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Thse de Doctorat de lEcole Polytechnique

Spcialit : Chimie
Prsente par

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Xavier Lefvre

Grafting of push-pull systems on germanium: towards


the electric passivation

Greffage de molcules 'push-pull' sur germanium: vers


la passivation dilectrique

Soutenue le 22 Octobre 2012 lEcole Polytechnique


Composition du jury :

Dr. Philippe Blanchard

Moltech Anjou Angers

Rapporteur

Dr. Vincent Huc

Universit Paris 11

Rapporteur

Dr. Dominique Vuillaume

IEMN Lille

Examinateur

Dr. Yvan Bonnassieux

Ecole Polytechnique

Examinateur

Dr. Arnaud Etcheberry

Universit Versailles-St Quentin

Examinateur

Dr. Bruno Jousselme

CEA Saclay

Directeur de thse

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Remerciements

Pour commencer, je remercie Serge Palacin pour mavoir accueilli au sein de son groupe pour
cette thse ainsi que pour son aide prcieuse lors des rdactions darticles et de chapitres de
thse. Merci aussi pour les nombreuses discussions passionnes autour des sciences mais
aussi du rugby ou du Vieux-Port et du Qatar.

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Ensuite, je remercie Bruno Jousselme, mon directeur de thse pour la confiance quil ma
accorde. Ces trois ans tes cts mauront beaucoup appris mais ont galement t
loccasion de passer de bons moments ensemble. Merci toi pour toute cette belle aventure et
jespre que tu auras autant apprci de travailler ensemble que moi. Enfin, jespre que nos
supers colorants finiront par donner des rsultats !!
Pour continuer, je remercie Philippe Blanchard, Vincent Huc, Yvan Bonnassieux, Arnaud
Etcheberry et Dominique Vuillaume davoir accept dvaluer mon travail ainsi que pour les
discussions fructueuses lors de la soutenance.
Je remercie ensuite tous ceux qui mont apport leur expertise technique pour raliser un
certain nombre de caractrisations : Dominque Vuillaume et Stphane Lenfant pour les
mesures lectriques lIEMN (merci pour laccueil au passage), Olivier Segut pour les
images AFM et surtout Pascale Jgou pour les multiples mesures XPS sur mes chantillons
tartines de confiture .
Ces trois ans au LCSI sont passs trs vite mais ont t trs agrables surtout grce la bonne
humeur qui rgnait au 462-466. Merci donc Papito Guy pour les discussions scientifiques
autour dun rafraichissement et pour les debriefings rugby du lundi matin ainsi que pour les
farces et autres canulars pour dtendre latmosphre, attention lacide actique !! Merci
Pascal, mini-chef, pour tout ce quil ma appris au labo et en dehors et pour les nombreuses
discussions, gare aux semelles cloutes de la piscine !! Merci Tata Brigitte pour la vitesse
dexcution des commandes et des coups de main au labo, ralentis un peu Tata, on ne suit
plus !! Merci Pascale pour son aide prcieuse pour lanalyse des spectres XPS et pour sa
disponibilit, bon vent dans ta nouvelle aventure !! Merci Ccile pour les nombreuses
discussions et pour son souci du bien-tre des autres, on nira plus en RMN mais je suis sr
que tu me trouveras un remplaant !! Enfin, un merci tout particulier mon chauve prfr,
Thomas, merci pour tout ce que tu mas appris et pour toutes les parties de rigolades, big up
mon loulou et bientt !!
Pour continuer, je tiens remercier galement tous mes camarades de fortune au LCSI et
notamment Alex (vive Paris !!), Julie (vive Batman !!), Adina et Claudia (la touche roumaine)
mes co-bureaux pour la bonne humeur quils ont su prserver. Merci galement Alice,
Romain, Federico, Dimitri, Caue, les Pegastech (Frida, Lorraine, Matthieu, Fabien et
Sbastien), Siddharth et Nabila. Un merci particulier Olivier qui non content de mavoir
appris normment de choses fut aussi le troisime larron de la fine quipe. Enfin, merci aux

membres actuels du LCSI : mini-pouce Tiphaine, Romain, Cdric, Thomas, Thibaut et mon
petit Renaud et ses pulls. Bon vent tous !! Pour terminer, jadresse un clin dil amical
tous les stagiaires que jai pu croiser au LCSI ainsi quaux collgues des autres groupes et
notamment Stphane, Fabien, Jrme, Ludo, Moslem et Amandine et Catherine, notre
secrtaire.
Grce vous tous, ces trois ans ont t riches en excellents moments mais aussi en
dcouvertes, merci pour tout !!

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Enfin, je remercie ma famille pour son soutien de tous les instants pendant cette aventure. Si
jen suis l, cest aussi grce eux. Merci galement tous mes amis et notamment aux
Kinder. Enfin, merci Lucie de mavoir accompagn pendant ces trois ans. Ma Lulu,
laventure de la thse se termine mais une nouvelle commence pour nous et ta prsence mes
cts me permettra daller encore plus loin. Vivement la suite !!
Voil, ce chapitre de ma vie est maintenant termin, le suivant souvre dj et promet dtre
tout aussi intressant. Merci tous et bientt !!

Table of contents

Abbreviations, notations and acronyms..7


Chemicals compounds..9
Introduction.11
I. State of the art..14
I.1 Dielectrics.15

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I.1.1 Inorganic dielectrics...16


I.1.2 Polymer dielectrics.18
I.1.3 Molecular dielectrics..20
I.1.3.1 Self-assembled monolayers (SAMs)...20
I.1.3.2 Self-assembled nanodielectrics (SANDs)...21
I.1.4 Hybrid dielectrics...22
I.1.4.1 Polymer-based composites..........22
I.1.4.2 Organic-Inorganic bilayers..24
I.2 Surface functionalization......25
I.2.1 SAMs..26
I.2.2 Activated monolayer formations27
I.2.3 Diazonium salts..28
I.2.4 Ge surfaces functionalization.29
I.3 Position of the subject.......31
II. Synthesis of push-pull systems..47
II.1 Tetracarboxylic naphthalenediimide derivatives (-- model systems)...50
II.1.1 Thiols derivatives..51
I.1.2 Diazonium salt derivatives.52
I.2 Push-pull systems..53
5

II.2.1 Azobenzene derivatives54


II.2.2 Stilbazolium derivatives...56
III. Chemical grafting of diazonium salts on germanium...63
Introduction to the spontaneous grafting of diazonium salts on Ge.....64
Towards organic film passivation of germanium wafers using diazonium salts:
mechanism and ambient stability..65
IV. Electrochemical grafting of diazonium salts on Ge and grafting of the push-pull
systems.89
IV.1 Electrografting of diazonium salts on Ge..91

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IV.1.1 Influence of the group in para-position..97


IV.1.2 Absolute coverage...99
IV.2 Comparison with spontaneous grafting on Ge.100
IV.3 Grafting of the push-pull systems101
IV.4 Conclusion...107
V. Grafting and I/V characterization of model compounds.113
V.1 Grafting of model molecules.114
V.1.1 Grafting on germanium..115
V.1.2 Grafting on gold.116
V.2 Electric measurements on the model molecules grafted on gold.120
V.3 Conclusion.124
Conclusion..127
Appendixes.130

Abbreviations, notations and acronyms

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a) Chemicals, synthesis and materials


Ac

Acetyl group (CH3CO)

ACN

Acetonitrile

A.G.

Anchoring Group

BST

Barium Strontium Titanate

Bu

Butyl group

BZT

Barium Zirconium Titanate

C8-BTBT

Dioctylbenzothienobenzothiophene

CR-V

Cyanoethylated poly(vinyl alcohol)

CYEPL

Cyanoethylpullulan

DCM

Dichloromethane / methylene chloride

DLC

Diamond Like Carbon

DMF

N,N- dimethylformamide

Et

Ethyl group

H.G.

Head Group

HMDS

Hexamethyldisilazane

HOPG

Highly Ordered Pyrolitic Graphite

ITO

Indium Tin Oxide

Me

Methyl group

ODPA

Octadecylphosphonic acid

OTS

Octadecyltrichlorosilane

P3HT

Poly(3-hexylthiophene)

PEO

Poly(ethylene oxide)

PMMA

Poly(methyl methacrylate)

Pr

Propyl group
7

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PS

Poly(styrene)

PTrFE

Poly(trifluoroethylene)

PVA

Poly(vinyl alcohol)

PVAc

Poly(vinyl acetate)

PVDF

Poly(vinylidene fluoride)

PVP

Poly(4-vinylphenol)

RT

Room Temperature

SAM

Self-Assembled Monolayer

SAND

Self-Assembled Nano-Dielectric

THF

Tetrahydrofuran

ZITO

Zinc Indium Tin Oxide

b) Characterization techniques
AFM

Atomic Force Microscopy

CV

Cyclic Voltammetry

DSC

Differential Scanning Calorimetry

IR

Infrared spectroscopy

LEED

Low-energy Electron Diffraction

NMR

Nuclear Magnetic Resonance

STM

Scanning Tunneling Microscope

XPS

X-Ray Photoelectron Spectroscopy

c) Others
FET

Field Effect Transistor

OFET

Organic Field Effect Transistor

RMS

Root Mean Square

Chemical compounds

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Diazonium salts

Model molecules

Push-pull systems

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Stilbazolium derivatives

Azobenzene derivatives

10

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INTRODUCTION

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Introduction
In everyday life, micro- and nano-electronics are ubiquitous. Indeed, from cars to smart
phones and computers, we are surrounded by devices containing miniaturized electronic
components. For now, the microelectronic market is dominated by the silicon technology.
Silicon takes advantage from its native oxide SiO2 which presents very good insulating and
protecting properties. No other couple metal or semiconductor oxide presents such
interesting features. However, SiO2 is reaching its limits in terms of size reduction. Creating a
thinner layer will induce great leakage currents through the material generating on
overconsumption. Therefore, if one wants to further reduce the size of the device, the use of
another insulating substrate is required, and a new protecting and insulating material must be
created. However, the future use of the device in a smart phone or in embedded
microelectronic component requires some properties. First of all, the protective and insulating
layer must be resistant and stable under harsh conditions (heat, humidity, electrical field).
Indeed, the coating must remain adhesive during all the life of the device without altering its
performances. The second point concerns the energy consumption: the lowest energy the
device needs, the best the layer is. Of course, no one wishes to charge his smart phone every
day; therefore, the components must use as little energy as possible. For example, in fieldeffect transistor technology, this corresponds to a decrease of the operating voltage. Finally,
due to industrial constraint, the layer will have to be created by soft and easy ways.
Thus, important work has been made during the last decades to develop new dielectric
materials presenting better properties at reduced size compared to SiO2. This domain is much
studied and numerous applications are targeted on a huge market present in every single
electronic device. Due to the increasing need for new dielectric materials, numerous
compounds and various deposition techniques have been developed. Meanwhile, different
electronic characterization methods have been introduced, conferring all the tools to fully
analyze the created material.
Regarding the nature of the compound used to passivate and insulate a surface, the scope is
dominated by inorganic oxide such as HfO2, Al2O3, or Ta2O5. However, particularly for
flexible substrates such as polymers, the deposition technique remains critical. Indeed,
inorganic oxides are usually deposited at high temperature. Therefore, numerous methods
were developed to form the layer from a solution based process. Nevertheless, the
introduction of self-assembled monolayers as dielectric material is a real breakthrough
opening the scope for very thin organic insulation layers. Following this trend, various
organic films were developed to create the desired coating. Surface chemistry which was less
concerned with the deposition of inorganic oxides becomes the crucial actor of the process.
Indeed, surface chemistry intends to confer new properties to a material by changing its
interface. For example, hydrophobicity can be controlled by tuning the surface of a material
by different molecules. Surface chemistry is thus of great interest if one wants to create an
organic thin insulating film on a surface. Various methods are available to attach organic
compounds on a surface, including SAMs or diazonium salts. However, the stability
requirement reduces the scope almost exclusively to the one promoting a covalent bond
between the substrate and the film. Therefore, thiols and diazonium salts are derivatives of
choice to be used in insulating layers. According to the Moores law, the size of the devices
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Introduction
will be further reduced (divided by 2 every 18 months), thus opening the field for organic
electronics.

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Finally, as the amazing Si-SiO2 couple is discarded due to the leakage current induced in the
too thin oxide layer, Si could also be replaced by other semiconducting materials such as
AsGa or germanium. Indeed, these compounds have better intrinsic properties than silicon in
terms of charge transport and band-gap. Moreover, they are compatible with a large variety of
surface chemistry techniques to deposit an organic film. Thus, even if they are not widely
used, they are of great interest for future portable applications. However, their surface must be
first prepared for the grafting, adding a step in the fabrication process. Nevertheless, their
excellent properties attract research as the studies on germanium and AsGa preparation and
functionalization are more and more numerous.
In this context, the main goal of this work is to create a passivating and insulating layer on
germanium surfaces. To realize this, germanium surfaces will be first etched (removal of
native oxide) before being grafted by specifically designed and synthesized push-pull
systems. Meanwhile, the electric properties of the formed layers will be investigated by
different techniques.
After a presentation of the current work on dielectric materials and surface functionalization,
the synthesis of the designed push-pull systems and of derived model molecules will be
presented. Then, the etching of germanium and its functionalization by thiols and diazonium
salts in a spontaneous process will be studied in details and presented through a published
article. In the fourth chapter, the electrografting of diazonium salts on germanium surfaces as
well as the grafting of the push-pull systems will be presented. Finally, the electronic
characterizations of the model molecules deposited on gold will be discussed.

13

I. State of the art

I.1 Dielectrics13
I.1.1 Inorganic dielectrics...14

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I.1.2 Polymer dielectrics.16


I.1.3 Molecular dielectrics..18
I.1.3.1 Self-assembled monolayers (SAMs)...18
I.1.3.2 Self-assembled nanodielectrics (SANDs)...19
I.1.4 Hybrid dielectrics...20
I.1.4.1 Polymer-based composites..20
I.1.4.2 Organic-Inorganic bilayers..22
I.2 Surface functionalization...23
I.2.1 SAMs..24
I.2.2 Activated monolayer formations25
I.2.3 Diazonium salts..26
I.2.4 Ge surfaces functionalization.27
I.3 Position of the subject.29

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I. State of the art


Micro- and nano-electronics are widely used nowadays in various domains such as new
technologies embedded in cellphones or computers. However, the size-reduction is a great
challenge for developing new devices with increased performance. For now, silicon is
commonly employed but is now reaching its limits in terms of mobility or high-frequency
operations. Furthermore, decreasing the thickness of the SiO2-dielectric layer induces greater
leakage currents which lead to overconsumption. This opened the way to the development of
electronics based on other substrates such as AsGa or germanium. However, germanium
oxide are neither stable nor insulating; thus, germanium surfaces must be passivated with a
dielectric layer. In this context, different approaches are currently studied. First, as SiO2 is no
longer the best dielectric candidate if the device size must be further reduced; intensive
research has been conducted on dielectrics. Organic dielectrics have been developed and
recently, molecular layers have been introduced to form a thin insulating film. These
molecules present a high dipolar moment ensuring a good charge separation. However,
turning on molecular electronics requires the development of surface chemistry. Indeed, the
molecules have to be attached to the surface to ensure a good stability of the insulating layer.
Therefore, new surface functionalization techniques were developed over the past decades. In
this chapter, we will describe the main results on dielectric materials and the different
techniques to form a thin organic film on a surface and in particular on germanium.

I.1 - Dielectrics
Dielectrics are mainly used as insulators in microelectronics. Therefore, most of the research
on dielectrics focused on large band-gap compounds The main applications of dielectrics are
in transistors (gate insulators in field effect transistors) and capacitors. SiO2 is the most
employed dielectric in micro-electronics but will soon reach its intrinsic material limits1.
Indeed, as the sharp decrease in size requires always thinner dielectric layers2, in the case of
SiO2, this induces greater leakage current (due to tunneling current) that dissipates large
amount of power. Thus, new materials must be developed to provide a thin dielectric layer
that prevents overconsumption. Those new dielectrics will have to fulfill the following
requirements: i) low leakage current and high stability, ii) efficient charge transport in the
(semi)conductive layer (high charge carrier mobility), iii) versatility (in particular
compatibility with both p- and n-type semiconductors), iv) high capacitance at low voltage
and v) soft fabrication method compatible with plastics and patterning. The latter led to
development of dielectrics processed in solution. Point i) can be addressed by both increasing
the dielectric constant of the material and forming a dielectric defect-free interface. Indeed,
those defects are at the origin of leakage currents. Moreover, dielectric surface defects are
also responsible for low charge carrier mobility; thus, point ii) can be solved by controlling
the dielectric resulting surface after formation of the layer. For the sought applications, there
are two crucial parameters to evaluate the dielectrics: the maximum possible electric
displacement and the capacitance. The first is given by: Dmax=0kEB where k is the dielectric
constant and EB the dielectric breakdown field. The capacitance is C=0k/d where d is the
insulator thickness. Knowing this, there are two ways to obtain high capacitance materials:
increasing k (high-k dielectrics) or reducing the thickness of the layer. Nevertheless, high-k
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I. State of the art

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dielectrics generally exhibit low carrier mobility due to randomly oriented dipole moments at
the interface. Low-k but high-ordered dielectric can, thus, compensate their reduced
capacitance with higher mobility. Furthermore, low-k dielectrics present a reduced hysteresis
in field-effect transistors and often decrease the threshold voltage. Dielectric materials are
usually characterized by their capacitance and the mobility of charge carriers achieved in field
effect transistors (FETs) in which they act as gate insulator (Scheme 1).

