasons for the microencapsulation of food ingredients are protection,
controlled release, processability, and taste masking. Historically, protection has
been the primary reason. Key ingredients can lose their functionality through
exposure to heat, light, or moisture. They can be degraded by physical contact
with other ingredients within the food item or by food processing. Often the reason
for protection is to increase the shelf life of the product. The encapsulation of
delicate ingredients can simply allow easier handling during production of a
product or the utilization of more aggressive processing techniques. Microencapsulation can also be used to release food ingredients at the right place in the GI tract.
Such a targeted release can dramatically improve the effectiveness of food additives
or the nutritional value of fortified foods.
Vitamins and minerals are increasingly being added to food to increase their
actual or perceived health benefits. Table 2 highlights the differing sensitivities of
different vitamins, both at the food incorporation stage and with lengthy storage.
Vitamins are a particularly pertinent example for mesoporous silicon, because the
food industry has relied on high surface area silica for many years to supply freeflowing vitamin powders (Schmidt et al. 1984; Krivak et al. 1988; Ponchon and
993
Table 2 External factors influencing vitamin stability (Adapted from Hoffmann (2005))
Vitamin
A (retinol)
B2 (riboflavin)
B6 (pyridoxine)
B9 (folic acid)
B12 (cobalamin)
C (ascorbic acid)
E (tocopherol)
K (phylloquinone)
Heat
xx
0
0
0
0
0
x
0
Oxidizing
agent
xx
0
0
xx
0
xx
0
0
Reducing
agent
0
x
0
xx
xx
0
0
xx
Humidity
0
0
0
0
x
xx
x
x
Light
xx
xx
x
x
x
0
x
x
pH
(acid)
x
0
x
x
xx
0
x
xx
pH
(alkali)
0
xx
x
x
xx
x
x
xx
0 stable, x sensitive, xx very sensitive

Table 3 Nutrient loading (vitamin E) in mesoporous silicon as a function of porosity (Pokale,
Skaria, Shabir, Canham, 2010, Vitamin E loading in porous silicon, unpublished data)
Porous silicon
mesoporosity (%)
38
41
63
87
Theoretical
loading (wt%)
20
22
41
73
Experimental loading
(wt%) (gravimetric data)
14
17
38
70
Experimental
loading (wt%)
(extraction & HPLC data)
10
13
31
65
Rabute 1997; Morris et al. 2001). Why use porous silicon rather than porous silica?
Porous silicon has very different mechanical and optical properties. One key
differentiator, for example, is the much higher degree of UV light protection offered
by a silicon matrix compared to a silica one. Table 2 entries for light sensitivity
would then suggest that retinol and riboflavin would be the most promising vitamins for mesoporous silicon entrapment in this regard. Vitamin A is a particularly
challenging nutrient with regard stabilization (Loveday and Singh 2008).
With mesoporous materials (both silica and silicon), one can provide
nanoentrapment of nutrients, as opposed to microencapsulation. This can provide
not only protection from environmental parameters (see Table 2) but also bioavailability improvements for hydrophobic nutrients (Canham 2007). Nutrients loaded
to date in mesoporous silicon include vitamin A, beta-carotene, vitamin E, fish oils,
lycopene, coenzyme Q10, and curcumin. Table 3 presents an example of loading
data for vitamin E, with analysis by two techniques. Very high nutrient loading
levels are achievable (6570 wt%) for high porosity material, and the pore volume
fill factors peaked around 90 % or higher for the highest porosity.
Table 4 summarizes controlled release studies of nutrients, virtually all of which
have utilized silica to date. Future studies using mesoporous silicon should use
mesoporous silica as controls.
Research activity on drug delivery using mesoporous materials currently far
exceeds that on nutrient delivery (Bernardos and Kourimska 2013). The widespread
994
L. Canham
Table 4 Nutrient entrapment and release studies in mesoporous silica and mesoporous silicon
Nutrient
Vitamin E
Carrier matrix
Silica
Vitamin E
Vitamin B1
Vitamin B2
Curcumin
Vitamin B3
Menthol
Vitamin C
Vitamin B9
Silica
Silica
Silica
Silica
Silica
Silica
Silica
Silicon
Motivation
Protection & controlled
migration in packaging
Optimizing adsorption
Controlled release
pH-gated release
Controlled release
pH-gated release
Sustained release
Controlled release
Controlled release
Example publication
Heirlings et al. (2004)
Chandrasekar et al. (2005)
Wu et al. (2007)
Bernados (2008)
Clifford et al. (2008)
Kapoor (2010)
Zhang (2012)
Rashidi (2013)
Haidary et al. (2013)
use of mesoporous silica as adsorbents for separating functional food ingredients

has also been hindered by insufficient chemical stability under typical food
processing conditions (Brady et al. 2007). In the food industry, bioseparation
media are typically cleaned and regenerated with sodium hydroxide solutions at
80 C. This specific application area does not look compatible with mesoporous
silicon.
Concluding Remarks
Research on the uses of porous silicon as a food additive is in its infancy, whereas
nanostructured silica is both approved and heavily utilized by the food industry.
Preliminary work described here on mesoporous silicon has briefly covered issues
such as material stability in food, oral toxicology, taste, mouthfeel, color, and cost.
Opportunities exist for both high-value nutrient protection and bioavailability
enhancement. In contrast, the use of mesoporous silicon as a filtration adsorbent
for functional food ingredients does not look viable. Continued studies on the
biological role of orthosilicic acid in humans are very important to this nutritional
field. If silicon becomes an approved essential nutrient, with an RDA, then a major
expansion of the silicon supplement market would seem inevitable.
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Porous Silicon for Oral Hygiene