Scheme 1. Generic structures of a capacitor (left) and a field effect transistor (right) used to
characterize a dielectric material.
In this part, we will focus on the most recent works in the field of dielectric materials and
discuss them regarding their chemical nature which is a key point for versatility and for soft
fabrication.
I.1.1 Inorganic dielectrics
Currently used in integrated circuit technologies, SiO2 has a relatively low dielectric constant
(k=3.9) and when films become thinner and thinner, leakage current appears, mainly due to
tunneling transport. Furthermore, when SiO2 is used as gate dielectric, devices require high
operating voltages. Considering the need to increase the surface density of devices, SiO 2 does
not appear as the best candidate as gate insulator. High-k inorganic dielectrics were thus
developed to replace SiO2 while affording comparable or greater capacitances. These
alternative materials can be classified in two groups: metal oxides and metal non oxides.
Silicon nitride (SiNx, k=6.2 for bulk) belongs to the latter family35. This material has a higher
dielectric constant than SiO2 and can be processed at room temperature providing good
mobility in pentacene-based field effect transistori (1 cm2 V-1 s-1). Furthermore, layer
significantly thinner (30 nm) than with SiO2 can be employed. Indeed, SiO2 can also be
processed at room temperature via a sol-gel synthesis but still require a thick layer (100 nm)
to prevent leakage current6.
i

In the text, the expression mobility with pentacene will be used to refer to mobility in pentacene-based
FETs

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I. State of the art

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Despite those encouraging results, metal oxides still draw most of the attention in inorganic
dielectrics. Along with silicon nitride, Dimitrakopolous et al. introduced high-k metal oxides
as dielectrics7,8. They used barium zirconium titanate (k=17.3) and barium strontium titanate
(k=16) in pentacene-based field effect transistors and obtained mobility greater than 0.3 cm2
V-1 s-1 at low operating voltage (5 V) and with high ON/OFF ratios ii. Recently, titanate
dielectrics were developed by Lehnert9 (BaTiO3 nanoparticles in a sol-gel matrix) and Cai10
(BaTiO3 and SrTiO3 nanoparticles in a solution process). Both achieved high dielectric
constants (k=100, k=9.3 and k=7.1 respectively), the latter also exhibited high mobility in
pentacene flexible field effect transistors (between 2 and 3.5 cm2 V-1 s-1 for BaTiO3 and
SrTiO3). Nanoparticles are easily processable in solution but must be used inside a matrix to
obtain the crucial smooth interface ensuring high mobility. Therefore, bulk oxides are still
materials of choice as dielectrics.
Tantalum oxide1117 (Ta2O5) was the first metal oxide dielectrics used as alternative to SiO2.
Indeed, its high dielectric constant (k=23) provided very low leakage current (less than 10 -8 A
cm-2) with low operating voltage (around 5 V). Moreover, high capacitances were obtained,
even with thin films. Finally, good mobilities were achieved in FET with pentacene (up to
0.45 cm2 V-1 s-1). In 2002, Al2O3 films were also reported as dielectrics18. Despite its low
dielectric constant (k=8), this metal oxide appeared promising because high-quality films can
be obtained at room temperature. Low leakage current (less than 10-9 A cm-2) and good
mobility (up to 0.2 cm2 V-1 s-1) were reported along with high capacitance1925. Last but not
least, Al2O3 films were also used as dielectric in germanium based transistors providing an
ultrathin equivalent oxide thicknessiii with germanium oxide allowing high hole mobility26,27.
Two years later, in 2004, TiO2 was used by Wang in FETs28. However, despite its very high
dielectric constant (k=41), this material exhibited large leakage current and low mobility with
pentacene (5 x 10-3 cm2 V-1 s-1)2932. This problem could be solved by using oleic acid-capped
TiO2 nanoparticles33 with a much lower dielectric constant (k=5.3) but also a much lower
leakage current (3 x 10-8 A cm-2) and better mobility (0.2 cm2 V-1 s-1); thus providing a good
candidate for dielectric applications. As the last widely investigated material, HfO2 has a high
dielectric constant (k=25) and a large band-gap3437. Unfortunately, devices based on HfO2
present large hysteresis and low mobility36 (2.2 x 10-2 cm2 V-1 s-1) even if using a sol-gel
process led to acceptable mobility37 (0.13 cm2 V-1 s-1) at low operating voltage. HfO2
dielectrics were also grown on germanium substrates giving lower leakage current than GeO2
or nitride passivated Ge38. An alternative to HfO2 is obtained by incorporating nitrogen in
amorphous HfO2 to form HfON39,40 in order to improve its properties. This material allowed
low leakage current with higher mobility compared to HfO2. Other metal oxide were
investigated such as Gd2O3 (k=7.3)41,42, ZrO2 (k=25)43,44 and CeO2 (k=23)4549 but all these
oxides exhibited drawbacks and their properties did not match those of the previous cited. All
the properties of high-k metal oxide dielectrics are summarized in Table 1 (see p. 22).
ii

the ON/OFF ratio in field effect transistor is the ratio between the current when the transistor is turned on
(bias applied on gate) and the current when the transistor is off (no bias on gate), it strongly depends on the
leakage current and thus on the nature of the dielectric
iii
The equivalent oxide thickness is the thickness of the layer of SiO 2 which would give the same properties than
the studied layer.

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I. State of the art

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Finally, one of the main drawbacks of oxide-metal dielectrics is the poor quality of their
surfaces. Indeed, surface defects act as charge traps and thus degrade the mobility in
semiconductors deposited at the interface. Chua et al.50 demonstrated that interface roughness
and mobility were correlated and the more organized the interface the higher the mobility.
The surface can be controlled by functionalization with a self-assembled monolayer (SAM).
SAMs are formed by specific adsorption of molecules on surfaces, the interactions between
molecules (Van der Walls, -interaction) promoting the organization of the layer. Their
general structure is depicted on Scheme 2.

Scheme 2. Ideal theoretical structure of a SAM


Incorporating a SAM at the interface dielectric/semiconductor in transistors mainly increases
the mobility in the semiconductor but also shifts the threshold voltage. The increase of
mobility was attributed to the passivation of hydroxyl groups at the surface50. These groups
can trap electrons thus preventing high mobility. Hydroxyl surface groups can be
functionalized with silanes, phosphonic acids or carboxylic acids. Furthermore, the
incorporation of a SAM often reduces leakage currents. SAMs are thus promising to improve
the properties of dielectric metal oxides51. For instance, SiO2 modified with octadecylsilane
greatly improved mobility with pentacene (from 0.31 to 3 cm2 V-1 s-1) still with large ON/OFF
ratio52,53. Same tendency is observed with hexamethyldisalazane52 (up to 3.4 cm2 V-1 s-1) or
other silanes. Following this trend, functionalizing other metal oxide surfaces also induced
larger mobilities. So, HMDS-treated Ta2O5 dielectric54,55 exhibited mobility of 0.51 cm2 V-1 s1
(against 0.45 cm2 V-1 s-1 for bare Ta2O5), phosphonic acid-treated HfO2 gave mobility as
high as 1.6 cm2 V-1 s-1 (to be compared with 0.28 cm2 V-1 s-1 with bare)5659, and eicosanoic
acid-treated Al2O3 showed mobility of 5 cm2 V-1 s-1 (versus 0.2 cm2 V-1 s-1 on bare)60. To sum
up, even if SAMs passivation reduces the capacitance of the dielectric, it also dramatically
reduces leakage current and increases breakdown field and mobility without requiring high
operating voltage. Table 1 summarizes some of the main results obtained with SAM
passivation.
I.1.2 Polymer dielectrics
Polymer dielectrics are good candidates for use in FETs because they are solution processable
and easily patternable. Unfortunately, they also have lower dielectric constants than oxidebased materials and thus, a much thicker layer of dielectric is needed to reduce leakage
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I. State of the art

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current, which decreases the capacitance and increases the operating voltage. Therefore,
research was put on high capacitance polymers (which can be obtained either by reducing the
thickness or by increasing the dielectric constant) allowing low leakage current together with
low operating voltage. Typical dielectric constants are in the range of 10 which is rather high
for organic-based dielectrics and allows their use as an alternative to inorganic dielectrics.
Furthermore, with polymers, smooth transparent films can be obtained both on rigid and on
flexible substrates. These two features are also of high interest due to the tight dependence
between the morphology of the interface and the field-effect mobility but also for
optoelectronic applications. We will now briefly describe some of the most interesting results
obtained with polymer dielectrics.
The first use of polymers as dielectrics was reported in 1990 by Peng et al.61. They obtained
good results in field-effect transistors with high-k polymers such as polyvinylalcohol (k=7.8)
and cyanoethylpullulan (CYEPL, k=18.5) whereas no field-effect was detected in the same
conditions with low-k polymers (polymethylmethacrylate, PMMA, k=3.5 and polystyrene,
PS, k=2.6). They even fabricated with CYEPL the first all-organic FET on flexible substrate
(poly(parabanic acid) resin) and mobilities with sexithienyl up to 4.3 x 10 -1 cm2 V-1 s-1. Later,
Bao et al.62 reported a high-performance plastic transistor using polyimide as dielectric and
poly(3-hexylthiophene) (P3HT) as semiconductor. This transistor was fully made by printing
on a plastic substrate. Polyimides were further developed by Pyo et al.63 who reported a
patternable low-temperature processable gate dielectric based on a photosensitive polyimide.
Mobilities up to 0.2 cm2 V-1 s-1 were obtained with pentacene with high ON/OFF ratios and
very low leakage current (5 x 10-8 A/cm2). Very recently, polyimide dielectric was modified
by solvent vapor annealing allowing a reorganization with a higher degree of order of
dioctylbenzothienobenzothiophene (C8-BTBT, p-type semiconductor) films64. Very high
mobilities were obtained (average 3 cm2 V-1 s-1, up to 9.1 cm2 V-1 s-1) among the highest for
organic single crystals. PMMA was also employed as dielectric and led to good mobility with
pentacene (up to 0.241 cm2 V-1 s-1) with a high ON/OFF ratio65. Later, polymers such as
polyvinyl alcohol (PVA), poly 4-vinyl phenol (PVP) and polystyrene also yielded good
results66. However, PVP, the most employed polymer as dielectric, presents a hysteresis
shifting the threshold voltage. This problem was addressed by Park et al.67 using a bilayer of
PVP and polyvinylacetate (PVAc). PVP allowed a favorable growth of pentacene whereas
PVAc reduced the hysteresis. Other candidates for reducing hysteresis with high mobilities
are poly(vinylidene fluoride) (PVDF) and its copolymer with trifluoroethylene (P(VDFTrFE))68. This copolymer exhibited dielectric constant of about 10 and was successfully used
in organic thin-film transistors. Other fluorinated polymers also exhibited good performances,
thus driving attention on those particular polymers. Finally, two interesting classes of
polymers were recently introduced: parylene and biopolymers. The former (k=3.1) allows
conformal coatings but, more interestingly, can also act as a barrier towards moisture or
oxygen69. Biopolymers are of interest due to their biodegradability that allows applications in
medical diagnosis or implants but also in packaging. Indeed, nucleobases such as adenine and
guanine, sugars (glucose, lactose, and sucrose) and even caffeine are dielectric materials (k
between 3.85 and 6.55) and have shown good properties in field-effect transistors (mobilities
up to 0.55 cm2 V-1 s-1 with C60 and caffeine)70,71.
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All those polymers exhibit quite high dielectric constants but, to obtain large capacitances,
thick layers (few hundreds nm up to few m) must be deposited. A way to improve the
capacitance of thinner films consists in cross-linking the polymer. Furthermore, cross-linking
decreases the solubility of the polymers thus allowing spin-coating, printing or solution
deposition of the subsequent layers on the dielectric. Cross-linked PVP72, for instance, gave
mobility with pentacene up to 3 cm2 V-1 s-1. Low-voltage devices have been fabricated with
cyanoethylated poly(vinyl alcohol) (CR-V) as dielectric73. This polymer exhibited a high
dielectric constant (k=12.6) allowing a high capacitance even with a thin layer (92.9 nF cm -2
with 120 nm). Lower leakage current than in bulk CR-V (1 x 10-7 A cm-2 vs 3 x 10-4 A cm-2)
and good mobility with pentacene (0.62 cm2 V-1 s-1) were obtained. Other polymers, such as
PMMA and PS, were also cross-linked and providing better results than their bulk
counterparts. Low operating voltage, high mobility and low leakage current were obtained
together with a low thickness of the dielectric (below 100 nm). Finally, Marks and his group
studied several cross-linking reagents with PVP and PS to form cross-linked polymer blends
allowing ultrathin films (10 to 20 nm) to exhibit low leakage current (down to 2 x 10 -8 A cm2
), high mobility with pentacene (up to 0.85 cm2 V-1 s-1) and good ON/OFF ratio (up to
107)74,75. Table 1 highlights some results with polymeric dielectrics.
I.1.3 Molecular dielectrics
The main shortcoming of the previously described classes of dielectrics is the high-operating
voltage: indeed, a relatively high thickness (above 100 nm) is needed to reduce leakage
current, thus resulting in low capacitance. Hence a compromise between the lowest operating
voltage and the smallest leakage current achievable by the device has to be found. High-k
dielectrics are highly desirable and were developed both in inorganic and polymeric substrate.
However, the thickness, and by the way the operating voltage, could be further reduced by
using a thin film of high-k molecules. In this part, we will describe two approaches to form
high-k thin dielectric films: simple self-assembled monolayers and self-assembled
nanodielectrics.
I.1.3.1 Self-assembled monolayers (SAMs)
As previously discussed, SAMs can be used to obtain smooth dielectric surfaces from oxidebased materials, thus enhancing the mobility in FETs, but they can also serve as dielectric
layer by themselves. This feature was introduced by Vuillaume et al.76 in 1996. Indeed,
contrary to very thin films of SiO2 (few nm), SAMs of similar thickness still exhibit low
leakage current (in the range of 10-8 A cm-2). For instance, an octadecyltrichlorosilane (OTS)
SAM, with a thickness of 2.8 nm, is a good insulator that can be further enhanced by
annealing to obtain a well-ordered SAM. Furthermore, SAM deposition is a versatile method
that allows forming layers with various head groups77,78 possibly available for subsequent
post-functionalization. Good performances were obtained in organic thin film transistors with
sexithiophene. These performances were improved by using aromatic terminated SAMs such
as 18-phenoxyoctadecyltrichlorosilane (PhO-OTS)79,80. Pentacene transistor performances
were drastically enhanced regarding the OTS SAM exhibiting high mobility (up to 1 cm 2 V-1
cm-1), high ON/OFF ratio (106), low leakage current (8 10-7 A cm-2) and low operating voltage
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(2 V). PhO-OTS SAM also provided very high capacitance (900 nF cm-2). The improvement
of performances is thought to come from a better and tighter organization of the PhO-OTS
SAM than in the OTS SAM. Recently, phosphonic acid-based SAMs were developed due to
their better stability compared to silane-based SAMs81,82. Microcontact-printing of
octadecylphosphonic acid SAM on Al2O3 gave a 2.1 nm thick dielectric with 700 nF cm-2
capacitance allowing mobility up to 0.4 cm2 V-1 s-1 for pentacene82. SAMs are compatible
with different substrates ranging from bare metal or silicon to inorganic oxides but also with
most of the known organic semiconductors from pentacene to carbon nanotubes83 or
fullerenes84 through n-type semiconductors such as naphthalene diimide85. Finally, -
systems were also introduced in SAMs as dielectric layer. Anthracene-terminated SAMs56
exhibit larger capacitance than their alkyl counterparts together with lower leakage current
thus allowing very low operating voltage (1.5 V). Multi-layering of SAMs (up to 100 nm
thick) further decreased the operating voltage (1 V) with ensuring good mobility with
pentacene (1.3 cm2 V-1 s-1) taking advantage of the high dielectric constant of the SAM
(k=17)86.
I.1.3.2 Self-assembled nanodielectrics (SANDs)
The concept of SAND was introduced by Marks and Facchetti in 200587. It consists in selfassembled multilayers cross-linked between each layer by octachlorotrisiloxane. The SAM
layers can be of different nature: alkyl chains or highly polarizable stilbazolium (push-pull
system). The structures of the SANDs are depicted on Scheme 3.

Scheme 3. Structure of the SANDs developed by Marks and Facchetti extracted from their
work87.
Different combinations of layers were investigated and provided good results8890. For
instance, capacitance up to 710 nF cm-2 were obtained together with leakage current as low as
10-9 A cm-2. These values, obtained with SAND thickness between 2.3 and 5.5 nm, are far
better than those observed with a 300 nm thick SiO2 film. OFETs with p- and n-type
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semiconductors were fabricated with SANDs leading to much lower operating voltage than
with inorganic or polymer dielectrics with similar mobility (2-3 cm2 V-1 s-1 at 1 V with
pentacene). SANDs also favorably compared to polymer cross-linked blends in terms of
capacitance or leakage current. Furthermore, they are versatile and deposited from solution
thus allowing the use of plastic substrates. Another interesting feature is the possibility to tune
the properties by associating different components in the layer or by increasing the number of
deposited layers. For instance, combining three layers of SAND III (Scheme 3) led to a
transparent 16.5 nm thick dielectric layer91 allowing large field-effect mobility (up to 196 cm2
V-1 s-1 with ZnO nanowires) at low-operating voltage (1.5 V) with a high ON/OFF ratio (108).
Adding another layer of SAND III further increased the mobility (258 cm2 V-1 s-1) but also the
operating-voltage (3 V) and also decreased the ON/OFF ratio (105). Another way to improve
the achieved mobility was to reinforce the SAND with a thicker capping layer of
chlorosiloxane-derived SiOx (5 nm instead of 0.8)92. This leaded to a dramatically improved
field effect mobility with amorphous zinc-indium-tin oxide (a-ZITO). Finally, new molecules
were developed to allow vapor phase deposition93 leading to high performance devices
(capacitance up to 425 nF cm-2 and field-effect mobility up to 150 cm2 V-1 s-1 with a-ZITO).
Table 1 summarizes the results achieved with SAMs and SANDs.
I.1.4 Hybrid dielectrics
The development of hybrid dielectrics originates with combining the advantages of inorganic
and organic dielectrics. Indeed, inorganic metal oxides present high dielectric constants but
often require annealing process at high temperature making them incompatible with plastic
substrates. Furthermore, they are also non-compatible with flexible applications. On the
opposite, polymers are solution processable and have good mechanical properties adapted to
flexible application on plastic substrates. However, they also present relatively lower
dielectric constants than inorganic counterparts, thus requiring thicker layers to prevent
leakage currents. Unfortunately, these thicker layers induce a lower capacitance thus
increasing the operating voltage. The aim of hybrid dielectrics is to combine the mechanical
and processing properties of organic materials together with the high permittivity of inorganic
dielectrics. The main approaches are based either on a polymeric matrix filled with
nanoparticles, molecules or ionic gels or on organic-inorganic bilayers.
I.1.4.1 Polymer-based composites
In this part, we will describe dielectrics based on a polymer matrix which electric properties
were improved by incorporating a filler inside the matrix. The filler can be metal
nanoparticles, inorganic oxide nanoparticles, molecules or ionic liquids.
In 1988, the first polymer-based hybrid dielectric was introduced94. It consisted in an
inhomogeneous dispersion of TiO2 nanoparticles in polystyrene. Progress in dispersion
control led to improving the homogeneity and, in 2004, Chen et al.95 reported a dielectric
composed by a cross-linked poly-4-vinylphenol matrix filled with TiO2 nanoparticles. They
obtained good mobilities with pentacene (0.2 to 0.4 cm2 V-1 s-1) with spin-coated dielectric
layer. However, a shortcoming of this kind of hybrid dielectrics is the apparition of greater
leakage current compared to the bulk polymer. This decreases the ON/OFF ratio thus limiting
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I. State of the art


the performances of the device. Furthermore, the solubility of nanoparticles also limits the
range of achievable performances due to aggregation at high concentration. Maliakal et al.96
used phosphonate-terminated styrene to coat TiO2 nanoparticles enhancing the dispersion
even at high concentration thus reducing leakage current and operating voltage. They reported
mobility as high as 1.3 cm2 V-1 s-1 with pentacene with TiO2-PS composite. More efforts were
then put on improving the dispersion of nanoparticles. Marks et al.97 reported a method based
on in-situ polymerization initiated from the nanoparticles coated by a catalyst. Lee et al.98
proposed to incorporate surfactants thus enhancing the dispersion but they still could not
prevent the aggregation and apparition of leakage current. Kim et al.99 changed PS for a
Nylon-6 matrix but a PVP layer was still needed to cut off the leakage current. Mobility was
improved up to 0.7 cm2 V-1 s-1 with pentacene. Lee et al.100 also incorporated TiO2
nanoparticles in a polymeric matrix but composed of polyimide. They achieved some of the
highest mobilities on polyimide with pentacene without decreasing the ON/OFF ratio. Other
high-k metal oxide nanoparticles such as BaTiO3 were also used in polymer hybrid
dielectrics. Phosphonic acid coated BaTiO3 nanoparticles were dispersed in cross-linked PVP
forming good dielectrics101. Indeed, mobility of 0.17 cm2 V-1 s-1 was reported with pentacene.
Dispersion of BaTiO3 in poly(vinyl alcohol) also lead to high mobility (0.4 cm2 V-1 s-1) with
pentacene. Al2O3 nanoparticles were also dispersed in PVP providing good results102104.
Finally, Marks et al.105 recently reported a matrix of siloxane cross-linked by ZrO2
nanoparticles. Low leakage currents (10-6 to 10-7 A cm-2) and high pentacene mobilities (up to
1.6 cm2 V-1 s-1) were achieved, even on flexible plastic substrates.
Besides nanoparticles, organic molecules were also incorporated in polymer matrixes to form
dielectric materials. For instance, bromoadamantane was introduced in a triblock copolymer
matrix, forming a dielectric with very low leakage current (5.5 x 10-11 A cm-2) with a 10 nm
thick film106. Notably, this composite material exhibited good resistance towards flexion,
keeping its properties even after strong torsion. Concomitantly, Nuckolls et al.107 reported the
incorporation of spiropyrans in a PMMA matrix. The spiropyrans were photoactive molecules
thus allowing a control on the properties of the hybrid dielectric. Indeed, switching the
spiropyrans from open to closed conformation led to a decrease of the dielectric constant from
3.67 to 2.84 also dramatically impacting the mobility of pentacene. This hybrid material can
also be used on flexible substrates to tune the properties of the dielectric layer.
Finally, polymer matrixes were also filled with ionic gels or electrolytes to form highcapacitance materials thanks to the translation of mobile ions under electric fields which
induces very high polarization. This technique was first introduced with LiClO4 and
poly(ethylene oxide) leading to fabrication of low-voltage transistors108114. However, the
speed of the device was limited by the polarization response time of the electrolyte. Frisbie et
al.115 addressed this drawback using a polymer network of PS-PEO-PS as matrix. They
reported high-capacitance material (up to 4.5 F cm-2 for a 30 nm-thick film). Finally,
incorporation of lithium imidazolium salts in a triblock PS-PEO-PS matrix gave rise to
mobilities up to 1.8 cm2 V-1 s-1 with P3HT116,117. Those hybrid dielectrics were demonstrated
to be printable without altering the mobility. The features of polymer-based hybrid dielectrics
are summarized in Table 1.
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I. State of the art

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I.1.4.2 Organic-Inorganic bilayers


Besides filling of polymer matrixes, another developed approach is to deposit two successive
layers, one from a polymer and one from an inorganic oxide to combine their properties. The
first bilayer was reported by Tardy et al.118 in 2005, consisting in a PMMA layer spin-coated
on a Ta2O5 layer. Mobility in pentacene OFET was found to be better on the bilayer than on
bulk PMMA even if its growth and ordering were identical. All the traditional metal oxide
dielectrics were combined with polymers to improve their properties. For instance, HfO2 was
combined with PVP and epoxy resin to afford large capacitance and low leakage current 119.
SiO2 and PVA yielded to better pentacene mobility120 than bare SiO2 whereas SiO2
functionalized with PMMA brushes gave high capacitance, low leakage current and high
pentacene mobility121. Furthermore, bilayer dielectrics are compatible with soft processing
and flexible substrates. Indeed, incorporation of a thin HfO2 layer between two PVP layers
leads to high mobility of pentacene, but more importantly greatly reduced leakage current
without altering the flexibility of the device122. Finally, Hong et al.123 reported a bilayer
composed of diamond-like carbon and cyclohexene. This hybrid material exhibited low
leakage current and high mobility with pentacene. Finally, the latest extension of bilayers is
the formation of a SAM on thin oxide films which was already discussed. Table 1 presents the
main features of organic-inorganic bilayers together with all the other dielectrics.
Table 1. Properties (thickness d, capacitance C, dielectric constant k and pentacene mobility
of transistors with gate dielectric ) of the different dielectrics.
Ref
124
3,5
7,8
7,8
9

10

10
11
22
125
126
38
42
127
52,53
52
54
57,56,128,129
66
130
65
66

Dielectric
SiO2
SiNx
BZT
BST
BaTiO3 nanoparticles
sol-gel
BaTiO3 nanoparticles
solution
SrTiO3 nanoparticles
Ta2O5
Al2O3
TiO2
TiO2 nanoparticles
HfO2
Gd2O3
ZrO2
SiO2+OTS SAM
SiO2+HMDS SAM
Ta2O5+HMDS SAM
HfO2+ODPA SAM
PVA
CYEPL
PMMA
PS

d (nm)
100
30
122
122

C (nF cm-2)
40.73
54.9

K
3.9
6.2
17.3
16
100

(cm2 V-1 s-1)


0.2-0.4
1
0.32
0.4-0.5

280-350

15-25

9.3

3.5

280-350
50
250
97

15.4
109-248
79.97

20
90
250
300

1040
280

7.1
23
8
41
5.3
25
7.3
25

5+2.1

580-690
10
6
5.06
23.02

3
0.45
0.2
0.15
0.2
0.28
0.1
0.12
3
3.4
0.51
1.6

560
500-700

12

7.8
18.5
3.5
2.6

0.43a
0.241

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I. State of the art


63

Polyimide
2000
20
0.2
Polyimide + SVA
9.1b
66
PVP
400-500
4.2
67
PVP + PVAc
20+1000
0.1
68
PVDF
100
119.53
8.4-13.5
68
P(VDF-TrFE)
100
88.24
10
69
Parylene
540
3.1
71
Biopolymers
117-1300
3.1-81.6
3.85-6.55
0.1-0.55c
72
Cross-linked PVP
260
3.6
3
73
CR-V
120
12.6
0.62
75
Cross-linked PS
10-20
0.85
76
OTS SAM
2.8
153
3
79,80
PhO-OTS SAM
2.5
900
2.5
1
82,131
ODPA SAM
2.1
700
0.4
86
Multilayer SAM
up to 100
17
1.3
87
SAND I
2.3
400
0.04d
87
SAND II
3.2
710
0.02d
87
SAND III
5.5
390
0.06d
132
SAND III three layers
16.5
220
196e
92
Reinforced SAND
21
180-200
136-175f
95
PVP-TiO2
700
5.4
0.2-0.4
133
TiO2-PS
500-1200
8-9.4
1.3
99
TiO2-Nylon 6
350
14
0.1-0.7
101
BaTiO3-PVP
406
31
14
0.04
102
Al2O3-PVP
290
7.2
0.25
105
ZrO2-siloxane
19-43
95-365
5-10
0.2-1.6
106
Bromoadamantane-triblock
10
0.002
1.9
107
Spiropyran-PMMA
150-1200
2.84-3.67
0.0017-0.019
116,117
Imidazolium-PS-PEO-PS
10000
20000
1.8g
134
LiClO4-PS-PEO-PS
30
4500
118
PMMA/Ta2O5
37+120
39
0.3
135
PVA/SiO2
950+350
0.12
122
PVP/HfO2/PVP
200+10+200
0.56
136
DLC/cyclohexene
200
0.84
a
Sexithienyl (6T)-based FET; b dioctylbenzothienobenzothiophene (C8-BTBT)-based FET;
c
C60-based FET; d dihexyl sexithiophene (DH-6T)-based FET; e ZnO nanowire-based FET; f
amorphous Zn-In-Sn-O (a-ZITO)-based FET; g poly(3-hexylthiophene) (P3HT)-based FET.

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64

I.2 Surface functionalization


Surface modification or functionalization can be achieved by several techniques using
different interactions between the coating and the surface. This domain has been widely
studied due to the possibility to confer to a bulk material some interesting surface properties
(protection against corrosion, biocompatibility, insulating properties, adhesion). The
stability of the coating and particularly the robustness of the link between the surface and the
coating are key parameters required. Techniques are thus classified in two groups depending
on the interactions that exist between the coating and the surface. The first one concerns all
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I. State of the art


the physisorption techniques (mostly vapor-deposition methods and Langmuir-Blodgett films
formation) and will not be discussed here as the corresponding interactions are weak, thus
being potential drawbacks for passivation and insulation applications which require high
stability and strong links between the surface and the coating. The second is composed of
chemisorption techniques providing covalent binding of the coating, thus ensuring a strong
link and often a great stability. This part will discuss the main surface functionalization
methods described to date before focusing on the functionalization of Ge, the substrate
studied in this work.

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I.2.1 SAMs
As depicted before, SAMs are highly ordered assemblies of molecules formed by specific
adsorption on surfaces137. They are mainly used to confer some properties to a surface (for
example, hydrophobicity or functionality). But they are also used as dielectric layers or to
tune the interface of bulk materials. The field attracted tremendous interest only over the last
30 years whereas SAMs were firstly reported in 1946 by Zisman with the preparation of a
self-assembled monolayer by adsorption of a surfactant on platinum138. In 1980, Sagiv
reported the formation of SAMs of chloro- and alkoxysilanes on hydroxyl-terminated surfaces
of oxidized substrates139. Silanes require the use of hydroxyl-terminated substrates allowing
their deposition on native oxides but often needing an oxidation step. Due to the amorphous
nature of the substrates, the packing and ordering of SAMs grown on oxides is tightly related
to the surface state. However, organosilanes SAMs on oxide have been widely studied
particularly on SiO2 (mostly for patterning applications)140147, Al2O3148,149, and ITO150,151 but
also on germanium oxide147. However, in the latter case, the poor quality of the oxide layer
prevents the use of organosilanes SAMs as passivating layer due to the presence of pinholes
generated from the irregular chemical composition of the oxide. Along with silanes,
carboxylic152157 and phosphonic acids158160 were also widely used to create SAMs on oxide
surfaces. Phosphonic acids solved the problem of moisture-sensitivity encountered with
silanes. Indeed, phosphonic acids SAMs exhibited high stability, comparable to stability
obtained with thiols. All these SAMs form nicely ordered layers with high stability but none
was more investigated than alkanethiolates SAMs and in particular on gold. The difference
with previous works lied in using alkanethiolates (instead of organosilanes) that allow
forming SAMs on metallic surfaces (initially reported on gold) via non moisture-sensitive
bonds whereas organosilanes where only used on oxides via sensitive Si-O-M bonds (M being
Si, Ag, Al, Ti, In, Sn). After being reported on gold by Nuzzo and Allara161, alkanethiolates
SAMs were further extended to silver162169, copper164166,170172, palladium173,174, iron175,176,
and platinum177179, but also on semiconductors like AsGa180,181, InP182185 or germanium186
189
. Moreover, precursor molecules can be thiols but also sulfides190,191 and disulfides161, and
the affinity of those various surfaces for the sulfur atom is so strong that any functional group
can be present on the molecule without interfering with the adsorption process. This
versatility allows the easy functionalization of those substrates. However, where silanes or
phosphonic acids SAMs are based on a strong chemical binding, alkanethiolates SAMs are
based on a much weaker binding and can be removed under quite harsh conditions (high
temperature, boiling solvent, strong oxidant, large oxidative or reductive potential) but remain
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I. State of the art


stable in ambient. Finally, for all the SAMs described here, the density of the packing is
strongly related to the length of the alkyl chain, the nature of the molecule and the terminal
group. The longer the alkyl chain and the more intermolecular interactions (Van der Walls, interaction) are promoted, the more ordered the SAM. Concomitantly, depending on the
interaction and the size of the terminal group, the SAM will be more or less densely packed.
SAMs are the most popular system to functionalize a surface due to the almost perfect control
they allow on the formation of the layer and their easy.

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I.2.2 Activated monolayer formations


Even if the surface monolayer functionalization field is dominated by SAMs, others methods
were also developed to confer designated properties to a surface. The two techniques we will
describe here require a special surface preparation that narrows their scope to metals,
inorganic semi-conductors and inorganic oxides. The first method consists in reacting
unsaturated bond (alkene or alkyne) with H-terminated surfaces (M-H terminal bonds). This
route, called hydrosilylation on silicon192200, leads to formation of SAM-like layers with
high-stability and a large range of compatible functionalities (Scheme 4). However, hightemperature and ultra-high vacuum are often needed to functionalize the surface making this
method not adapted for thermosensitive substrates. These drawbacks did not prevent the use
of this method particularly in the case of silicon. Indeed, layers obtained by hydrosilylation
were the most robust among all the SAMs formed on this substrate. Unfortunately, the
difficulty to prepare H-terminated surfaces on other surfaces than Si almost limits the use of
alkynes and alkenes functionalization to silicon.

Scheme 4. Functionalization with alkenes (top) and alkyne (bottom) of H-terminated surfaces.
The final popular functionalization route involves organometallic reagents such as Grignard
or organolithium reagents (Scheme 5)194,195,201,202. Reaction of these compounds with halogenterminated surfaces leads to the formation of SAM-like layers via a mechanism similar to the
transmetallation in organometallic chemistry. As Grignard and organolithium compounds are
highly reactive and incompatible with a wide range of functional groups, this method is
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I. State of the art


principally used to introduce alkyl chains on a surface to tune its surface energy. Layers
obtained by this mean are also very stable and quite compact ensuring a good coating of the
surface. However, once again, the needed halogen-terminated surface prevents a wide
utilization of this functionalization route.