and Cosmetics
Leigh Canham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Multifunctional Dentifrice (Toothpaste) Abrasive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sunscreens and Bronzers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Foundation and Makeup Additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Anti-aging Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1000
1001
1003
1004
1005
1006
1006
Abstract
Porous silicon particles could be utilized in a variety of consumer care applications if their cost of manufacture becomes low enough. Silica and porous silica
are already widely used by the toothpaste and cosmetic industries, and porous
silicon offers superior mechanical properties for teeth cleaning and very different optical properties for cosmetics. Partial thermal oxidation has been used
to improve shelf life in liquid formulations and to match brown skin tones.
Preliminary mouthfeel testing for oral hygiene products has been carried out,
but formalized skin-feel testing and optimization is required for numerous
dermatological products. Product examples discussed include multifunctional
dentifrice abrasives, sunscreens, bronzers, foundation and makeup additive, and
anti-aging formulations.
L. Canham (*)
DOI 10.1007/978-3-319-05744-6_102
999
1000
L. Canham
Introduction
Poor oral health may have a profound effect on general health but also a major
impact on peoples daily lives and well-being. Dental caries remains the most
common disease worldwide and more than 500 million people utilize fluoride
toothpaste worldwide (Peterson et al. 2005; Goldman et al. 2008). Modern toothpaste formulations are surprisingly complex with abrasives, fluoride, detergent,
humectant, thickener, preservative, flavoring agent, sweetener, and pigments,
among other ingredients.
Cosmetics can have a profound effect on peoples well-being and self-esteem.
The growth of cosmeceuticals (Bissett 2009), oral cosmetics such as tooth whitening (Joiner 2004, 2006; Goldberg et al. 2010), and novel oral delivery forms for
APIs has blurred the boundaries between oral hygiene, cosmetics, and pharmaceutical science (see Fig. 1). It is in these interfacial regions where there could be most
potential for porous silicon.
Experiments with model porous silicon powders and membranes prepared by
anodization are summarized in this review. Although such studies have shown the
potential of porosified silicon in selected applications, these cosmetic tests will
need to be repeated with less expensive forms, such as those derived from biogenic
silicas (Batchelor et al. 2012), if the promising technical effects seen are to be
translated into commercial products. The creation of cosmetic-grade porous silicon
from plants looks particularly attractive, since there is great consumer interest in
botanically derived actives and formulations.
PHARMACEUTICS
ORAL HYGIENE
Cf. Toothpaste, mouthwash,
dental floss, tooth whiteners.....
Cf. controlled release of actives

in the oral cavity or into the skin
COSMETICS
Cf. Foundation, make-up, lipstick
bronzer, sunscreen, nail varnish,
mascara, moisturiser, face scrub,
aftershave, shampoo....
Fig. 1 Potential application areas for multifunctional porous silicon at the interfaces between oral
hygiene, cosmetics, and pharmaceutics
Porous Silicon for Oral Hygiene and Cosmetics
1001
Multifunctional Dentifrice (Toothpaste) Abrasive

Modern toothpastes or dentifrices nearly always contain an abrasive substance for
controlled mechanical cleaning and polishing of teeth. Its primary function is to
remove various deposits including the pellicle film without damaging the underlying enamel, dentin or neighboring gums. The ideal abrasive is thus soft enough to not
scratch enamel but strong enough to avoid fracture during brushing. Unfortunately,
soft materials tend to be also mechanically weak. The literature describes a wide
variety of materials that were tried over decades: calcium carbonate, pumice stone,
calcium and magnesium phosphates, zeolites, kaolin, and even alumina. Amorphous
silica in various forms is now by far the dominant abrasive in commercial toothpaste.
Table 1 shows the comparative hardness of some materials, including that of apatite
(human enamel), human dentin, silicon, and silica. The introduction of sufficient
mesoporosity has the benefit of lowering the hardness of silicon to values comparable
with that of enamel, or possibly even dentin. Mesoporous silicon should have lower
hardness and yet higher strength than mesoporous silica of a similar porosity (see
handbook chapter Mechanical Properties of Porous Silicon). It should therefore
perform as a more gentle but still effective mechanical cleaning agent (Canham 2006).
The abrasivity and cleaning efficiency of toothpaste formulations are quantified
using standardized methods, approved by the appropriate regulatory authorities
and dental associations (Wulknitz 1997). Two such techniques yield the RDA
(Radioactive Dentin Abrasion) and PCR (Pellicle Cleaning Ratio) values, widely
recognized as performance standards by the toothpaste industry.
Initial screening tests on the compatibility of mesoporous silicon with toothpaste
formulations included studies of its corrosion rate in various commercial brands to
ascertain whether the abrasive would have an acceptable toothpaste shelf life. Table 2
shows the significant variation in pH found between selected brands. Some formulations, like tooth whitening products (Price et al. 2000), are surprisingly alkali. The
corrosion rate of mesoporous silicon in aqueous environments is known to be strongly
pH dependent, increasing dramatically at alkali pH (Canham 2007). Significant gas
generation (hydrogen) during toothpaste storage, associated with skeleton oxidation,
was observed from hydride terminated (as-etched) powders, but this could be effectively prevented by passivation via thermal oxidation in the 500700 C range.
Table 1 Comparison of
the relative hardness of
tooth components with
selected inorganic
materials including
nonporous silicon
Material
Diamond
Alumina
Silica (nonporous)
Silicon (nonporous)
Apatite (tooth enamel)
Dentin
Kaolin
Talc
Mohs hardness value

10
9
8
7
5
3
2
1
1002
L. Canham
Table 2 Commercial toothpaste formulations pH variation. All brands shown with the exception of Original Coolmint contain silica powders for their thickening and abrasive properties
Toothpaste brand
Roche P&J (children)
Colgate Total, Sensodyne Total, Crest Complete, Macleans Milk Teeth (children)
Original Coolmint
Clinomyn (smokers)
pH (paste)
6.1
6.66.8
8.9
9.1
Cleaning efficiency trials, in collaboration with a major toothpaste manufacturer,