Scheme 5. Functionalization with organometallic reagents of halogen-terminated surfaces

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I.2.3 Diazonium salts


Along with SAMs, use of diazonium salts is widely employed to functionalize surfaces, the
main drawback being a lower control of the film organization with respect to SAMs.
Diazonium salts have drawn attention since the covalent modification of carbon electrodes by
electroreduction of diazonium salts was first reported by Delamar203 in 1992. It was further
demonstrated that this process leads to the formation of grafted polyphenylene-like films.
Main advantages of diazonium salts are their versatility (all the available anilines can be
converted in diazonium salts) and their ease of grafting. Indeed, metals and conducting
materials can be functionalized by electrochemistry but non-conductive materials can be
functionalized via in situ chemical reduction of diazonium salts (Scheme 6). For instance,
carbon204207, gold208210, iron211213, semi-conductors and conductive oxides214,215 have been
functionalized by electrochemistry whereas plastics were functionalized via chemical
reduction216,217. The grafting through chemical reduction has been achieved with iron216,218,219,
hypophosphorous acid220225 and ascorbic acid226,227. Besides electrochemical and chemical
reduction, spontaneous grafting of diazonium salts was also reported on carbon228234,
metals228,229,234238 and semiconductors239 like AsGa240 and Si241243 (Scheme 6). That process,
although not fully understood, is of great interest for surface modification. Indeed, a simple
dipping of the samples in a solution of diazonium salt leads to the grafting of polyphenylene
films. The obtained coatings are thinner than in the case of electro- or chemically-assisted
grafting but still highly stable and robust, their stability being comparable to the one of SAMs.
However, diazonium salts derived films are less organized and homogenous than SAMs
coatings. The recent development of in situ generation of diazonium salts244,245 has expanded
the scope of attachable functionality. For instance, auto-adhesive surfaces were reported using
1,4-phenylenediamine as precursor: a first diazoniation was used to graft a
polyaminophenylene layer followed by a second diazoniation of the surface amino groups to
provide a diazonium surface that can further attach other molecules219. Even if the control of
the growth of films is less precise than with SAMs, the easy formation of diazonium salts as
well as the different methods available for their grafting makes them valuable candidates for
surface modification. They are indeed widely studied and employed even if the mechanism of
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I. State of the art

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grafting (especially for spontaneous grafting) remains under debate. Moreover, the large
variety of substrates together with the wide scope of functional groups that can be borne by
the diazonium reagents make the diazonium-based grafting a method of choice to develop
generic coatings for surface functionalization.

Scheme 6. Different grafting methodes of diazonium salts on surfaces.


With this technique, we finish our overview of general surface functionalization and will now
turn our attention on specific functionalization of germanium.
I.2.4 Ge surfaces functionalization
Due to its good electrical properties, Ge has drawn attention since the leading position of
silicon may be jeopardized due to the scaling down of devices. However, prior to their
functionalization with dielectrics, Ge surfaces must be treated to remove the poor quality
native oxide layer246. Indeed, contrary to silicon, the Ge/GeOx interface is very defective, thus
preventing good charge transport, but, moreover, the oxide layer is neither insulating nor
protective against oxidation. Last but not least, Ge is very sensitive towards reoxidation 186,247
250
, thus, freshly prepared Ge surfaces must be immediately functionalized before subsequent
dielectric deposition. In this part, we will discuss the functionalization aspects on Ge surfaces,
giving the state of the art regarding this substrate at the beginning of this work.
This step can be done by different manners and could be compatible with direct deposition of
the dielectric layer if the dielectric material combines insulating and passivating properties. In
1962, Cullen reported the first organic functionalization of Ge surfaces251. For this purpose,
he used a Grignard reagent to introduce ethyl groups on Cl-terminated surfaces. The
functionalization occurred by simple dipping of Ge surfaces in the Grignard reagent solution.
The main shortcomings are the low versatility of Grignard reagents towards organic
29

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I. State of the art


functionalities (incompatibility with carbonyl groups, amines, alcohols, thiols) that prevents
their use with most of push-pull systems or post-functionalizable groups. Functionalization of
Ge via Grignard reagents was further improved by He et al.252 leading to densely packed
monolayers. Recently, Lewis et al.253 demonstrated the quality, the stability, and the electrical
properties of alkyl monolayers obtained with alkylmagnesium and alkyllithium. For instance,
their electrical properties depicted a good insulating behavior, sign of a densely packed
organization of the alkyl layer. Nanowires were also modified by Grignard reagents showing
incomplete functionalization of the surface but good stability254. However, to improve the
versatility of the coating method, alternative ways were developed. Thus, in 2000, Buriak and
Choi reported the counterpart of hydrosilylation on germanium255. This functionalization
method, called hydrogermylation, involves H-terminated Ge surfaces which are achieved with
HF treatment followed by alkenes or alkynes reaction. Hydrogermylation can be promoted by
different activations: UV photoinduction194, thermal induction253,256 and Lewis acid
mediation255. All these techniques require an inert atmosphere and reaction times from 1 h up
to 12 h. Furthermore, their versatility is still limited due to the conditions of reaction. For
instance, EtAlCl2 used as Lewis acid will react with amines or alcohols whereas thermal
induction proceeds at temperatures above 200 C. Surfaces modified through
hydrogermylation showed great stability compared to H- or halogen-terminated surfaces, the
more stable functionalization being obtained with the thermal route. Furthermore, the organic
layer exhibited great passivating properties as surface oxidation in air or water was found
negligible. Concomitantly, Maboudian et al.189 reported the formation of SAMs of
alkanethiolates on H-terminated Ge surfaces. Since SAM formation was known to provide
densely packed passivating organic layers, they adapted the method widely used with silicon
to germanium. However, the process of growth was found to be much slower as SAM
formation on Ge surfaces often requires few days to obtain a perfect coating. Moreover, the
latter two techniques depicted here are based on the least stable prepared Ge surfaces, the Hterminated ones obtained by HF treatment. Therefore, effort was put on the functionalization
of halogen-terminated surfaces via a versatile process. This quest led to the formation of
alkanethiolates SAMs on halogen-terminated surfaces reported by Bent et al.187,188 in 2009.
Dense layers were obtained by this process and exhibited high stability against corrosion or
heating, leaving this process with only one important shortcoming: the reaction time. Indeed,
three days were needed to obtain high quality SAMs on Ge surfaces. However, this process
being the most versatile was fully studied and applied to nanowires. Very recently, Weiss et
al.257 even published a process combining the removal of oxide and the growth of the SAM of
thiol in a water/ethanol mixture. This process leads to robust SAMs within one day without
degradation of the excellent properties of the organic layer obtained through traditional
pathway. Finally, whereas SAM formation was reported to proceed only on one site of the
dimer (dimers at the surface arose from 2x1 reconstruction on Ge(100) surfaces), they also
observed that soft heating (60 C) during SAM formation enabled the functionalization of
both sites, giving a even more densely packed layer. Finally, Holmes et al.258 addressed the
versatility and the long grafting times on Ge nanowires by using diazonium salts. Hterminated nanowires were thus functionalized with three different salts leading to different
morphologies in terms of thickness (from mono- to multilayers) and uniformity of the grafting
regarding the nature of the substituents. In the present work, both alkanethiolates SAMs
30

I. State of the art


deposition and diazonium salt grafting were used to covalently bind push-pull and --
systems in view to form a passivating and insulating dielectric layer on Ge surfaces.
In this chapter, we have presented the two main motivations of the present work: realization
of dielectrics based on push-pull systems and functionalization of germanium to passivate and
insulate it. Both will be now detailed starting with the synthesis of push-pull systems before
dealing with germanium surfaces modification (in particular through diazonium salt
chemistry) and ending with grafting and evaluation of our push-pull systems on gold and
germanium. Before going in the core of the results, we will finish this chapter by presenting
the aims of the subject and the strategy employed to achieve the different goals of this work.

tel-00782709, version 1 - 30 Jan 2013

I.3 - Position of the subject


The aim of this work is to achieve the protection and the insulation of germanium. Indeed,
due to its high sensitivity, germanium must be passivated before use. Concomitantly, it must
also be insulated if applications in electronics are sought. As germanium oxides are not stable
and not insulating, a dielectric protective material must be deposited on Ge. The dielectric
layer will be formed from molecular thin films of highly hyperpolarizable molecules.
Furthermore, the huge amount of defects at the Ge/GeOx interface makes it more suitable to
remove oxides before dielectric deposition. Therefore, in a first time, oxides will be etched to
obtain Ge smooth surfaces. Afterwards, these surfaces will be functionalized with the
dielectric molecules before cross-linking to achieve an efficient passivation together with the
insulating properties. The global strategy is illustrated on Scheme 7.

Scheme 7. Strategy for the passivation and the insulation of germanium


Thus, two different working axes were followed: the etching and functionalization of Ge
surfaces and the realization of a dielectric layer with highly hyperpolarizable molecules. As
stated before, Marks and Facchetti developed a new type of dielectrics called SANDs. The
main parameter for a molecular layer-based dielectric is the orientation of the dipoles with
respect to the surface. Ideally, all the dipoles should be oriented the same way to participate
favorably to the dielectric properties (Scheme 8). However, if the molecules are not tightly
bound or not restrained, a reorientation of the dipoles under polarization remains possible and
would degrade the dielectric properties. In the case of SANDs, the molecules are not strongly
bound to the surface but reorientation is prevented by cross-linking of the layer (Scheme 8).
Furthermore, Marks and Facchetti found that one single layer of molecules was not enough to
achieve good dielectrics, thus leading them to multi-layering. Finally, they built the dielectric
layer step by step beginning with molecules deposition, followed by cross-linking, then
31

I. State of the art

tel-00782709, version 1 - 30 Jan 2013

deposition again, cross-linking, and so on until the complete device was obtained.
Concomitantly, functionalization of germanium was achieved via alkanethiolates SAM
formation or hydrogermylation. Both of these technics lead to monolayer formation and might
be not suitable to grow the dielectric if multi-layering is required. However, the strong link
between the substrate and the molecule might prevent dipole reorganization under
polarization and thus could allow avoiding the cross-linking step.
In this context, we chose two different approaches for the coating formation: monolayers
through alkanethiolates SAM and multilayers via diazonium salts grafting. The first way is
convenient to study the orientation of the dipoles with respect to the surface but also the
functionalization of germanium by -- systems and push-pull molecules. Moreover, the
strong link between Ge and thiols could ensure a high stability and prevent the dipoles
reorientation under polarization (Scheme 8). However, as in the case of SANDs, monolayers
might be insufficient to provide a good dielectric. Diazonium salts grafting could solve this
drawback by leading to multilayers with controlled dipoles orientation. This route leading to
insulating films of about 8 nm thickness has never been studied as a way to form a dielectric
layer and could be employed to deposit few layers of molecules at the same time thus
realizing a multilayer with a high remaining bulk polarization in one unique step. Push-pull
and -- systems could be grafted by this method, either electrochemically or chemically.
Once again, the strong binding of the molecules to the substrate should prevent the
reorientation under polarization (Scheme 8), thus providing good dielectric properties.

Scheme 8. Influence of the dipoles orientation on the bulk polarization in the different
strategies envisaged to form the dielectric layer from high hyperpolarizable molecules. The

32

I. State of the art


molecules are represented by their dipolar moment (one arrow = one molecule with i as
dipolar moment).

tel-00782709, version 1 - 30 Jan 2013

Thus, by incorporation of a suitable head-group for Ge functionalization (either a thiol or a


diazonium salt) on a push-pull system, dielectric layers can be realized and characterized. To
sum up, in a first step, model -- molecules will be synthesized and grafted through SAM
formation and diazonium salts to study their organization on the surface and the properties of
the obtained layers. Afterwards, push-pull systems will be designed, synthesized and grafted
and the dielectric properties of the layer will be studied.

33

I. State of the art

tel-00782709, version 1 - 30 Jan 2013

References
(1)

Kingon, A.; Maria, J.; Streiffer, S. Nature 2000, 406, 1032-1038.

(2)

Packan, P. A. Science 1999, 285, 2079-2081.

(3)

Li, F. M.; Dhagat, P.; Haverinen, H. M.; McCulloch, I.; Heeney, M.; Jabbour, G. E.;
Nathan, A. Appl. Phys. Lett. 2008, 93, 073305.

(4)

Li, F. M.; Nathan, A.; Wu, Y.; Ong, B. S. Appl. Phys. Lett. 2007, 90, 133514.

(5)

Tan, H. S.; Cahyadi, T.; Wang, Z. B.; Lohani, A.; Tsakadze, Z.; Zhang, S.; Zhu, F. R.;
Mhaisalkar, S. G. IEEE Electr. Device L. 2008, 29, 698-700.

(6)

Tan, H. S.; Mathews, N.; Cahyadi, T.; Zhu, F. R.; Mhaisalkar, S. G. Appl. Phys. Lett.
2009, 94, 263303.

(7)

Dimitrakopoulos, C. D. Science 1999, 283, 822-824.

(8)

Dimitrakopoulos, C. D.; Kymissis, I.; Purushothaman, S.; Neumayer, D. A.;


Duncombe, P. R.; Laibowitz, R. B. Adv. Mater. 1999, 11, 1372-1375.

(9)

Lehnert, T.; Herbeck-Engel, P.; Adam, J.; Klein, G.; Kololuoma, T.; Veith, M. Adv.
Eng. Mater. 2010, 12, 379-384.

(10)

Cai, Q. J.; Gan, Y.; Chan-Park, M. B.; Yang, H. B.; Lu, Z. S.; Li, C. M.; Guo, J.; Dong,
Z. L. Chem. Mater. 2009, 21, 3153-3161.

(11)

Tate, J.; Rogers, J. A.; Jones, C. D. W.; Vyas, B.; Murphy, D. W.; Li, W.; Bao, Z.;
Slusher, R. E.; Dodabalapur, A.; Katz, H. E. Langmuir 2000, 16, 6054-6060.

(12)

Bartic, C.; Jansen, H.; Campitelli, A.; Borghs, S. Org. Electron. 2002, 3, 65-72.

(13)

Iino, Y.; Inoue, Y.; Fujisaki, Y.; Fujikake, H.; Sato, H.; Kawakita, M.; Tokito, S.;
Kikuchi, H. Jpn. J. App. Phys. 2003, 42, 299-304.

(14)

Yuan, J.; Zhang, J.; Wang, J.; Yan, X.; Yan, D.; Xu, W. Appl. Phys. Lett. 2003, 82,
3967-3969.

(15)

Inoue, Y.; Tokito, S.; Ito, K.; Suzuki, T. J. Appl. Phys. 2004, 95, 5795-5799.

(16)

Mizutani, F.; Takeuchi, S.; Takaha, H.; Ue, M.; Sugiyama, K.; Nishiwaki, T.; Yoshida,
Y.; Sato, N. J. Electrochem. Soc. 2001, 148, B419.

(17)

Fujisaki, Y.; Inoue, Y.; Kurita, T.; Tokito, S.; Fujikake, H.; Kikuchi, H. Jpn. J. App.
Phys. 2004, 43, 372-377.

(18)

Ha, W. H.; Choo, M. H.; Im, S. J. Non-Cryst. Solids 2002, 303, 78-82.

(19)

Majewski, L. A.; Schroeder, R.; Grell, M. J. Phys. D: Appl. Phys. 2004, 37, 21-24.
34

tel-00782709, version 1 - 30 Jan 2013

I. State of the art


(20)

Majewski, L. A.; Grell, M.; Ogier, S. D.; Veres, J. Org. Electron. 2003, 4, 27-32.

(21)

Richter, S.; Ploetner, M.; Fischer, W.-J.; Schneider, M.; Nguyen, P.-T.; Plieth, W.;
Kiriy, N.; Adler, H.-J. P. Thin Solid Films 2005, 477, 140-147.

(22)

Lee, J.; Kim, J. H.; Im, S. J. Appl. Phys. 2004, 95, 3733-3736.

(23)

Koo, J. B.; Ku, C. H.; Lim, S. C.; Kim, S. H.; Lee, J. H. Appl. Phys. Lett. 2007, 90,
133503.

(24)

Lim, J. W.; Koo, J. B.; Yun, S. J.; Kim, H.-T. Electrochem. Solid-State Lett. 2007, 10,
J136.

(25)

Kim, K. D.; Kim, D. S.; Kim, C. K.; Song, C. K. Jpn. J. App. Phys. 2008, 47, 64966501.

(26)

Jamil, M.; Oh, J.; Ramon, M.; Kaur, S.; Majhi, P.; Tutuc, E.; Banerjee, S. K. IEEE
Electr. Device L. 2010, 31, 1208-1210.

(27)

Zhang, R.; Iwasaki, T.; Taoka, N.; Takenaka, M. IEEE Trans. Electron Devices 2012,
59, 335-341.

(28)

Wang, G.; Moses, D.; Heeger, A. J.; Zhang, H.-M.; Narasimhan, M.; Demaray, R. E. J.
Appl. Phys. 2004, 95, 316-322.

(29)

Ramajothi, J.; Ochiai, S.; Kojima, K.; Mizutani, T. Jpn. J. App. Phys. 2008, 47, 82798283.

(30)

Kim, S. K.; Kim, W.-D.; Kim, K.-M.; Hwang, C. S.; Jeong, J. Appl. Phys. Lett. 2004,
85, 41124114.

(31)

Osada, M.; Ebina, Y.; Funakubo, H.; Yokoyama, S.; Kiguchi, T.; Takada, K.; Sasaki,
T. Adv. Mater. 2006, 18, 1023-1027.

(32)

Khan, M. Z. R.; Hasko, D. G.; Saifullah, M. S. M.; Welland, M. E. J. Vac. Sci. Tech. B
2008, 26, 1887-1891.

(33)

Cai, Q. J.; Gan, Y.; Chan-Park, M. B.; Yang, H. B.; Lu, Z. S.; Song, Q. L.; Li, C. M.;
Dong, Z. L. Appl. Phys. Lett. 2008, 93, 113304.

(34)

Beckx, S.; Demand, M.; Locorotondo, S.; Henson, K.; Claes, M.; Paraschiv, V.;
Shamiryan, D.; Jaenen, P.; Boullart, W.; Degendt, S.; Biesemans, S.; Vanhaelemeersch,
S.; Vertommen, J.; Coenegrachts, B. Microelectron. Reliab. 2005, 45, 1007-1011.

(35)

Gusev, E. P.; Cabral, C.; Copel, M.; DEmic, C.; Gribelyuk, M. Microelectron. Eng.
2003, 69, 145-151.

(36)

Tardy, J.; Erouel, M.; Deman, A. L.; Gagnaire, A.; Teodorescu, V.; Blanchin, M. G.;
Canut, B.; Barau, A.; Zaharescu, M. Microelectron. Reliab. 2007, 47, 372-377.

35

tel-00782709, version 1 - 30 Jan 2013

I. State of the art


(37)

Deman, A.-L.; Erouel, M.; Lallemand, D.; Phaner-Goutorbe, M.; Lang, P.; Tardy, J. J.
Non-Cryst. Solids 2008, 354, 1598-1607.

(38)

Seo, J. W.; Dieker, C.; Locquet, J.-P.; Mavrou, G.; Dimoulas, A. Appl. Phys. Lett.
2005, 87, 221906.

(39)

Liao, M.; Ishiwara, H.; Ohmi, S. IEEE Electr. Device L. 2011, 32, 1600-1602.

(40)

Tsai, L. S.; Wang, C. H.; Chen, W. Y.; Wang, W. C.; Hwang, J. Org. Electron. 2010,
11, 123-126.

(41)

Johnson, J. W.; Luo, B.; Ren, F.; Gila, B. P.; Krishnamoorthy, W.; Abernathy, C. R.;
Pearton, S. J.; Chyi, J. I.; Nee, T. E.; Lee, C. M.; Chuo, C. C. Appl. Phys. Lett. 2000,
77, 3230-3232.

(42)

Kang, S. J.; Chung, K. B.; Park, D. S.; Kim, H. J.; Choi, Y. K.; Jang, M. H.; Noh, M.;
Whang, C. N. Synth. Met. 2004, 146, 351-354.

(43)

Javey, A.; Kim, H.; Brink, M.; Wang, Q.; Ural, A.; Guo, J.; McIntyre, P.; McEuen, P.;
Lundstrom, M.; Dai, H. Nat. Mater. 2002, 1, 241-246.

(44)

Javey, A.; Qi, P.; Wang, Q.; Dai, H. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 1340813410.

(45)

Nishikawa, Y.; Yamaguchi, T.; Yoshiki, M.; Satake, H.; Fukushima, N. Appl. Phys.
Lett. 2002, 81, 4386-4388.

(46)

Wang, J. C.; Hung, Y. P.; Lee, C. L.; Lei, T. F. J. Electrochem. Soc. 2004, 151, F17.

(47)

Kim, C. S.; Jo, S. J.; Lee, S. W.; Kim, W. J.; Baik, H. K.; Lee, S. J. Adv. Funct. Mater.
2007, 17, 958-962.

(48)

Kim, C. S.; Jo, S. J.; Lee, S. W.; Kim, W. J.; Baik, H. K.; Lee, S. J.; Hwang, D. K.; Im,
S. Appl. Phys. Lett. 2006, 88, 243515.

(49)

Kim, C. S.; Jo, S. J.; Lee, S. W.; Kim, W. J.; Baik, H. K.; Lee, S. J.; Hwang, D. K.; Im,
S. Semicond. Sci. Technol. 2006, 21, 1022-1025.

(50)

Chua, L. L.; Zaumseil, J.; Chang, J. F.; Ou, E. C. W.; Ho, P. K. H.; Sirringhaus, H.;
Friend, R. H. Nature 2005, 434, 194-199.

(51)

Chabinyc, M. L.; Lujan, R.; Endicott, F.; Toney, M. F.; McCulloch, I.; Heeney, M.
Appl. Phys. Lett. 2007, 90, 233508.

(52)

Islam, M. M.; Pola, S.; Tao, Y.-T. ACS App. Mater. Interfaces 2011, 3, 2136-2141.

(53)

Ito, Y.; Virkar, A. A.; Mannsfeld, S.; Oh, J. H.; Toney, M.; Locklin, J.; Bao, Z. J. Am.
Chem. Soc. 2009, 131, 9396-9404.

(54)

Jeong, Y. T.; Dodabalapur, A. Appl. Phys. Lett. 2007, 91, 193509.


36

tel-00782709, version 1 - 30 Jan 2013

I. State of the art


(55)

Ohta, S.; Chuman, T.; Miyaguchi, S.; Satoh, H.; Tanabe, T.; Okuda, Y.; Tsuchida, M.
Jpn. J. App. Phys. 2005, 44, 3678-3681.

(56)

Acton, O.; Ting, G.; Ma, H.; Ka, J. W.; Yip, H. L.; Tucker, N. M.; Jen, A. K. Y. Adv.
Mater. 2008, 20, 3697-3701.

(57)

Acton, O.; Acton, B. O.; Ting, G. G.; Shamberger, P. J.; Ohuchi, F. S.; Ma, H.; Jen, A.
K.-Y. ACS App. Mater. Interfaces 2010, 2, 511-520.

(58)

Acton, O.; Osaka, I.; Ting, G.; Hutchins, D.; Ma, H.; McCullough, R. D.; Jen, A. K.-Y.
Appl. Phys. Lett. 2009, 95, 113305.

(59)

Acton, O.; Ting, G.; Ma, H.; Jen, A. K.-Y. Appl. Phys. Lett. 2008, 93, 083302.

(60)

Kelley, T. W.; Boardman, L. D.; Dunbar, T. D.; Muyres, D. V.; Pellerite, M. J.; Smith,
T. P. J. Phys. Chem. B 2003, 107, 5877-5881.

(61)

Peng, X.; Horowitz, G.; Fichou, D.; Garnier, F. Appl. Phys. Lett. 1990, 57, 2013-2015.

(62)

Bao, Z.; Feng, Y.; Dodabalapur, A.; Raju, V. R.; Lovinger, A. J. Chem. Mater. 1997, 9,
1299-1301.

(63)

Pyo, S.; Son, H.; Choi, K.-Y.; Yi, M. H.; Hong, S. K. Appl. Phys. Lett. 2005, 86,
133508.

(64)

Liu, C.; Minari, T.; Lu, X.; Kumatani, A.; Takimiya, K.; Tsukagoshi, K. Adv. Mater.
2011, 23, 523-526.

(65)

Huang, T.-S.; Su, Y.-K.; Wang, P.-C. Appl. Phys. Lett. 2007, 91, 092116.

(66)

Chang, J. W.; Hsu, W. L.; Wu, C. Y.; Guo, T. F.; Wen, T. C. Org. Electron. 2010, 11,
1613-1619.

(67)

Park, S. Y.; Park, M.; Lee, H. H. Appl. Phys. Lett. 2004, 85, 2283-2285.

(68)

Tien, N. T.; Seol, Y. G.; Dao, L. H. A.; Noh, H. Y.; Lee, N. E. Adv. Mater. 2009, 21,
910-915.

(69)

Jakabovic, J.; Kovac, J.; Weis, M.; Hasko, D.; Srnanek, R.; Valent, P.; Resel, R.; Kova,
J.; Srna, R. Microelectron. J. 2009, 40, 595-597.

(70)

Irimia-Vladu, M.; Troshin, P. A.; Reisinger, M.; Schwabegger, G.; Ullah, M.;
Schwoediauer, R.; Mumyatov, A.; Bodea, M.; Fergus, J. W.; Razumov, V. F.; Sitter,
H.; Bauer, S.; Sariciftci, N. S. Org. Electron. 2010, 11, 1974-1990.

(71)

Irimia-Vladu, M.; Troshin, P. A.; Reisinger, M.; Shmygleva, L.; Kanbur, Y.;
Schwabegger, G.; Bodea, M.; Schwodiauer, R.; Mumyatov, A.; Fergus, J. W.;
Razumov, V. F.; Sitter, H.; Sariciftci, N. S.; Bauer, S. Adv. Funct. Mater. 2010, 20,
4069-4076.

37

tel-00782709, version 1 - 30 Jan 2013

I. State of the art


(72)

Klauk, H.; Halik, M.; Zschieschang, U.; Schmid, G.; Radlik, W.; Weber, W. J. Appl.
Phys. 2002, 92, 5259-5263.

(73)

Kim, S. H.; Yang, S. Y.; Shin, K.; Jeon, H.; Lee, J. W.; Hong, K. P.; Park, C. E. Appl.
Phys. Lett. 2006, 89, 183516.

(74)

Yoon, M.-H.; Yan, H.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2005, 127, 1038810395.

(75)

Kim, C.; Wang, Z.; Choi, H.-J.; Ha, Y.-G.; Facchetti, A.; Marks, T. J. J. Am. Chem.
Soc. 2008, 130, 6867-6878.

(76)

Vuillaume, D.; Boulas, C.; Collet, J.; Davidovits, J. V.; Rondelez, F. Appl. Phys. Lett.
1996, 69, 1646-1648.

(77)

Collet, J.; Tharaud, O.; Chapoton, A.; Vuillaume, D. Appl. Phys. Lett. 2000, 76, 19411943.

(78)

Collet, J.; Vuillaume, D. Appl. Phys. Lett. 1998, 73, 2681-2683.

(79)

Halik, M.; Klauk, H.; Zschieschang, U.; Schmid, G.; Dehm, C.; Schutz, M.; Maisch,
S.; Effenberger, F.; Brunnbauer, M.; Stellacci, F. Nature 2004, 431, 963-966.

(80)

Weitz, R. T.; Zschieschang, U.; Effenberger, F.; Klauk, H.; Burghard, M.; Kern, K.
Nano Lett. 2006, 7, 22-27.

(81)

Wobkenberg, P. H.; Ball, J.; Kooistra, F. B.; Hummelen, J. C.; de Leeuw, D. M.;
Bradley, D. D. C.; Anthopoulos, T. D. Appl. Phys. Lett. 2008, 93, 013303.

(82)

Zschieschang, U.; Halik, M.; Klauk, H. Langmuir 2008, 24, 1665-1669.

(83)

Robert, G.; Derycke, V.; Goffman, M. F.; Lenfant, S.; Vuillaume, D.; Bourgoin, J.-P.
Appl. Phys. Lett. 2008, 93, 143117.

(84)

Burkhardt, M.; Jedaa, A.; Novak, M.; Ebel, A.; Voitchovsky, K.; Stellacci, F.; Hirsch,
A.; Halik, M. Adv. Mater. 2010, 22, 2525-2528.

(85)

Shukla, D.; Nelson, S. F.; Freeman, D. C.; Rajeswaran, M.; Ahearn, W. G.; Meyer, D.
M.; Carey, J. T. Chem. Mater. 2008, 20, 7486-7491.

(86)

Lee, B. H.; Ryu, M. K.; Choi, S.-Y.; Lee, K.-H.; Im, S.; Sung, M. M. J. Am. Chem.
Soc. 2007, 129, 16034-16041.

(87)

Yoon, M.-H.; Facchetti, A.; Marks, T. J. PNAS 2005, 102, 4678-4682.

(88)

DiBenedetto, S. A.; Frattarelli, D. L.; Facchetti, A.; Ratner, M. A.; Marks, T. J. J. Am.
Chem. Soc. 2009, 131, 11080-11090.

(89)

DiBenedetto, S. A.; Paci, I.; Facchetti, A.; Marks, T. J.; Ratner, M. A. J. Phys. Chem. B
2006, 110, 22394-22399.
38

tel-00782709, version 1 - 30 Jan 2013

I. State of the art


(90)

Byrne, P. D.; Facchetti, A.; Marks, T. J. Adv. Mater. 2008, 20, 2319-2324.

(91)

Ju, S. H.; Lee, K.; Janes, D. B. Nano Lett. 2005, 5, 2281-2286.

(92)

Liu, J.; Hennek, J. W.; Buchholz, D. B.; Ha, Y. G.; Xie, S. J.; Dravid, V. P.; Chang, R.
P. H.; Facchetti, A.; Marks, T. J. Adv. Mater. 2011, 23, 992-997.

(93)

Liu, J.; Buchholz, D. B.; Chang, R. P. H.; Facchetti, A.; Marks, T. J. Adv. Mater. 2010,
22, 2333-2337.

(94)

Khastgir, D.; Maiti, H. .; Bandyopadhyay, P. Mater. Sci. Engin. 1988, 100, 245-253.

(95)

Chen, F.-C.; Chu, C.-W.; He, J.; Yang, Y.; Lin, J.-L. Appl. Phys. Lett. 2004, 85, 32953297.

(96)

Maliakal, A.; Katz, H.; Cotts, P. M.; Subramoney, S.; Mirau, P. J. Am. Chem. Soc.
2005, 127, 14655-62.

(97)

Guo, N.; DiBenedetto, S. A.; Kwon, D.-K.; Wang, L.; Russell, M. T.; Lanagan, M. T.;
Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 766-767.

(98)

Lee, K.-H.; Park, B. J.; Choi, H. J.; Park, J.; Choi, J. S. Mol. Cryst. Liq. Cryst. 2007,
471, 173-179.

(99)

Kim, C.-H.; Bae, J.-H.; Lee, S.-D.; Choi, J. S. Mol. Cryst. Liq. Cryst. 2007, 471, 147154.

(100) Lee, W.-H.; Wang, C.-chieh; Chen, W.-ting; Ho, J.-C. Jpn. J. App. Phys. 2008, 47,
8955-8960.
(101) Kim, P.; Zhang, X. H.; Domercq, B.; Jones, S. C.; Hotchkiss, P. J.; Marder, S. R.;
Kippelen, B.; Perry, J. W. Appl. Phys. Lett. 2008, 93, 013302.
(102) Noh, H. Y.; Seol, Y. G.; Kim, S. I.; Leez, N. E. Electrochem. Solid State Lett. 2008, 11,
H218-H221.
(103) Huang, X.; Kim, C.; Jiang, P.; Yin, Y.; Li, Z. J. Appl. Phys. 2009, 105, 014105.
(104) Huang, X. Y.; Jiang, P. K.; Kim, C. U. J. Appl. Phys. 2007, 102, 124103.
(105) Ha, Y.-G.; Jeong, S.; Wu, J.; Kim, M.-G.; Dravid, V. P.; Facchetti, A.; Marks, T. J. J.
Am. Chem. Soc. 2010, 132, 17426-17434.
(106) Tiwari, J. N.; Meena, J. S.; Wu, C. S.; Tiwari, R. N.; Chu, M. C.; Chang, F. C.; Ko, F.
H. Chemsuschem 2010, 3, 1051-1056.
(107) Shen, Q. A.; Wang, L. J.; Liu, S.; Cao, Y.; Gan, L.; Guo, X. F.; Steigerwald, M. L.;
Shuai, Z. G.; Liu, Z. F.; Nuckolls, C. Adv. Mater. 2010, 22, 3282-3287.
(108) Panzer, M. J.; Frisbie, C. D. Adv. Funct. Mater. 2006, 16, 1051-1056.
39

I. State of the art


(109) Dhoot, A. S.; Yuen, J. D.; Heeney, M.; McCulloch, I.; Moses, D.; Heeger, A. J. Proc.
Natl. Acad. Sci. U. S. A. 2006, 103, 11834-11837.
(110) Panzer, M. J.; Newman, C. R.; Frisbie, C. D. Appl. Phys. Lett. 2005, 86, 103503.
(111) Panzer, M. J.; Frisbie, C. D. J. Am. Chem. Soc. 2005, 127, 6960-6961.
(112) Panzer, M. J.; Frisbie, C. D. Appl. Phys. Lett. 2006, 88, 203504.
(113) Shimotani, H.; Asanuma, H.; Takeya, J.; Iwasa, Y. Appl. Phys. Lett. 2006, 89, 203501.
(114) Takeya, J.; Yamada, K.; Hara, K.; Shigeto, K.; Tsukagoshi, K.; Ikehata, S.; Aoyagi, Y.
Appl. Phys. Lett. 2006, 88, 112102.

tel-00782709, version 1 - 30 Jan 2013

(115) Chen, J.; Frisbie, C. D.; Bates, F. S. J. Phys. Chem. C 2009, 113, 3903-3908.
(116) Cho, J. H.; Lee, J.; He, Y.; Kim, B.; Lodge, T. P.; Frisbie, C. D. Adv. Mater. 2008, 20,
686-690.
(117) Cho, J. H.; Lee, J.; Xia, Y.; Kim, B.; He, Y. Y.; Renn, M. J.; Lodge, T. P.; Frisbie, C.
D. Nat. Mater. 2008, 7, 900-906.
(118) Deman, A.-L.; Tardy, J. Org. Electron. 2005, 6, 78-84.
(119) Cao, Q.; Xia, M.-G.; Shim, M.; Rogers, J. A. Adv. Funct. Mater. 2006, 16, 2355-2362.
(120) Park, D.-W.; Lee, C. A.; Jung, K.-D.; Park, B.-G.; Shin, H.; Lee, J. D. Appl. Phys. Lett.
2006, 89, 263507.
(121) Li, L. Q.; Hu, W. P.; Chi, L. F.; Fuchs, H. J. Phys. Chem. B 2010, 114, 5315-5319.
(122) Seol, Y. G.; Noh, H. Y.; Lee, S. S.; Ahn, J. H.; Lee, N.-E. Appl. Phys. Lett. 2008, 93,
013305.
(123) Park, Y. S.; Cho, S.-J.; Boo, J.-H.; Hong, B. Appl. Surf. Sci. 2009, 256, 1023-1027.
(124) Tsumura, A.; Koezuka, H.; Ando, T. Appl. Phys. Lett. 1986, 49, 1210-1212.
(125) Majewski, L. A.; Schroeder, R.; Grell, M. Adv. Funct. Mater. 2005, 15, 1017-1022.
(126) Cai, Q. J.; Gan, Y.; Chan-Park, M. B.; Yang, H. B.; Lu, Z. S.; Song, Q. L.; Li, C. M.;
Li Dong, Z. Appl. Phys. Lett. 2008, 93, 113304.
(127) Kim, J.-M.; Lee, J.-W.; Kim, J.-K.; Ju, B.-K.; Kim, J.-S.; Lee, Y.-H.; Oh, M.-H. Appl.
Phys. Lett. 2004, 85, 6368-6370.
(128) Acton, O.; Ting, G.; Ma, H.; Jen, A. K. Y. Appl. Phys. Lett. 2008, 93, 083302.
(129) Acton, O.; Osaka, I.; Ting, G.; Hutchins, D.; Ma, H.; McCullough, R. D.; Jen, A. K. Y.
Appl. Phys. Lett. 2009, 95, 3231445.
40

I. State of the art


(130) Garnier, F.; Horowitz, G.; Peng, X.; Fichou, D. Adv. Mater. 1990, 2, 592-594.
(131) Wobkenberg, P. H.; Ball, J.; Kooistra, F. B.; Hummelen, J. C.; de Leeuw, D. M.;
Bradley, D. D. C.; Anthopoulos, T. D. Appl. Phys. Lett. 2008, 93, 013303.
(132) Wang, L.; Yoon, M. H.; Lu, G.; Yang, Y.; Facchetti, A.; Marks, T. J. Nat. Mater. 2006,
5, 893-900.
(133) Jung, C.; Maliakal, A.; Sidorenko, A.; Siegrist, T. Appl. Phys. Lett. 2007, 90, 062111.
(134) Chen, J.; Frisbie, C. D.; Bates, F. S. J. Phys. Chem. C 2009, 113, 3903-3908.
(135) Kim, C.; Facchetti, A.; Marks, T. J. Adv. Mater. 2007, 19, 2561-2566.
(136) Park, Y. S.; Cho, S. J.; Boo, J. H.; Hong, B. Appl. Surf. Sci. 2009, 256, 1023-1027.

tel-00782709, version 1 - 30 Jan 2013

(137) Ulman, A. Chem. Rev. 1996, 96, 1533-1554.