confirmed high efficacy, but such studies need to be repeated with less expensive
forms of porous silicon than those produced by anodization and with porous silicon
of colors that are more acceptable to toothpaste consumers (see handbook chapter
Color of Porous Silicon).
A secondary attribute of a porous silicon abrasive with regard toothpaste is
worthy of discussion the potential to deliver chemically active agents, as well
as physically clean teeth.
Sustained fluoride delivery to teeth is one example. Among various cariespreventing strategies, the use of fluorides has proved to be the most clinically
effective (Marinho et al. 2003). A clear correlation has been established between
anticaries status and saliva concentrations of fluoride (Toumba et al. 2001). Without
fluoride supplement, salivary fluoride concentrations are quite low, ranging from
0.01 to 0.04 ppm. Outstanding challenges result from the significant oral toxicity of
many fluoride compounds and thus a relatively narrow therapeutic window for
saliva levels (Pessan et al. 2009). Dentifrices typically contain 02,500 g F/g. The
majority of fluoride in toothpaste provides burst release into saliva during
brushing and elevated but only transient levels of retention on teeth, gums, and
oral crevices. This has led to many approaches being investigated to provide slowrelease fluoride devices attached to teeth (Castioni et al. 1998; Chung et al. 1998;
Aaltonen et al. 2000; Pessan et al. 2009; Toumba et al. 2009). Such fluoride depots
have great potential for high caries-risk groups, but lack convenience for the
general public. In this regard, a microparticulate depot strategy via toothpaste
would be of much wider applicability.
Anodized and stain-etched mesoporous silicon already contains trace fluoride
from the etch process. Fluoride levels in as-etched and oxidized material were tuned
by washing processes and covered the range 3006,000 ppm, quantified by ion
chromatography (Loni, 2010, Intrinsiq materials Ltd, unpublished data). Subsequent NaF doping was shown to be capable of loading up to 14 wt% in 70 %
porosity particles. Fluoride ion electrode monitoring in simulated saliva showed
encouraging levels of release, but enamel uptake in vitro needs to be quantified
using FDA-approved test methods and labeled particles (Shabir et al. 2010,
Mesoporous silicon as a fluoride delivery agent in toothpaste: in vitro fluoride
loading and particle uptake on teeth, Intrinsiq Materials Ltd report, unpublished).
Particularly interesting in this regard is an early published study, proposing a linear
association between silicon and fluoride in enamel (Levy and Koritzer 1976).
1003
A second example are the antibacterial and antifungal agents like triclosan (see
Wang et al. 2010 and the handbook chapter Melt Intrusion in Porous Silicon).
Another would be flavoring agents. For all these uses, efficient retention of porous
silicon in the mouth is perhaps the major challenge to achieving sustained delivery.
Its apatite-inducing bioactivity (Canham et al. 1997; Pietak et al. 2007) could be
very relevant here in enabling durable adhesion of nanoparticles or microparticles to
teeth. Another option would be to apply mucoadhesive coatings to the fluoride-loaded
particles (see handbook chapter Functional Coatings of Porous Silicon).
Sunscreens and Bronzers

Protection against long-wave and shortwave UV radiation is the major function of
sunscreen lotions that typically contain both organic and inorganic components.
Titanium dioxide and zinc oxide are the dominant inorganic pigment materials used
by the sunscreen industry for decades (Morabito et al. 2011) with nanoparticle
grades being utilized more recently for transparency on the skin in the visible range.
The optical properties of crystalline silicon have not received attention until
recently in this regard. Although its lowest optical bandgap is indirect, solid
silicon absorption coefficients in the ultraviolet are actually as high as those of zinc
oxide (see Table 3). It also has a higher refractive index than both titania and zinc
oxide, which is important in UV light scattering. Porous silicon (Canham and Aston
2003; Pavlikov et al. 2012), solid silicon nanoparticles (Popov et al. 2008), and
silicon colloids (Rodriguez et al. 2010) have all been proposed as useful sunscreen
agents. Using Monte Carlo simulations, silicon nanoparticles have been reported to
outperform titania nanoparticles across the entire UV range (Popov et al. 2008).
Experimental quantification of the SPF (sun protection factor) values attainable at
varying loading levels, using industry approved methods, is a key next step for this
application.
A consumer acceptance barrier to the use of solid silicon in virtually all
dermatological formulations is its dark gray color. While with brown porous silicon
powders one can match skin tones, it still remains a challenge with sunscreen
lotions to maintain the white color that consumers associate with this product,
before application to the skin. In this regard, bronzer (self-tan) formulations
(see Fig. 2) could be a more suitable target for mesoporous silicon.
Table 3 Selected optical properties of zinc oxide, titanium dioxide, and silicon
Powder color
Density (g/cm3)
Refractive index
Optical gap (eV)
Absorption coeff. @ 315 nm (cm 1)
Absorption coeff. @ 400 nm (cm 1)
Titania
White
4.3
2.9
3.2
106
103
Zinc oxide
White
5.6
2.0
3.3
106
105
Silicon
Dark gray
2.3
3.5
1.1
106
105
1004
L. Canham
Fig. 2 Bronzer product examples. Increasingly, such self-tan formulations are incorporating
sunscreens
Foundation and Makeup Additive

Human skin is coated by a protective liquid layer of approximately 50 % sweat and
50 % sebum. Of the two surface liquids, sebum tends to be the more cosmetically
problematic because it causes skin to appear shiny or greasy in light and it
distributes unevenly over the skin in layers that can be tens of microns thick in areas
such as the face. Not only is sebum cosmetically undesirable, but it can also be
medically undesirable in that excessive amounts of sebum collecting on the face can
aggravate existing acne conditions. There remains a need to improve cosmetic facial
powders that will reduce the amount of sebum (and therefore shiny appearance)
collecting on the face, but that will not disrupt the natural look and feel of the skin.
Many facial powders today face the problem of caking when the powder-to-oil
ratio on the face is so high that that the powder-to-oil mixture creates a thick layer
on the skin surface. This layer very often becomes discolored and uneven in texture.
Development of a novel facial powder that will have a low powder-to-oil ratio (high
oil uptake capacity for very little powder), little volume change after oil uptake, and
little to no color change after oil addition is needed to solve this cosmetic problem.
High porosity silicon microparticles have potential in this regard for brown
cosmetic facial products like foundation (Canham and Monga 2010).
The sebum uptake capacity of mesoporous silicon microparticles of 80 % porosity
was compared with that of a commercial product (Sunjin SH219 silica powder).
Artificial sebum (43.5 % decyl oleate, 27 wt% oleic acid, 18 wt% squalene, 7 wt%
corn oil, 2.5 wt% cholesterol, 1 wt% cholesterol palmitate, 1 wt% glycerol dioleate:oleic
acid (1:1)) was used with the wet point method of adsorption capacity (see handbook
chapter Pore Volume (Porosity) in Porous Silicon). Sebum adsorption capacities of
mesoporous silicon were more than double those of the silica product (1.762.14 ml/g
compared with 0.720.79 ml/g). In addition, no significant volume changes accompanied high sebum adsorption in mesoporous silicon (see Fig. 3). Such studies should be
extended to even higher porosity silicon (e.g., 8090 % porosity) to ascertain likely
maximum adsorptive performance, combined with skin-feel assessment.
1005
Fig. 3 Artificial sebum (Stefaniak and Harvey 2006) uptake capacity in mesoporous silicon (Lee
et al., 2009, Preliminary study of mesoporous silicon capacity to adsorb skin sebum, Intrinsiq
Materials Ltd TM0902, unpublished report). From left to right: dry mesoporous silicon
(80 % porosity), sebum volume that can be adsorbed prior to wet point, sebum adsorbed powder.
Note how the volume of powder has not reduced appreciably that would signify skeleton collapse
Anti-aging Formulations
The anti-aging market sector of facial cosmetics is a very large and dynamic one
with high value products (Mintel 2011). There are a number of light-sensitive
ingredients that could be protected when entrapped within mesoporous silicon,
and formulations are applied to the skin. Some data showing protection of retinol
is provided as an example.
Retinol, the dermatologically active form of vitamin A, is extensively used by
the cosmetic industry for anti-aging formulations but is very sensitive to ultraviolet
radiation, thereby drastically reducing its shelf life. Over the past several years,
various carriers or formulations have been developed to improve the stability and
bioavailability of the retinoids and have included entrapment in silica particles (Lee
et al. 2001; Hwang et al. 2005), chitosan nanoparticles (Kim et al. 2006), and solid
lipid nanoparticles (Jenning et al. 2000). Most of these methods however have not
been that successful, and the long-term stability of retinoids against light, oxygen,
and heat is often still compromised.
A model porous silicon membrane structure was utilized to study the extent of light
protection for this active. The retinol-loaded silicon membrane was placed under a
long-wave UV lamp (7 W cm 2 365 nm light at 15 cm in air at 40 5 C for 1 h).
The control sample (covered with aluminum foil) served to protect the membrane
from UV light and to a limited extent reflected the heat away. The absorbance scans
are shown in Fig. 4. It is evident that the impregnated retinol has avoided the drastic
UV-induced degradation that the free retinol has undergone. A comparison of
curves A with C and D shows that the reduction in peak height still observed is
1006
L. Canham
Fig. 4 UV Absorption scans of free retinol and retinol entrapped within mesoporous silicon
(Skaria, 2009, Photoprotection of retinol in porous silicon, Intrinsiq Materials Ltd report,
unpublished). (A) Undegraded, (B) free retinol degraded by long-wave UV light, (C) retinolloaded pSi membrane exposed to UV light, (D) retinol-loaded pSi membrane covered with
aluminum foil and exposed to UV light
dominated by thermal and oxidative effects, not light. Porous silicon would appear
to have significant potential in protecting light-sensitive cosmetic ingredients.
In addition, photoluminescent particles are utilized in anti-ageing formulations as
optical brightness (Cassin and Simonnet 2006; Gelloz et al. 2012).
Concluding Remarks
Use of mesoporous silicon as an effective toothpaste abrasive exploits its highly
tunable hardness and relatively high strength compared to silica. Remaining challenges are its cost of manufacture and color manipulation. Controlled delivery
opportunities exist in oral hygiene, but particle adhesion to teeth or other oral
surfaces needs to be quantified and optimized.
A number of potential cosmetic application examples have also been presented.
These use primarily the UV absorption, adsorption capacity, and/or controlled
release via biodegradability on the skin.
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Index
A
Ab initio molecular orbital calculation, 475
Ablation, 526
Acoustic distributed Bragg reflectors
(ADBRs), 840
Acoustic microscopy, 215, 420
Administration route, 910
Adsorbents, 734, 735
Affinity mass spectrometry, 876877
Ag-induced chemical etching, 950
Air drying, 560561
Alcohol, 180181
Alcohol-based surfactant, 17
Aluminium, 89
Amorphous drug, 452
Amplified spontaneous emission (ASE), 347
Anisotropy, 217218
Annealing, 264, 265
Anode etching (AE), 25, 949, 969
Anodization, 4, 1213, 130, 164, 165, 168,
264, 562
Anodization cells, 1314
Anti-ageing formulations, 1006
Antibacterial agents, 1003
Antifungal agents, 1003
Applications, 981982
of porosity, 139
Aqueous stability, 364365
Atmospheric pressure mass spectrometry,
872874
Atomic force microscopy (AFM), 417418
Attenuated total reflection (ATR), 477
Auger electron spectroscopy (AES), 464
B
Back-bond oxidation, 476
Back-side-illumination electrochemical
etching (BIEE), 781
Ball lightning, 981

Ball milling, 94, 96, 698701, 703
Band transport, 266
Barillaros technique, 726
Binding assays for small molecules
detection, 861
Bioactive, 910
Bioactivity, 1003
Bioavailability, 988
Biocompatibility, 381382, 396, 910
Biodegradability, 395400
Biodegradable materials, 396
Biodegradable porous silicon, 909
Biodegradation kinetics, 398400
Bio-filtration, 941942
Biogenic silica, 89
BioMEMS, 788
Biomolecule attachment, 372373
Bioresorbable property, 910
Biosensors, 386387
Black silicon, 259250
Bolometer, 761
Bond and etch-back SOI process (BESOI), 570
Bone health, 985
Bottom-up techniques, 4
BrachySilTM, 902, 904
Brachytherapy, 901902
Bragg gratings, 825
Bronzers, 10031004
Bulk density, 136, 138
C
Calcium, 89
Calorimetry, 449
Capillary forces, 560
Carbon dioxide, 563
Carbonization, 370371
Cassie Baxter mode, 889