(138) Bigelow, W. C.; Pickett, D. L.; Zisman, W. A. J. Colloid Sci. 1946, 1, 513-538.
(139) Sagiv, J. J. Am. Chem. Soc. 1980, 102, 92-98.
(140) Haensch, C.; Ott, C.; Hoeppener, S.; Schubert, U. S. Langmuir 2008, 24, 10222-10227.
(141) Liu, S.; Maoz, R.; Schmid, G.; Sagiv, J. Nano Lett. 2002, 2, 1055-1060.
(142) Maoz, R.; Cohen, S. R.; Sagiv, J. Adv. Mater. 1999, 11, 55-61.
(143) Silberzan, P.; Leger, L.; Ausserre, D.; Benattar, J. J. Langmuir 1991, 7, 1647-1651.
(144) Wasserman, S. R.; Tao, Y. T.; Whitesides, G. M. Langmuir 1989, 5, 1074-1087.
(145) Le Grange, J. D.; Markham, J. L.; Kurkjian, C. R. Langmuir 1993, 9, 1749-1753.
(146) Maoz, R.; Sagiv, J. J. Colloid Interface Sci. 1984, 100, 465-496.
(147) Gun, J.; Sagiv, J. J. Colloid Interface Sci. 1986, 112, 457-472.
(148) Gun, J.; Iscovici, R.; Sagiv, J. J. Colloid Interface Sci. 1984, 101, 201-213.
(149) Tillman, N.; Ulman, A.; Schildkraut, J. S.; Penner, T. L. J. Am. Chem. Soc. 1988, 110,
6136-6144.
(150) Cui, J.; Huang, Q.; Veinot, J. C. G.; Yan, H.; Wang, Q.; Hutchison, G. R.; Richter, A.
G.; Evmenenko, G.; Dutta, P.; Marks, T. J. Langmuir 2002, 18, 9958-9970.
(151) Li, J.; Wang, L.; Liu, J.; Evmenenko, G.; Dutta, P.; Marks, T. J. Langmuir 2008, 24,
5755-5765.
(152) Allara, D. L.; Nuzzo, R. G. Langmuir 1985, 1, 45-52.
41

I. State of the art


(153) Allara, D. L.; Nuzzo, R. G. Langmuir 1985, 1, 52-66.
(154) Ogawa, H.; Chihara, T.; Taya, K. J. Am. Chem. Soc. 1985, 107, 1365-1369.
(155) Schlotter, N. E.; Porter, M. D.; Bright, T. B.; Allara, D. L. Chem. Phys. Lett. 1986, 132,
93-98.
(156) Shnidman, Y.; Ulman, A.; Eilers, J. E. Langmuir 1993, 9, 1071-1081.
(157) Laibinis, P. E.; Hickman, J. J.; Wrighton, M. S.; Whitesides, G. M. Science 1989, 245,
845-847.
(158) Spori, D. M.; Venkataraman, N. V.; Tosatti, S. G. P.; Durmaz, F.; Spencer, N. D.;
Zrcher, S. Langmuir 2007, 23, 8053-8060.

tel-00782709, version 1 - 30 Jan 2013

(159) Folkers, J. P.; Gorman, C. B.; Laibinis, P. E.; Buchholz, S.; Whitesides, G. M.; Nuzzo,
R. G. Langmuir 1995, 11, 813-824.
(160) Tsud, N.; Yoshitake, M. Surf. Sci. 2007, 601, 3060-3066.
(161) Nuzzo, R. G.; Allara, D. L. J. Am. Chem. Soc. 1983, 105, 4481-4483.
(162) Ulman, A. J. Mater. Educ. 1989, 11, 205.
(163) Laibinis, P. E.; Whitesides, G. M.; Allara, D. L.; Tao, Y. T.; Parikh, A. N.; Nuzzo, R.
G. J. Am. Chem. Soc. 1991, 113, 7152-7167.
(164) Laibinis, P. E.; Whitesides, G. M. J. Am. Chem. Soc. 1992, 114, 1990-1995.
(165) Laibinis, P. E.; Whitesides, G. M. J. Am. Chem. Soc. 1992, 114, 9022-9028.
(166) Walczak, M. M.; Chung, C.; Stole, S. M.; Widrig, C. A.; Porter, M. D. J. Am. Chem.
Soc. 1991, 113, 2370-2378.
(167) Rusu, P. C.; Giovannetti, G.; Brocks, G. J. Phys. Chem. C 2007, 111, 14448-14456.
(168) Shaporenko, A.; Ulman, A.; Terfort, A.; Zharnikov, M. J. Phys. Chem. B 2005, 109,
3898-3906.
(169) Weiss, E. A.; Chiechi, R. C.; Kaufman, G. K.; Kriebel, J. K.; Li, Z.; Duati, M.; Rampi,
M. A.; Whitesides, G. M. J. Am. Chem. Soc. 2007, 129, 4336-4349.
(170) Hoque, E.; DeRose, J. A.; Houriet, R.; Hoffmann, P.; Mathieu, H. J. Chem. Mater.
2007, 19, 798-804.
(171) Jennings, G. K.; Yong, T.-H.; Munro, J. C.; Laibinis, P. E. J. Am. Chem. Soc. 2003,
125, 2950-2957.
(172) Vollmer, S.; Witte, G.; Wll, C. Langmuir 2001, 17, 7560-7565.

42

I. State of the art


(173) Stapleton, J. J.; Daniel, T. A.; Uppili, S.; Cabarcos, O. M.; Naciri, J.; Shashidhar, R.;
Allara, D. L. Langmuir 2005, 21, 11061-11070.
(174) Love, J. C.; Wolfe, D. B.; Haasch, R.; Chabinyc, M. L.; Paul, K. E.; Whitesides, G. M.;
Nuzzo, R. G. J. Am. Chem. Soc. 2003, 125, 2597-2609.
(175) Stratmann, M. Adv. Mater. 1990, 2, 191-195.
(176) Volmer, M.; Stratmann, M.; Viefhaus, H. Surf. Interface Anal. 1990, 16, 278-282.
(177) Noguchi, H.; Ito, M.; Uosaki, K. Chem. Lett. 2005, 34, 850-851.
(178) Lee, S.; Park, J.; Ragan, R.; Kim, S.; Lee, Z.; Lim, D. K.; Ohlberg, D. A. A.; Williams,
R. S. J. Am. Chem. Soc. 2006, 128, 5745-5750.

tel-00782709, version 1 - 30 Jan 2013

(179) Shimazu, K.; Sato, Y.; Yagi, I.; Uosaki, K. Bull. Chem. Soc. Jpn. 1994, 67, 863-865.
(180) Mcguiness, C. L.; Blasini, D.; Masejewski, J. P.; Uppili, . S.; Cabarcos, O. M.;
Smilgies, D.; Allara, D. L. ACS Nano 2007, 1, 28-32.
(181) Mcguiness, C. L.; Diehl, G. A.; Blasini, D.; Smilgies, D.-M.; Zhu, M.; Samarth, N.;
Weidner, T.; Ballav, N.; Zharnikov, . M.; Allara, D. L. ACS Nano 2010, 4, 34473465.
(182) Lim, H.; Carraro, C.; Maboudian, R.; Pruessner, M. W.; Ghodssi, R. Langmuir 2004,
20, 743-747.
(183) Schvartzman, M.; Sidorov, V.; Ritter, D.; Paz, Y. J. Vac. Sci. Tech. B 2003, 21, 148155.
(184) Yamamoto, H.; Butera, R. A.; Gu, Y.; Waldeck, D. H. Langmuir 1999, 15, 8640-8644.
(185) Gu, Y.; Lin, Z.; Butera, R. A.; Smentkowski, V. S.; Waldeck, D. H. Langmuir 1995,
11, 1849-1851.
(186) Bodlaki, D.; Yamamoto, H.; Waldeck, D. H.; Borguet, E. Surf. Sci. 2003, 543, 63-74.
(187) Ardalan, P.; Musgrave, C. B.; Bent, S. F. Langmuir 2009, 25, 2013-2025.
(188) Ardalan, P.; Sun, Y.; Pianetta, P.; Musgrave, C. B.; Bent, S. F. Langmuir 2010, 26,
8419-8429.
(189) Han, S. M.; Ashurst, W. R.; Carraro, C.; Maboudian, R. J. Am. Chem. Soc. 2001, 123,
2422-2425.
(190) Troughton, E. B.; Bain, C. D.; Whitesides, G. M.; Nuzzo, R. G.; Allara, D. L.; Porter,
M. D. Langmuir 1988, 4, 365-385.
(191) Katz, E.; Itzhak, N.; Willner, I. J. Electroanal. Chem. 1992, 336, 357-362.

43

I. State of the art


(192) Aswal, D. K.; Lenfant, S.; Guerin, D.; Yakhmi, J. V.; Vuillaume, D. Anal. Chim. Acta
2006, 568, 84-108.
(193) Linford, M. R.; Chidsey, C. E. D. J. Am. Chem. Soc. 1993, 115, 12631-12632.
(194) Buriak, J. M. Chem. Rev. 2002, 102, 1271-1308.
(195) Bent, S. F. Surf. Sci. 2002, 500, 879-903.
(196) Linford, M. R.; Fenter, P.; Eisenberger, P. M.; Chidsey, C. E. D. J. Am. Chem. Soc.
1995, 117, 3145-3155.
(197) Sieval, A. B.; Demirel, A. L.; Nissink, J. W. M.; Linford, M. R.; van der Maas, J. H.;
de Jeu, W. H.; Zuilhof, H.; Sudhlter, E. J. R. Langmuir 1998, 14, 1759-1768.

tel-00782709, version 1 - 30 Jan 2013

(198) Sung, M. M.; Kluth, G. J.; Yauw, O. W.; Maboudian, R. Langmuir 1997, 13, 61646168.
(199) Terry, J.; Linford, M. R.; Wigren, C.; Cao, R.; Pianetta, P.; Chidsey, C. E. D. Appl.
Phys. Lett. 1997, 71, 1056-1058.
(200) Cicero, R. L.; Linford, M. R.; Chidsey, C. E. D. Langmuir 2000, 16, 5688-5695.
(201) Song, J. H.; Sailor, M. J. J. Am. Chem. Soc. 1998, 120, 2376-2381.
(202) Kim, N. Y.; Laibinis, P. E. J. Am. Chem. Soc. 1999, 121, 7162-7163.
(203) Deiamar, M.; Hitmi, R.; Pinson, J.; Savbnt, J. M. J. Am. Chem. Soc. 1992, 114, 58835884.
(204) Bahr, J. L.; Yang, J.; Kosynkin, D. V.; Bronikowski, M. J.; Smalley, R. E.; Tour, J. M.
J. Am. Chem. Soc. 2001, 123, 6536-6542.
(205) Kariuki, J. K.; McDermott, M. T. Langmuir 1999, 15, 6534-6540.
(206) Gooding, J. J. Electroanal. 2008, 20, 573-582.
(207) Downard, A. J. Electroanal. 2000, 12, 1085-1096.
(208) Lyskawa, J.; Blanger, D. Chem. Mater. 2006, 18, 4755-4763.
(209) Liu, G. Z.; Bocking, T.; Gooding, J. J. J. Electroanal. Chem. 2007, 600, 335-344.
(210) Laforgue, A.; Addou, T.; Belanger, D. Langmuir 2005, 21, 6855-6865.
(211) Adenier, A.; Bernard, M.-C.; Chehimi, M. M.; Cabet-Deliry, E.; Desbat, B.;
Fagebaume, O.; Pinson, J.; Podvorica, F. J. Am. Chem. Soc. 2001, 123, 4541-4549.
(212) Boukerma, K.; Chehimi, M. M.; Pinson, J.; Blomfield, C. Langmuir 2003, 19, 63336335.
44

I. State of the art


(213) Chauss, A.; Chehimi, M. M.; Karsi, N.; Pinson, J.; Podvorica, F.; Vautrin-Ul, C.
Chem. Mater. 2001, 14, 392-400.
(214) Maldonado, S.; Smith, T. J.; Williams, R. D.; Morin, S.; Barton, E.; Stevenson, K. J.
Langmuir 2006, 22, 2884-2891.
(215) Merson, A.; Dittrich, T.; Zidon, Y.; Rappich, J.; Shapira, Y. Appl. Phys. Lett. 2004, 85,
1075-1076.
(216) Garcia, A.; Berthelot, T.; Viel, P.; Polesel-Maris, J.; Palacin, S. ACS App. Mater.
Interfaces 2010, 2, 3043-3051.
(217) Combellas, C.; Kanoufi, F.; Mazouzi, D.; Thiebault, A.; Bertrand, P.; Medard, N.
Polymer 2003, 44, 19-24.

tel-00782709, version 1 - 30 Jan 2013

(218) Le, X. T.; Viel, P.; Jegou, P.; Garcia, A.; Berthelot, T.; Bui, T. H.; Palacin, S. J. Mater.
Chem. 2010, 20, 3750-3757.
(219) Viel, P.; Le, X. T.; Huc, V.; Bar, J.; Benedetto, A.; Le Goff, A.; Filoramo, A.;
Alamarguy, D.; Nol, S.; Baraton, L.; Palacin, S. J. Mater. Chem. 2008, 18, 59135920.
(220) Abiman, P.; Wildgoose, G. G.; Compton, R. G. J. Phys. Org. Chem. 2008, 21, 433439.
(221) Heald, C. G. R.; Wildgoose, G. G.; Jiang, L.; Jones, T. G. J.; Compton, R. G.
ChemPhysChem 2004, 5, 1794-1799.
(222) Masheter, A. T.; Wildgoose, G. G.; Crossley, A.; Jones, H.; Compton, R. G.; Jones, J.
H. J. Mater. Chem. 2007, 17, 3008-3014.
(223) Pandurangappa, M.; Ramakrishnappa, T. Mater. Chem. Phys. 2010, 122, 567-573.
(224) Wildgoose, G. G.; Lawrence, N. S.; Leventis, H. C.; Jiang, L.; Jones, T. G. J.;
Compton, R. G. J. Mater. Chem. 2005, 15, 953-959.
(225) Wildgoose, G. G.; Leventis, H. C.; Davies, I. J.; Crossley, A.; Lawrence, N. S.; Jiang,
L.; Jones, T. G. J.; Compton, R. G. J. Mater. Chem. 2005, 15, 2375-2382.
(226) Galli, C. Tetrahedron Lett. 1980, 21, 4515-4516.
(227) Mesnage, A.; Esnouf, S.; Jegou, P.; Deniau, G.; Palacin, S. Chem. Mater. 2010, 22,
6229-6239.
(228) Adenier, A.; Barre, N.; Cabet-Deliry, E.; Chausse, A.; Griveau, S.; Mercier, F.; Pinson,
J.; Vautrin-Ul, C. Surf. Sci. 2006, 600, 4801-4812.
(229) Adenier, A.; Cabet-Deliry, E.; Chausse, A.; Griveau, S.; Mercier, F.; Pinson, J.;
Vautrin-Ul, C. Chem. Mater. 2005, 17, 491-501.