DOI 10.1007/978-3-319-05744-6
1009
1010
Catalysis, 734735
Cell culture, 481
Centrifugation/filtration, 527
Characterization, 406, 409
Chemical colors, 259
Chemical composition, 463
Chemical etching, 2324, 36
Chemical instability, 410
Chemical oxidation, 362363
Chemical oxidizer, 17
Clinical trials, 904905
Colloidal lithography, 543, 545547
Colorimetric sensors, 256
Color matching, 260, 992
Composites, 203
structures, 914
Concentrated hydrofluoric acid, 129
Consumer care, 735
Controlled release, 992994
Coplanar waveguides (CPW), 744
Cosmetics, 735, 737
Coulomb blockade, 266, 273, 276
Coulombic efficiency, 970
Coulombic forces, 666667
Covalent chemistry, 358
Crystalline drug, 452
Crystallography, 104
Curie-paramagnetism, 283
Cytotoxicity, 383384
D
2D arrays of colloidal spheres formation, 543
Data evaluation, 232236
DC conductivity, 265, 271
Dealloying, 6
Defects, 265, 267268
Degradation products, 916
Degree of anodisation, 12
Density-functional theory (DFT), 500, 640
Dental caries, 1000
Dentifrice (Toothpaste) abrasive, 10011003
Dermatological formulations, 1003
Desorption/ionization mechanism, 871
Desorption/ionization on silicon, (DIOS),
891892
Diagnostics, 735, 737738
Diamagnetic materials, 282
Diamagnetism, 281283
of silicon and porous silicon, 283284
Dielectric mismatch effect, 641
Dietary intake and excretion, 987988
Differential scanning calorimetry (DSC), 450
Index
Differential thermal analysis (DTA), 450
Diffraction, 825826
Diffusion, 222224
Direct hydrogen fuel cells (DHFC), 958
Direct imprinting of porous substrates (DIPS),
552, 554, 556
Disordered layer, 451
Dispersibility, 527
Dispersions, 191
Displacement deposition, 631632
Doping, 179, 501502
Dosimetry, 339343
Double electrochemical cell, 14
2D oxidation, 590
Droplets, 666
Drug delivery, 388389, 909
Drug load, 452
Drying, 1415
techniques, 561
2D structure formation
of deposits, 633
and deposition control, 634
3D view of microphotoluminescence
(microPL) 419
E
Effective mass theory (EMT), 499
Effective medium approximation (EMA),
267, 273
Effective optical thickness (EOT), 860861
Effective reflectance, 948
Effect of metal, 176178
Effect of oxidizers, 174176
Effect of substrate, 179180
Efficiency, 684
Electrical contacts to PS, 706707
Electrical ignition, 979
Electrical sensors, 848
Electrical transport properties, 264265,
268, 270, 272273
anisotrophy, 272273
contact dependence, 265267
porosity dependence, 273274
temperature dependence, 265, 270272
voltage dependence, 265, 268270
Electric field, 180
Electrochemical etching (EE) technique,
25, 78, 948, 950
Electrochemical functionalization methods, 685
Electrochemical grafting, 367369
Electrochemical micromachining (ECM),
780783
Index
Electrochemical oxidation, 363
Electrochemical reaction, 689
Electro-coextrusion, 667
Electrode material, 19
Electrodeposition, 6, 290, 630
Electroencapsulation, 666668
Electrografting, 484
Electroless deposition (ELD), 178
Electroless etching, 2527
Electroless method deposition (EMD), 50
Electroless techniques, 316
Electroluminescence, 321329
Electrolyte resistivity, 109
Electron affinity, 68
Electronics, 735, 737
Electronic trap detection, 336337
Electron paramagnetic resonance (EPR)
spectroscopy, 932
Electron spin resonance (ESR), 640
Electrospinning, 191
Electrospraying (ES), 666, 969
Electrostatic forces, 666
ELTRAN process, 570

Encapsulation, 676677
Energetic properties, 975
Energy conversion, 735, 737
Energy-dispersive X-ray spectroscopy
(EDX), 463
Energy-filtering TEM (EFTEM), 414
Enzymatic activities measurement, 876
Epitaxial layer, 953
Epitaxial Layer TRANsfer (ELTRAN)
process, 604
Epitaxy, 569
on annealed porous Si surface layer,
569570
Si layers, characteristics, 569
Etching, 949, 953
Etch rate, 39, 181
Euclidean porosity, 407408
Exothermic reaction, 89
Explosive devices, 977
Explosive properties, 979980
External gettering, 768
F
Fabrication methods, 189193
Fabrication techniques, 58
Facial powders, 1004
F-band, 313
Feedstocks, 4
Fermi level, 267, 269
1011
Ferromagnetic nanostructures, 289291
Ferromagnetism, 288289
Filtration, 735, 737
First-principles studies (FP), 500
Flavoring agents, 1003
Fluorescence quenching assay, 894895
Fluoride toothpaste, 1000
Food, 735, 737
additive, 992
Foundation, 10041005
Fourier transform infrared (FTIR)
spectroscopy, 369, 474
Fractal porosity, 407408
Fracture toughness, 217
Free carrier absorption (FCA), 346
Free-standing silicon nanocrystals, 673
Free-standing structures, 164
Freeze drying, 561
Fresh porous silicon, 236238
Full isolation by porous oxidized silicon
(FIPOS) technique, 574
Functional coatings, 647649
definiton, 647
functionalities and application, 649
methods, 648
spectroscopic and analytical techniques, 648
types, 649
Functional foods, 986
G
GaAs films, 584
Galvanic etching, 4, 2627, 129
GaN films, 584
Gas adsorption analysis, 436
Gas diffusion layers (GDL), 959, 962
Gas flow sensor, 760761
Gas and liquid doping, 639643
Gas sensors, 845
Ge epitaxy, 585
Gettering, 767, 950, 952
Glancing angle deposition, 6
Glitter, 257
Global processing, 716721
GMP manufacturing, 903
Gradient refractive index, 948
Grafting, 191
Gratings, 823
H
Hand-milling, 696
Hardness, 216217
1012
Health and safety, 1920
Hepatocellular carcinoma, 904
Heteroepitaxial film, 581
Heteroepitaxy, 582
Heterojunction, 268269, 946
Hierarchical porosity, 407
High-energy ball-milling (HEBM), 9697
High-performance bulk acoustic wave (BAW)
resonators, 840841
High resolution TEM (HRTEM), 414
High surface area, 129
High-value product, 4
High-volume products, 4
HNO3/HF vapor-etching, 76
Holographic methods, 829
Homoepitaxy, 572576, 585
applying ion assisted deposition, 575576
applying liquid phase epitaxy, 573
applying LPCVD, 572573
on non-reorganized porous Si, 574575
Homojunction, 946
Hopping, 266, 270271
Hot isostatic pressing (HIP) process, 98
Hydrofluoric acid (HF)-resistance test,
369370
Hydrogen peroxide, 174176
Hydrogen termination, 474
Hydrosilylation, 366, 485
Hydrothermal etching, 6
Hydrothermal treatment, 38
Hysteresis, 433
I
Ideality factor, 269
Immunocapture and MALDI
(iMALDI MS), 892
Immunoisolation, 938939
Impregnation, 203
Imprintable film fraction, 554
Imprintable patterns, 552
Imprint(ing), 552
Imprint depths, 554
Imprinted regions, 554
Industrial and academic activity, 735, 737
Infrared spectroscopy (IR), 474
Interface roughness, 148
Interferometric lithography, 810
Intravenous delivery, 912913
Intravitreal delivery, 913914
Intrinsic gettering (IG), 768
In vitro biodegradation, 396397
In vitro drug, 911
Index
In vitro testing, 933934
In vivo biodegradation, 397398
In vivo drug, 911
In vivo tests, 940
Ion irradiation, 511513
Iron oxide nanoparticles, 299
Irradiation, 506
J
Jet-milling, 701702
K
Kleimanns method, 725
L
Lactate dehydrogenase (LDH), 384
Lamor diamagnetism, 282
Landau diamagnetism, 282
Langevin diamagnetism, 282
Laser, 345
Layer transfer processes (LTP), 604
Lehmanns model, 108
Light-emitting diodes (LED), 323324
Liquid electrolyte, 322
Lithium, 89
Lithium-ion batteries (LIBs), 965
Lithography, 552, 556
Loaded/infiltrated porous Si, 427428
Local processing, 721726
Long term stability, 981
Lorentz microscopy, 459
Losses, 818
Low strength, 409
Low thermal conductivity, 409410
Luminescence, 418, 952
M
MACE porous nanowires properties, 182183
Macropore formation, 104
Macroporous, 266
silicon, 103110, 524, 590, 592, 594, 716
silicon deformations, 592594
silicon kinetics, 590591
silicon microstructures, 594596
Magnesiothermic fabrication, 86
Magnesiothermic reduction, 89, 969
Magnesium vapor, 88
Magnetic force microscope (MFM), 457458
Magnetic properties, 292294
Index
Magnetic remanence, 293
Magnetization, 460
Magneto-optical Kerr effect, 459
Magnetostatic energy, 292
Make-up additive, 10041005
Mask, 533
Mass-spectrometry detection, 871872
Mass spectrometry imaging (MSI), 874875
Matrix assisted laser desorption/ionization
mass spectrometry (MALDI), 892893
Mechanical properties, 214, 218, 561
Mechanochemical reduction, 6
Medical domain, 734735, 737
Melt gasification, 6
Melting, 452
Melt intrusion, 623626
calculation of payload, 624625
loading of free-standing flakes, 625626
loading of powders, 626
Mesenchymal cells (MSC), 490
Mesoporous, 130, 266, 272273
silicon, 116, 395, 405, 441, 524, 799
silicon film, 560
silicon layers, 258
silicon membranes, 259
structures, 165166
transport, 222
Metal-assisted chemical etching (MACE), 969
Metal-assisted etching (MAE), 27, 49, 58
applications, 58
Metal contacts, 950
Metal deposition, 632
Metal-insulator-metal (MIM) capacitor, 749
Metal particles, 50
Meyer-Neldel rule (MNR), 271
Micro-and nanostructure formation, 632
Microdevices, 800801
Micro-electro mechanical sytems (MEMS),
28, 958
Microencapsulation, 992
Micro-fuel cells, 958
Micro-hotplates, 759760
Micromachining, 165, 168
Micro-optics, 738
Microparticles, 556, 910
Microporous silicon, 133
Microsystems, 738, 798
Micro-total-analysis-systems
(micro-TAS), 798
Microwave processing, 526
Moderate-size biomolecules, detection and
recognition, 862
Modes, 816819
1013
Molecular beam epitaxy (MBE), 585
Molecular doping, 640
Molecular dynamics approach, 758
Monocrystalline, 512
Monte Carlo simulation, 758
Morphology of nanostructures, 173181
Multilayer porous silicon, 240242
Multiphoton microscopy, 420
Multiple internal reflection infrared
spectroscopy (MIR-FTIR), 477
N
Nanocrystals, 308
Nanoexplosions, 979980
Nanoindentation, 215
Nanomembranes, 164
Nanoparticles, 552, 910
Nanoporous, 266267, 271272, 274
Nanostructuration of thin films and surfaces,
543, 545547
Nanostructure-initiator mass spectrometry
(NIMS), 874
Near-field scanning optical microscopy
(NSOM), 419
Neuroblastoma cells, 490
Non-aqueous electrolytes, 16
Noncontact optical probing, 208
Non-imprinted regions, 554
Nuclear magnetic resonance (NMR), 222,
224, 227
cryoporometry, 116, 117, 123, 440442
Nutrient protection, 992994
O
OncoSilTM 906
3 method, 208
Optical gain, 346347, 350
in porous silicon, 350352
in silicone nanocrystals, 347
Optical microscopy, 816
Optical sensors, 849
Optical structures, 816
Optical waveguides, 816
Optics, 738
Optoelectronic functionality, 818
Optoelectronics, 738, 816
Optofluidic platform, 782
Oral delivery, 665, 910911
Oral health, 1000
Organophosphorus compounds (OPCs), 862
Oscillator strength, 500
1014
Osteoporosis, silicic acid and, 989990
Ottow process, 722, 724
Oxidants, 40
Oxidation, 483
Oxidation rate, 591
Oxidized porous Si (porous silicon), 238240,
250251
Oxidizers, 978
P
32
P, 902903
Pancreatic cancer, 902
Paramagnetic materials, 298299
Particles, 556
Passivation, 535
Patterned boundaries, 556
Patterned stamp, 554
Patterned structures, 556
Patterning, 157, 552, 554, 556
Pattern transfer, 532533