45

I. State of the art


(230) Allongue, P.; Delamar, M.; Desbat, B.; Fagebaume, O.; Hitmi, R.; Pinson, J.; Saveant,
J. M. J. Am. Chem. Soc. 1997, 119, 201-207.
(231) Barrire, F.; Downard, A. J.; Barriere, F. J. Solid State Electrochem. 2008, 12, 12311244.
(232) Brooksby, P. A.; Downard, A. J. Langmuir 2004, 20, 5038-5045.
(233) Lomeda, J. R.; Doyle, C. D.; Kosynkin, D. V.; Hwang, W.-F.; Tour, J. M. J. Am.
Chem. Soc. 2008, 130, 16201-16206.
(234) Lehr, J.; Garrett, D. J.; Paulik, M. G.; Flavel, B. S.; Brooksby, P. A.; Williamson, B.
E.; Downard, A. J. Anal. Chem. 2010, 82, 7027-7034.

tel-00782709, version 1 - 30 Jan 2013

(235) Be, D.; Chamoulaud, G.; Blanger, D. J. Phys. Chem. C 2007, 111, 7501-7507.
(236) Combellas, C.; Delamar, M.; Kanoufi, F.; Pinson, J.; Podvorica, F. I. Chem. Mater.
2005, 17, 3968-3975.
(237) Lehr, J.; Williamson, B. E.; Flavel, B. S.; Downard, A. J. Langmuir 2009, 25, 1350313509.
(238) Shewchuk, D. M.; McDermott, M. T. Langmuir 2009, 25, 4556-4563.
(239) Charlier, J.; Clolus, E.; Bureau, C.; Palacin, S. J. Electroanal. Chem. 2009, 625, 97100.
(240) Stewart, M. P.; Maya, F.; Kosynkin, D. V.; Dirk, S. M.; Stapleton, J. J.; McGuiness, C.
L.; Allara, D. L.; Tour, J. M. J. Am. Chem. Soc. 2003, 126, 370-378.
(241) Allongue, P.; de Villeneuve, C. H.; Cherouvrier, G.; Cortes, R.; Bernard, M. C. J.
Electroanal. Chem. 2003, 550, 161-174.
(242) Allongue, P.; de Villeneuve, C. H.; Pinson, J.; Ozanam, F.; Chazalviel, J. N.; Wallart,
X. Electrochim. Acta 1998, 43, 2791-2798.
(243) Haight, R.; Sekaric, L.; Afzali, A.; Newns, D. Nano Lett. 2009, 9, 3165-3170.
(244) Chen, B.; Flatt, A. K.; Jian, H. H.; Hudson, J. L.; Tour, J. M. Chem. Mater. 2005, 17,
4832-4836.
(245) Lin, W.; Lin, W.; Wong, G. K.; Marks, T. J. Thin Solid Films 1996, 7863, 8034-8042.
(246) Schmeisser, D.; Schnell, R. D.; Bogen, A.; Himpsel, F. J.; Rieger, D.; Landgren, G.;
Morar, J. F. Surf. Sci. 1986, 172, 455-465.
(247) Sun, S.; Sun, Y.; Liu, Z.; Lee, D.-I.; Peterson, S.; Pianetta, P. Appl. Phys. Lett. 2006,
88, 021903.
(248) Lu, Z. H. Appl. Phys. Lett. 1996, 68, 520-522.
46

I. State of the art


(249) Swain, B. P.; Takato, H.; Liu, Z.; Sakata, I. Sol. Energy Mater. Sol. Cells 2011, 95, 8488.
(250) Park, K.; Lee, Y.; Lee, J.; Lim, S. Appl. Surf. Sci. 2008, 254, 4828-4832.
(251) Cullen, G. W.; Amick, J. A.; Gerlich, D. J. Electrochem. Soc. 1962, 109, 124-127.
(252) He, J.; Lu, Z.-H.; Mitchell, S. A.; Wayner, D. D. M. J. Am. Chem. Soc. 1998, 120,
2660-2661.
(253) Knapp, D.; Brunschwig, B. S.; Lewis, N. S. J. Phys. Chem. C 2010, 114, 12300-12307.
(254) Collins, G.; Fleming, P.; Barth, S.; ODwyer, C.; Boland, J. J.; Morris, M. A.; Holmes,
J. D. Chem. Mater. 2010, 22, 6370-6377.

tel-00782709, version 1 - 30 Jan 2013

(255) Choi, K.; Buriak, J. M. Langmuir 2000, 16, 7737-7741.


(256) Holmberg, V. C.; Korgel, B. A. Chem. Mater. 2010, 22, 3698-3703.
(257) Hohman, J. N.; Kim, M.; Bednar, H. R.; Lawrence, J. A.; McClanahan, P. D.; Weiss, P.
S. Chem. Sci. 2011, 2, 1334-1343.
(258) Collins, G.; Fleming, P.; ODwyer, C.; Morris, M. A.; Holmes, J. D. Chem. Mater.
2011, 23, 1883-1891.

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II. Synthesis of push-pull systems

II.1 Tetracarboxylic naphthalenediimide derivatives (-- model systems)48


II.1.1 Thiols derivatives..49
I.1.2 Diazonium salt derivatives.50
I.2 Push-pull systems51
II.2.1 Azobenzene derivatives52
II.2.2 Stilbazolium derivatives...54

II. Synthesis of push-pull systems

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Since the introduction of SANDs by Marks and Facchetti1, push-pull systems (-conjugated
systems with a donor on one side and an acceptor on the other side, Scheme 1) gained a new
field of application. Indeed, they can be incorporated in insulating layers ensuring a high
dielectric constant. Push-pull systems were already employed in organic photovoltaic devices
as dye27; thus, a large variety of compounds was developed in literature821. However, their
use as dielectric underlines a new technical challenge: the orientation of dipoles versus the
surface22. This led to the development of model molecules to study their grafting on surfaces.
These compounds, -- systems, mimic the push-pull systems but are far easier to
synthetize, making them more suitable than push-pull systems for the complete study of the
formation of layers on the surface.

Scheme 1. General structures of the push-pull systems (top) and the -- systems (bottom).
In this work, model molecules were synthesized to study the grafting of -- systems on
germanium. These compounds were based on n- or p-type conjugated organic
semiconductors. In the same time, elaborated push-pull systems were also synthesized and
evaluated as SANDs-like layers. Table 1 summarizes the dipolar moment and
hyperpolarizability of several push-pull systems synthesized in this work.

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II. Synthesis of push-pull systems

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Table 1. Theoretical dipolar moment and hyperpolarizability of different push-pull systems


modeled with Gaussian

From the results of the calculations, pyridinium systems exhibit the highest dipolar moment
and hyperpolarizability. However, azobenzene derivatives appear to be also good candidates
whereas naphthaleneimide based compounds, some of them already described in literature1,23,
show lower dipolar moment and hyperpolarizability. Therefore, even if the model molecules
will be based on the naphthaleneimide core, the final push-pull systems will be derived from
the azobenzene skeleton.

II.1 Tetracarboxylic naphthalenediimide derivatives (-- model


systems)
Naphthalenediimide derivatives are known to be n-type semiconductors2330. Due to the
relative facile access to a large variety of molecules based on this backbone (illustrated on
Scheme 2), we chose to synthesize some naphtalenediimide based compounds as model
systems for the study of their organization on surfaces through two different anchoring
processes: thiolate SAM formation or diazonium salt grafting. Different -- systems were
thus obtained with various alkyl chains and various anchoring groups.

50

II. Synthesis of push-pull systems

Scheme 2. General structure of the naphthalenediimide derivatives. The -conjugated core is


shown in red and the two acceptor parts in purple.

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II.1.1 Thiols derivatives


Thiols derivatives of naphthalenediimide were obtained through two condensation reactions
of amines on tetracarboxylic naphthalene dianhydride, the first one with alkylamine and the
second with the corresponding ,-thioalkylamine. The latter was prepared in three steps
starting from the ,-dibromoalkane which experienced two successive nucleophilic
substitutions, the first with potassium phtalimide, the second with potassium thioacetate, to
give the -phtalimido--thioacetatoalkane. The amine and thiol groups are then deprotected
with hydrazine yielding to the ,-thioalkylamine. The synthesis of thiols derivatives of
naphthalenediimide is illustrated on scheme 3. To study the influence of the alkyl chains on
the organization of the SAM and the orientation of the conjugated systems regarding the
surface, we synthesized molecules with 6 or 7 aliphatic carbons on both side of the aromatic
core.

Scheme 3. Synthesis of thiol derivatives of naphthalenediimide


Dithiols derivatives with 6 or 7 carbons were also synthesized to study the influence of the
presence of a terminal functional group on the organization of the layer. These compounds
were obtained by double condensation of ,-thioalkylamine on tetracarboxylic naphthalene
dianhydride as depicted in scheme 4. However, as for the first step of the previous synthesis,
due to the low solubility of tetracarboxylic naphthalene dianhydride, the yields were limited.
Furthermore, the product also has a poor solubility in usual solvents thus complicating its use
to form SAMs.

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II. Synthesis of push-pull systems

Scheme 4. Synthesis of the dithiol derivatives.

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Beside naphthalenediimide derivatives, terthiophene compounds synthesized by Fabrice


Moggia were also employed as model -- systems. Their synthesis is depicted in scheme 5.

Scheme 5. Synthesis of the terthiophene derivatives


II.1.2 Diazonium salt derivatives
The diazonium salt derivatives were obtained by diazoniation of corresponding amine
derivatives. The preparation was similar to those of thiols except that 4-(2-aminoethyl)aniline
was used instead of ,-thioalkylamine (Scheme 6).

Scheme 6. Synthesis of the amine precursors of diazonium salt derivatives.


However, the choice of the diazoniation method was made considering the properties of the
substrate. Indeed, the most common way for diazoniation is to solubilize the amine in acidic
media (typically HCl or HBF4) and slowly add sodium nitrite at low temperature before
precipitating the salt in diethyl ether31,32. This method is very convenient but only adapted to
52

II. Synthesis of push-pull systems

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small aniline derivatives soluble in acidic aqueous solutions. Unfortunately, in the case of our
naphthalene derivatives, the solubility of the amine compound is very poor in HBF4
preventing the use of this method for diazoniation. Due to the relative sensitivity of diazonium
salts, only few methods in organic solvent are available to synthesize them. The most wellknown involves nitrosyl tetrafluoroborate in acetonitrile at low temperature33 but, here again;
our compounds are not soluble in acetonitrile. Therefore, we chose a method performed in
THF at low temperature. This route proceeds in two steps; first, the amine was reacted with
excess boron trifluoride diethyl etherate then ter-butylnitrite was added34. BF3.OEt2 acts as a
Lewis acid forming the diazoniation agent NOBF4 from t-BuONO but also quenching the
water produced during the reaction. The salt was finally precipitated in diethyl ether with high
yield (above 85 %). This way is adaptable to almost all amine precursors except those
presenting a second free amine group or a pyridine (in this case, acidic media is required to
keep the amine or the pyridine moiety protonated thus preventing the use of boron trifluoride).
This method was used to synthesize almost all the diazonium salts used in this work.
Diazonium salt synthesis is depicted in Scheme 7.

Scheme 7. Diazoniation reactions used

II.2 Push-pull systems


Push-pull systems are composed of a donor and an acceptor separated by a conjugated spacer.
Typical donor groups are amines (anilines, piperidine) and aliphatic ethers (methoxy,
ethoxy)3540. On the other hand, the most well-known acceptor moieties are carbonyls,
nitro, fluorinated groups and nitriles4144. Finally, the spacers are usually aromatic rings such
as phenyl or thiophene directly linked together or linked through an alkene or an azo bridge45
51
. In the view to graft them on surfaces, an anchoring group was also introduced on the
molecule. This group, either a thiol or an amine precursor of the diazonium salt, was linked
with a small alkyl chain to avoid coupling of the molecular dipole with the surface and to
insure, with thiols, a better organization of the SAM. Moreover, this functionalization ensures

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II. Synthesis of push-pull systems

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that the push-pull properties of the system are not altered. The general structure of the pushpull systems synthesized in this worked is presented on Scheme 8.

Scheme 8. General structure of the push-pull systems synthesized.


II.2.1 Azobenzene derivatives
The first azobenzene derivative synthesized was the diazonium salt of Disperse Orange 3 (4[(4-nitrophenyl)diazenyl]aniline). However, more elaborated structures were also envisaged.
The structure and synthesis of these compounds are presented on Scheme 9. The donor part
lies in the O-alkyl group and the acceptor sides is located on the fluorinated group. Both are
linked through an azo bridge connecting the two benzene rings bearing the functional groups.
Two different strategies were envisaged for the synthesis of these compounds. For the first
one, a double nucleophilic substitution of 1,10-diiododecane with 4-nitrophenol in presence of
potassium carbonate leads to the diether formation34. The nitro groups are then reduced with
hydrazine and Pd/C52 to give the diamino compound. One of the amines will serve for
diazonium salt formation whereas the other will be reacted with nitroso compounds obtained
by oxidation of corresponding amines by Oxone (KHSO5.0.5KHSO4.0.5K2SO4). The
condensation of the nitroso and the amine groups53 leads to the azobenzene derivatives. The
alternative way involves a diazo coupling5456 between the diazonium salt of the fluorinated
aniline (prepared with BF3OEt2 and t-BuONO) and phenol to form the azobenzene. The latter
is then reacted with 1,10-diiododecane to provide the O-alkylated azobenzene. Another
nucleophilic substitution with 4-nitrophenol followed by reduction with hydrazine and Pd/C
conducts to the targeted product.

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II. Synthesis of push-pull systems

Scheme 9. Synthesis of the azobenzene derivatives.


The first path gave better yield than the second even if the nitroso preparation provided low
yield with 4-trifluoromethylaniline. This is probably due to the diazo coupling step in which
the phenol is not activated enough but could also interact with the diazonium salt to form
diazoethers. Moreover, quenching of the diazo coupling reaction with NaOH usually leads to
precipitation of the azobenzene but, here, due to the formation of a phenolate, the compounds
55

II. Synthesis of push-pull systems


were soluble, thus complicating the work-up and further decreasing the yield. Therefore, the
first path was chosen to synthesize these derivatives. Finally, even if they were not
synthesized, thiol derivatives can be envisaged by substitution of one of the two iodine atoms
by a thioacetate moiety with potassium thioacetate.

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II.2.2 Stilbazolium derivatives


The SANDs reported by Marks and Facchetti1 were based on the stilbazolium core. In these
molecules, an amine moiety constitutes the donor part whereas a pyridinium cation stands for
the acceptor side. Once again, the two are linked by an azo bridge between the two aromatic
rings bearing the donor/acceptor parts. These derivatives combine some of the best donor
groups (disubstituted amines) with one of the best acceptor ones. Three different amines as
well as three different anchoring systems were tested. In a view to graft these derivatives on
Ge clean surfaces, thiol (for a better control of dipole organization and a strict mono-layering)
and diazonium salt (for multi-layering) were envisaged. In the same time, the possibility to
graft those systems on oxides (such as TiO2 or native Ge oxide) was probed with a carboxylic
acid. Meanwhile, dimethyl-, diethanol- and diphenylamine were tested as donor part.
Diethanolamine group presents the advantage of a potential subsequent cross-linking of the
layer by octadecyltrichlorosilane which could prevent a reorganization of the dipoles under
polarization. On the other hand, with diazonium salts, diphenylamine derivatives could lead to
multi-layering which could enhance the dielectric properties of the layer. Dimethylamine
derivatives will stand as reference both for the reorganization of dipoles under polarization
and for the grafting through diazonium salt and thiol. Thus, the three derivatives were
synthesized with both thiol and diazonium salt anchoring groups. Carboxylic acid group was
limited to dimethyl- and diphenylamine derivatives to prevent any adventitious esterification.
For diethanol- and dimethylamine derivatives, the synthesis began with an azo coupling of
diazonium salt of 4-aminopyridine generated in-situ and respectively N-phenyldiethanolamine
and N,N-dimethylaniline (Scheme 10). The formed azobenzene pyridine was then reacted
with either 4-nitrophenethylbromide or 6-bromohexanethiol to provide pyridinium precursor
for the stilbazolium amine derivative and the stilbazolium thiol derivative respectively. The
nitro group was reduced with H2 and Pd/C57 in amine which was then diazotized with sodium
nitrite in HBF4. Other techniques to reduce the nitro group, such as hydrazine with Pd/C52 or
Na2S5860, led to decomposition of the product (loss of the pyridinium).

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II. Synthesis of push-pull systems

Scheme 10. Synthesis of the stilbazolium derivatives.


Unfortunately, with diphenylamine derivatives, this route led to very poor yields for the azo
coupling of the diazonium salt on triphenylamine (first step of the synthesis). Therefore, an
alternative path was developed via the condensation of 4-aminopyridine on 4bromonitrosobenzene, the latter being prepared by oxidation of 4-bromoaniline with Oxone
(Scheme 11). A Buchwald-Hartwig coupling6166 with palladium(II) acetate, tri(tbutyl)phosphine and t-BuONa led to the formation of the azobenzene pyridine intermediate
similar to the one obtained with the previously described procedure. From this compound, the
thiol and diazonium salt derivatives were obtained through the same pyridine alkylations
followed by reduction and diazoniation in the latter case. Finally, the carboxylic acid
derivatives were also obtained via pyridine alkylation with 3-bromopropionic acid (Scheme
11).

Scheme 11. Alternative route for preparing the diphenylamine precursor.