Pellicle cleaning ratio (PCR), 1001
Pentane, 561
Peptide, 911
Percolation, 272275
Phase-sensitive detection, 248
Phase state, 225227
Phase transitions, 449
Phonon transport, 209
Photochemical functionalization methods, 686
Photochemical reaction, 690
Photo-dissolution, 534535
Photodynamic therapy (PDT), 929, 933934
Photoelectrochemical etching, 25
Photo-electrodissolution, 533534
Photoetching, 4, 68
Photo-excitation process, 310
Photoirradiation, 507511
Photolithography, 532, 552
Photoluminescence (PL), 308, 338, 418, 950
Photoluminescence-based transducers, 859
Photoluminescence of porous silicon, 349
Photonic crystals, 256257
Photonic device, 761
Photooxidation, 509
Photoresist, 532
Photosensitization properties, 931932
Photothermal therapy (PTT), 930931, 935
Photovoltaics, 570572
pH-triggered delivery systems, 914
Planar inductors, 744, 747749
Index
Plastic deformation, 218
Polarizing elements, 249250
Polymer colloid, 542
Polymer composites for tissue engineering, 923
Polypyrrole (PPy), 614
Poole-Frenkel (PF) transport, 266270, 272
Poorly soluble drugs, 911
Pore diameter distribution, 202
Pore geometry, 116
Pore morphology, 449
Pore size, 118, 439446
Pore structure, 439
Pore volume, 135139, 432
Porosity, 1718, 135139, 147, 214, 216217
Porous multilayer, 154, 157159
depth homogeneity, 159160
fabrication, 154157
functionalization and stabilization, 158
problems in fabricating thick, 159
types, 157
Porous silicon (PSi), 15, 68, 208210,
263277, 288, 381, 435, 463468,
506, 582, 672, 788
in chip-based systems, 788
diode, 268270
formation, 8589
functionalities, 788
material epitaxy, 582
nanostructures-sensing concept, 860861
in brachytherapy, 901906
reduction, 89
scaffolds, 922923
substrates, 582, 584585
Porous silicon (PSi) templates, 613616,
618619
classes of, 613
dissolution of, 618619
filling, 614
materials infiltrated into, 616
polymer impregnation into, 615
Porous silicon based mass spectrometry,
869880
Porous silicon nanocomposites, 297303
biomedical applications, 302303
iron oxide nanoparticles, 299
magnetic behavior, 299302
paramagnetic materials, 298299
Porous silicon powders, 96100
compacting and consolidation of, 98100
mechanical synthesis of, 9698
positive aspects of, 100
Index
Porous Si-polymer composites, 188189
Post-anodization treatment, 717
Process variation, 18
Property, 204205
Property survey, 204
Prostate specific antigen (PSA), 889891
Protein, 911
Proximity gettering (PG), 768
Q
Quantum confinement, 264266, 274, 276
Quantum dot (QD), 274275
Quantum efficiency, 308
Quantum wells, 270
Quantum wire (QW), 274
Quasimonocrystalline silicon process
(QMS), 604
R
Radioactive dentin abrasion (RDA), 1001
Raman microscopy studies, 418
Reaction propagation velocity, 980
Reactive ion etching (RIE) technique, 958
Reactive oxygen species (ROS), 933
Rectifying behavior, 265, 267
Reduction chemistries, 85
Reflectance, 946, 949950
Reflectance-based transducers, 859861
Reflection, 947
Refractive index, 947, 949
anisotropy of porous Si, 246247
of porous silicon, 232
Residual stress, 590
Resistivity, 264, 267, 269
Retinol, 1005
RF electrical isolation, 741749
Rinsing, 1415
Room temperature, 754757
Rotor-milling, 696698, 703
Rugate filter(s), 250, 839
Rutherford backscattering spectroscopy
(RBS), 464
Rytov theory, 837
S
S-band, 314
Scanning electron microscopy (SEM),
291, 416417, 724725
1015
Scanning tunneling microscopy (STM), 417
Scanning tunneling microscopy light emission
(STM-LE), 418
Schottky, 265, 269
behavior, 265
junction, 269
Sebum, 1004
adsorption, 1004
Secondary ion mass spectroscopy (SIMS), 464
Sedimentation, 527
Self-assembly of nanospheres, 542
Semi-empirical methods (SE), 499500
Sensing, 816, 818, 830
Sensing of complex samples, 862864
Sensor(s), 819
Separation by ion implantation of oxygen
(SIMOX), 771
Shifted-excitation-spot (SES) measurement,
348
Short-lived high-energy fluctuations (SLEFs),
509
Si-C vs. Si-O chemistries, 373
SiGe epitaxy, 585
Si-H and Si-O bonds on pore surfaces, 952
Silica feedstocks, 87
silica reduction, 129
Silicic acid, 382, 916
Silicon-carbon bond formation, 683691
Silicon colloids, 1003
Silicon electrochemical etching, 962
Silicon nanocrystals (SiNCs), 672
Silicon nanoparticles, 1003
Silicon nitride (Si3N4), 371
Silicon-on-insulator (SOI) wafers, 570
Silicon-on-nothing (SON), 606
structures, 718
Silicon wafer, 1213
Sintering, 95, 98, 409, 599607
Size metrology, 407
Skeleton size distribution, 202
Skin-feel assessment, 1004
Skin tones, 1003
Small mesopore, 132
Sodium, 89
Solar cell, 946
Sol-gel aptamer microarrays, 895896
Solid-electrolyte interphase (SEI) layer,
970971
Solid/fluid interaction, 888889
Solid-state porous silicon, 323324
Solution casting, 189191
1016
Sonication, 526
Space charge limited current (SCLC), 269
Spark plasma sintering (SPS), 100
Spectroscopic ellipsometry, 147
Spintronics, 288
Spray drying, 666, 668
SQUID-magnetometer, 456
Stable metal contacts to PS, 707
Stain etching, 4, 35, 903, 949
Stain films, 256
Stamp, 552, 554, 556
Step-and-repeat imprinting, 554
Stimulated emission, 346347
in silicon nanocrystals, 346
Stoichiometry, 39
Storage time, 409
Strain, 501502
analysis, 426
Structural color, 256
Structural parameters, 202203
Structure characterization, 116
Subcutaneous delivery, 911912
Substrate orientation, 179
Sun protection factor (SPF), 1003
Sunscreens, 1003
Supercritical carbon dioxide, 526
Supercritical dryers/drying, 564
Superlattice multilayers, 427
Supermicropore, 133
Superparamagnetic (SPM) nanoparticles,
298299
Superparamagnetism, 298
Supramolecular self-assembly methods, 543
Surface area, 432
Surface-based chemical parameters, 203
Surface chemistry, 218, 501502
Surface energy, 602
Surface modification, 365366
Surface stabilization, 707711
Surfactant, 1617
Suspensions/colloids, 527
Sustained fluoride delivery, 1002
T
Taste and mouthfeel, 990
Techniques, 136
for meaning porosity, 137
Temperature dependence, 755757
Temperature in MACE, 180
Template synthesis, 612
Index
Thermal analysis, 449
Thermal conductivity, 207, 209, 753, 757
Thermal constants, 208210
Thermal flow sensor, 761
Thermal functionalization methods, 685
Thermal-Grignard and organolithium
reagents, 688
Thermal-heat reaction, 686
Thermal-hydride abstraction, 688
Thermal-Lewis acid catalysis, 687
Thermally isolating substrate, 759
Thermal oxidation, 359
Thermal-radical initiators, 686
Thermal-transition metal catalysis, 687
Thermionic emission, 266
Thermogravimetry (TG), 450
Thermoluminescence, 335343
Thermoporometry, 440442
Tight binding approach (TB), 499
Tissue engineering milestones for PSi, 922
Tissue reengineering, 387388
Titanium dioxide, 1003
Top-down techniques, 3
Topography, 488490
Transmission electron microscopy (TEM), 414
Trapping, 264, 266, 273
Triclosan, 1003
Tunability, 201, 203
Tunneling, 266, 270, 271, 276
U
UV band, 310
V
Vaccination, 389
Variable stripe length (VSL) technique, 347
Viability assays, 482
Visual color, 256
Vitamins, 992
W
Waffle solar cells, 575
Water oxidation, 361362
Waveguide, 816818
applications, 818819
geometries, 817818
theory, 816817
Wet etching, 76, 117
Index
1017
Wet-milling, 96
Wet point method, 1004
Work-function, 265
Y
Yield strength, 215216
Youngs modulus, 214215
X
X-ray diffraction (XRD), 424
X-ray photoelectron spectroscopy (XPS), 468
X-ray powder diffractometer, 424
X-ray reflectivity (XRR), 144
Z
Zinc oxide, 1003
ZnO films, 584

Leigh Canham (Eds.) - Handbook of Porous Silicon-Springer International Publishing (2014)

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Leigh Canham (Eds.) - Handbook of Porous Silicon-Springer International Publishing (2014)

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Leigh Canham

Handbook of Porous Silicon

Porous Silicon Formation by Anodization . . . . . . . . . . . . . . . . . . . . . . .

Porous Silicon Formation by Stain Etching . . . . . . . . . . . . . . . . . . . . . .

Routes of Formation for Porous Silicon

Porous Silicon Formation by Galvanic Etching

Porous Silicon Formation by Metal Nanoparticle-Assisted

Porous Silicon Formation by Photoetching . . . . . . . . . . . . . . . . . . . . . .

Porous Silicon Formation by HNO3/HF Vapor Etching . . . . . . . . . . . .

Porous Silicon Formation by Porous Silica Reduction . . . . . . . . . . . . .

Porous Silicon Formation by Mechanical Means

Pore Volume (Porosity) in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . .

Ultrathin Porous Silicon Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Porous Silicon Multilayers and Superlattices . . . . . . . . . . . . . . . . . . . .

Porous Silicon Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

MACE Silicon Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Polymer - Porous Silicon Composites

Thermal Properties of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . .

Mechanical Properties of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . .

Mesopore Diffusion Within Porous Silicon . . . . . . . . . . . . . . . . . . . . . .

Refractive Index of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Diamagnetic Behavior of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . .

Ferromagnetism and Ferromagnetic Silicon Nanocomposites . . . . . . .

Tunable Properties of Porous Silicon

Optical Birefringence of Porous Silicon

Electrical Transport in Porous Silicon

Paramagnetic and Superparamagnetic Silicon

Photoluminescence of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . .

Thermoluminescence of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . .

Optical Gain in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Electroluminescence of Porous Silicon

Chemical Reactivity and Surface Chemistry of

Biocompatibility of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Biodegradability of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Characterization Challenges with Porous Silicon . . . . . . . . . . . . . . . . .

Microscopy of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Gas Adsorption Analysis of Porous Silicon . . . . . . . . . . . . . . . . . . . . . .

X-Ray Diffraction in Porous Silicon

NMR Cryoporometry and Estimation of Pore Sizes in

Magnetic Characterization Methods for Porous Silicon . . . . . . . . . . . .

Chemical Characterization of Porous Silicon . . . . . . . . . . . . . . . . . . . .

Characterization of Porous Silicon by Infrared Spectroscopy . . . . . . .

Characterization of Porous Silicon by Calorimetry

Cell Culture on Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Electronic Band Structure in Porous Silicon . . . . . . . . . . . . . . . . . . . . .

Effects of Irradiation on Porous Silicon

Typical Processing Steps with Porous Silicon . . . . . . . . . . . . . . . . . . . .

Imprinting Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Drying Techniques Applied to Porous Silicon . . . . . . . . . . . . . . . . . . . .

Homoepitaxy on Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Heteroepitaxy on Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Oxidation of Macroporous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Sintering of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Photolithography on Porous Silicon

Porous Silicon and Conductive Polymer Nanostructures

Melt Intrusion in Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Gas and Liquid Doping of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . .

Functional Coatings of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . .

Porous Silicon and Electrochemical Deposition

Electroencapsulation of Porous Silicon . . . . . . . . . . . . . . . . . . . . . . . . .

Photoluminescent Nanoparticle Derivatization

Milling of Porous Silicon Microparticles . . . . . . . . . . . . . . . . . . . . . . . .

Ohmic and Rectifying Contacts to Porous Silicon . . . . . . . . . . . . . . . . .