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II. Synthesis of push-pull systems

Finally, the sensitive reduction step was replaced in an alternative route by the formation of
the triazene derivative. Triazenes are protected diazonium salts with higher stability allowing
heating or basic conditions6769. However, in acidic media, the triazene is cleaved to form the
corresponding diazonium salt7072 thus excluding low-pH media. In our case, the triazene only
underwent a nucleophilic substitution to obtain the desired compound thus making it a good
candidate to introduce the diazonium functionality. The corresponding diazonium salt was
recovered in situ for the grafting process. For this route, we firstly prepared a bromoethyl
substituted triazenyl compound from 4-(2-hydroxyethyl)aniline. The first step consisted in the
bromination of the alcohol in HBr to form the 4-(2-bromoethyl)aniline which was not isolated
to prevent degradation from nucleophilic attack of the amine groups on the bromine. This
aniline derivative was then diazotized with sodium nitrite in HBF4. The diazonium salt was
finally reacted with diethylamine in presence of sodium carbonate to furnish the desired
triazene. The nucleophilic attack of the pyridine intermediates synthesized previously led to
the formation of the push-pull triazenyl derivatives, precursors of the corresponding desired
diazonium salts. The synthetic route is presented on Scheme 12.

Scheme 12. Synthetic route for the triazenyl compounds.

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II. Synthesis of push-pull systems

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References
(1)

Yoon, M.-H. H.; Facchetti, A.; Marks, T. J. PNAS 2005, 102, 4678-4682.

(2)

de la Torre, G.; Claessens, C. G.; Torres, T. Chem. Commun. 2007, 2000.

(3)

Moon, S.-J.; Yum, J.-H.; Humphry-Baker, R.; Karlsson, K. M.; Hagberg, D. P.;
Marinado, T.; Hagfeldt, A.; Sun, L.; Gratzel, M.; Nazeeruddin, M. K. J. Phys. Chem. C
2009, 113, 16816-16820.

(4)

Grtzel, M. Acc. Chem. Res. 2009, 42, 1788-1798.

(5)

Alibabaei, L.; Kim, J.-H.; Wang, M.; Pootrakulchote, N.; Teuscher, J.; Di Censo, D.;
Humphry-Baker, R.; Moser, J.-E.; Yu, Y.-J.; Kay, K.-Y.; Zakeeruddin, S. M.; Grtzel,
M. Energy Environ. Sci. 2010, 3, 1757-1764.

(6)

Baik, C.; Kim, D.; Kang, M.-S.; Kang, S. O.; Ko, J.; Nazeeruddin, M. K.; Grtzel, M.
J. Photochem. Photobiol., A 2009, 201, 168-174.

(7)

Kim, S.; Lee, J. K.; Kang, S. O.; Ko, J.; Yum, J.-H.; Fantacci, S.; De Angelis, F.; Di
Censo, D.; Nazeeruddin, M. K.; Grtzel, M. J. Am. Chem. Soc. 2006, 128, 1670116707.

(8)

Bolink, H. J.; Cappelli, L.; Coronado, E.; Grtzel, M.; Ort, E.; Costa, R. D.; Viruela, P.
M.; Nazeeruddin, M. K. J. Am. Chem. Soc. 2006, 128, 14786-14787.

(9)

Murakami, T. N.; Ito, S.; Wang, Q.; Nazeeruddin, M. K.; Bessho, T.; Cesar, I.; Liska,
P.; Humphry-Baker, R.; Comte, P.; Pchy, P.; Gratzel, M. J. Electrochem. Soc. 2006,
153, A2255.

(10)

Berner, D.; Klein, C.; Nazeeruddin, M. K.; De Angelis, F.; Castellani, M.; Bugnon, P.;
Scopelliti, R.; Zuppiroli, L.; Graetzel, M. J. Mater. Chem. 2006, 16, 4468-4474.

(11)

Ito, S.; Ha, N.-L. C.; Rothenberger, G.; Liska, P.; Comte, P.; Zakeeruddin, S. M.;
Pchy, P.; Nazeeruddin, M. K.; Grtzel, M. Chem. Commun. 2006, 4004-4006.

(12)

Kay, A.; Grtzel, M. Sol. Energy Mater. Sol. Cells 1996, 44, 99-117.

(13)

Delcamp, J. H.; Yella, A.; Nazeeruddin, M. K.; Grtzel, M. Chem. Commun. 2012, 48,
2295-2297.

(14)

Li, C.; Yum, J.; Moon, S.; Herrmann, A.; Eickemeyer, F.; Pschirer, N. G.; Erk, P.;
Schneboom, J.; Mllen, K.; Grtzel, M.; Nazeeruddin, M. K. ChemSusChem 2008, 1,
615-618.

(15)

Qin, H.; Wenger, S.; Xu, M.; Gao, F.; Jing, X.; Wang, P.; Zakeeruddin, S. M.; Grtzel,
M. J. Am. Chem. Soc. 2008, 130, 9202-9203.

(16)

Shi, D.; Cao, Y.; Pootrakulchote, N.; Yi, Z.; Xu, M.; Zakeeruddin, S. M.; Gratzel, M.;
Wang, P. J. Phys. Chem. C 2008, 112, 17478-17485.
59

tel-00782709, version 1 - 30 Jan 2013

II. Synthesis of push-pull systems


(17)

Xu, M.; Li, R.; Pootrakulchote, N.; Shi, D.; Guo, J.; Yi, Z.; Zakeeruddin, S. M.;
Gratzel, M.; Wang, P. J. Phys. Chem. C 2008, 112, 19770-19776.

(18)

Yum, J.-H.; Hagberg, D. P.; Moon, S.-J.; Karlsson, K. M.; Marinado, T.; Sun, L.;
Hagfeldt, A.; Nazeeruddin, M. K.; Grtzel, M. Angew. Chem., Int. Ed. Engl. 2009, 48,
1576-1580.

(19)

Butler, R. S.; Cohn, P.; Tenzel, P.; Abboud, K. A.; Castellano, R. K. J. Am. Chem. Soc.
2009, 131, 623-633.

(20)

Ortiz, R. P.; Osuna, R. M.; Hernandez, V.; Navarrete, J. T. L.; Vercelli, B.; Zotti, G.;
Sumerin, V. V.; Balenkova, E. S.; Nenajdenko, V. G. J. Phys. Chem. A 2007, 111, 841851.

(21)

Imahori, H.; Umeyama, T.; Ito, S. Acc. Chem. Res. 2009, 42, 1809-1818.

(22)

DiBenedetto, S. A.; Frattarelli, D. L.; Facchetti, A.; Ratner, M. A.; Marks, T. J. J. Am.
Chem. Soc. 2009, 131, 11080-11090.

(23)

See, K. C.; Landis, C.; Sarjeant, A.; Katz, H. E. Chem. Mater. 2008, 20, 3609-3616.

(24)

Krger, B. H.; Janietz, S.; Sainova, D.; Dobreva, D.; Koch, N.; Kruger, H.; Vollmer, A.
Adv. Funct. Mater. 2007, 17, 3715-3723.

(25)

Chen, S.-ci C.; Zhang, Q. K.; Zheng, Q. D.; Tang, C. Q.; Lu, C.-Z. Z. Chem. Commun.
2012, 48, 1254-1256.

(26)

Tan, L. X.; Guo, Y. L.; Zhang, G. X.; Yang, Y.; Zhang, D. Q.; Yu, G.; Xu, W.; Liu, Y.
Q. J. Mater. Chem. 2011, 21, 18042-18048.

(27)

Jung, B. J.; Lee, K.; Sun, J.; Andreou, A. G.; Katz, H. E. Adv. Funct. Mater. 2010, 20,
2930-2944.

(28)

Laquindanum, J. G.; Katz, H. E.; Dodabalapur, A.; Lovinger, A. J. J. Am. Chem. Soc.
1996, 118, 11331-11332.

(29)

Katz, H. E.; Johnson, J.; Lovinger, A. J.; Li, W. J. Am. Chem. Soc. 2000, 122, 77877792.

(30)

Zhan, X. W.; Facchetti, A.; Barlow, S.; Marks, T. J.; Ratner, M. A.; Wasielewski, M.
R.; Marder, S. R. Adv. Mater. 2011, 23, 268-284.

(31)

Hanson, P.; Jones, J. R.; Taylor, A. B.; Walton, P. H.; Timms, A. W. J. Chem. Soc.,
Perkin Trans. 2 2002, 1135-1150.

(32)

Zollinger, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 141-150.

(33)

Kosynkin, D. V.; Tour, J. M. Org. Lett. 2001, 3, 993-995.

(34)

Min, M.; Bang, G. S.; Lee, H.; Yu, B.-C. Chem. Commun. 2010, 46, 5232-5234.
60

tel-00782709, version 1 - 30 Jan 2013

II. Synthesis of push-pull systems


(35)

Bessho, T.; Zakeeruddin, S. M.; Yeh, C.-Y.; Diau, E. W.-G.; Grtzel, M. Angew.
Chem., Int. Ed. Engl. 2010, 49, 6646-6649.

(36)

Tonshoff, C.; Bettinger, H. F. Chem. Eur. J. 2012, 18, 1789-1799.

(37)

Hutchison, G. R.; Ratner, M. A.; Marks, T. J. J. Am. Chem. Soc. 2005, 127, 1686616881.

(38)

Okamoto, T.; Suzuki, T.; Tanaka, H.; Hashizume, D.; Matsuo, Y. Chem.--Asian J.
2012, 7, 105-111.

(39)

Cho, N.; Kim, J.; Song, K.; Lee, J. K.; Ko, J. Tetrahedron 2012, 68, 4029-4036.

(40)

Hagberg, D. P.; Yum, J.-H.; Lee, H.; De Angelis, F.; Marinado, T.; Karlsson, K. M.;
Humphry-Baker, R.; Sun, L.; Hagfeldt, A.; Grtzel, M.; Nazeeruddin, M. K. J. Am.
Chem. Soc. 2008, 130, 6259-6266.

(41)

Nair, N.; Kim, W.-J.; Usrey, M. L.; Strano, M. S. J. Am. Chem. Soc. 2007, 129, 39463954.

(42)

Yang, Y.; Zhou, Y.; He, Q.; He, C.; Yang, C.; Bai, F.; Li, Y. J. Phys. Chem. B 2009,
113, 7745-7752.

(43)

Lelige, A.; Blanchard, P.; Rousseau, T.; Roncali, J. Org. Lett. 2011, 13, 3098-3101.

(44)

Wu, W. P.; Liu, Y. Q.; Wang, Y.; Xi, H. X.; Gao, X. K.; Di, C. G.; Yu, G.; Xu, W.;
Zhu, D. B. Adv. Funct. Mater. 2008, 18, 810-815.

(45)

Kurdyukova, I. V.; Ishchenko, A. A. Russ. Chem. Rev. 2012, 81, 258-290.

(46)

Facchetti, A.; Abbotto, A.; Beverina, L.; van der Boom, M. E.; Dutta, P.; Evmenenko,
G.; Marks, T. J.; Pagani, G. A. Chem. Mater. 2002, 14, 4996-5005.

(47)

Jan van der Molen, S.; Liljeroth, P. J. Phys.: Condens. Matter 2010, 22, 133001.

(48)

Yu, B.-C.; Shirai, Y.; Tour, J. M. Tetrahedron 2006, 62, 10303-10310.

(49)

Garcia-Amors, J.; Massad, W. A.; Nonell, S.; Velasco, D. Org. Lett. 2010, 12, 35143517.

(50)

Gup, R.; Giziroglu, E.; Krkan, B. Dyes Pigm. 2007, 73, 40-46.

(51)

Kreicberga, J.; Laipniece, L.; Berzina, G.; Kampars, V. Chem. Heterocycl. Compd.
2010, 46, 438-444.

(52)

Dewar, M. J. S.; Mole, T. J. Chem. Soc. 1956, 2556-2557.

(53)

Priewisch, B.; Rck-Braun, K. J. Org. Chem. 2005, 70, 2350-2352.

(54)

Hodgson, H. H.; Marsden, E. J. Soc. Dyers Colour. 1945, 61, 20-21.


61

tel-00782709, version 1 - 30 Jan 2013

II. Synthesis of push-pull systems


(55)

Zollinger, H. Chem. Rev. 1952, 51, 347-361.

(56)

Hodgson, H. H.; Ward, E. R. J. Chem. Soc. 1947, 1060-1062.

(57)

Figueras, F.; Coq, B. J. Mol. Catal. A: Chem. 2001, 173, 223-230.

(58)

Hashimoto, S.; Sunamoto, J. Bull. Chem. Soc. Jpn. 1966, 39, 1207-1211.

(59)

Hodgson, H. H.; Ward, E. R. J. Chem. Soc. 1945, 794-796.

(60)

Yu, X.; Gong, W.; Liu, X.; Shi, L.; Han, X.; Bao, H. J. Hazard. Mater. 2011, 198, 340346.

(61)

Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902.

(62)

Guram, A. S.; Rennels, R. A.; Buchwald, S. L. Angew. Chem., Int. Ed. Engl. 1995, 34,
1348-1350.

(63)

Louie, J.; Hartwig, J. F. Tetrahedron Lett. 1995, 36, 3609-3612.

(64)

Harris, M. C.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5327-5333.

(65)

Hartwig, J. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2046-2067.

(66)

Mann, G.; Hartwig, J. F.; Driver, M. S.; Fernndez-Rivas, C. J. Am. Chem. Soc. 1998,
120, 827-828.

(67)

Kimball, D. B.; Haley, M. M. Angew. Chem., Int. Ed. Engl. 2002, 41, 3338-3351.

(68)

Gross, M. L.; Blank, D. H.; Welch, W. M. J. Org. Chem. 1993, 58, 2104-2109.

(69)

Guillier, F.; Orain, D.; Bradley, M. Chem. Rev. 2000, 100, 2091-2158.

(70)

Chen, B.; Flatt, A. K.; Jian, H.; Hudson, J. L.; Tour, J. M. Chem. Mater. 2005, 17,
4832-4836.

(71)

Lu, M.; Chen, B.; He, T.; Li, Y.; Tour, J. M. Chem. Mater. 2007, 19, 4447-4453.

(72)

Hudson, J. L.; Jian, H.; Leonard, A. D.; Stephenson, J. J.; Tour, J. M. Chem. Mater.
2006, 18, 2766-2770.

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Germanium

III. Chemical grafting of diazonium salts on germanium


Introduction to the spontaneous grafting of diazonium salts on Ge.

X. Lefvre, O. Segut, P. Jgou, S. Palacin B. Jousselme. Towards organic film passivation of


Germanium wafers using diazonium salts: mechanism and ambient stability. Chem. Sci. 2012,
X, XX.
In this work, we first studied the preparation of germanium surfaces for grafting and second
the spontaneous grafting of several diazonium salts on the prepared surfaces.

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Different preparative techniques were used and we selected the one providing the best results
in terms of oxide removing but also in terms of roughness and residual carbon contamination.
The spontaneous grafting of diazonium salts was then studied and compared to the formation
of SAMs. Influence of the temperature and grafting time as well as importance of the group in
para-position were discussed. Finally, we also determined the absolute coverage of the film
and its stability against reoxidation.
We present here a first step towards the passivation of germanium surfaces by organic films.
Finally, within the article, a comparison with grafting on gold will be presented as this
substrate will be used together with germanium to study the films and the electronic
properties.

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III. Chemical grafting of diazonium salts on germanium

Towards organic film passivation of germanium wafers


using diazonium salts: mechanism and ambient stability
Xavier Lefvre*, Olivier Segut, Pascale Jgou, Bruno Jousselme* and Serge Palacin
CEA, IRAMIS, SPCSI Chemistry of Surfaces and Interfaces Group, F-91191, Gif-sur-Yvette, France
*Corresponding authors. Tel.: +33 1 69 08 91 91. Fax: +33 1 69 08 64 62.
E-mail: xavier.lefevre@cea.fr; bruno.jousselme@cea.fr

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Abstract
Germanium is well-known for its good electronic properties, but also for the poor passivation
quality of its natural or thermally-grown oxide layer. The robust passivation of Ge surfaces is
thus a crucial step on the way to its integration in electronics at nanoscale. Before passivation,
the natural oxide layer must be removed from the surface. Different methods were
investigated and compared. The surfaces were analysed by X-ray photoelectron spectroscopy
and by atomic force microscopy to determine the impact of the etching on the roughness.
Oxide-free Cl-terminated surfaces were chosen and functionalized with various
arenediazonium salts. The grafting is a fast reaction (less than 30 minutes) and proceeds in
soft conditions (room temperature in acetonitrile solutions). The functionalization was found
to proceed even at low temperature (-18C). The modified surfaces were mainly studied by
XPS and AFM. The morphology of the organic layer was influenced by the temperature and
duration of the grafting as well as by the presence of substituents on the aromatic ring. We
demonstrated that smooth oxide-free Ge surfaces could be prepared by a cyclic oxidationrinsing- etching procedure and could be functionalized with various arenediazonium salts.
The stability of the organic layer was compared to the stability of a self-assembled monolayer
of alkanethiolates. The absolute coverage was also determined. This constitutes a first step
towards Ge crystal passivation by organic thin films.
Keywords: Germanium, surface functionalization, diazonium salts, spontaneous grafting
INTRODUCTION
In the field of semiconductors, silicon has taken a strong leadership thanks to the properties of
the Si/SiO2 interface. Indeed, thermally grown silicon dioxide provides a high-quality
interface with silicon thus allowing its use in microelectronics. This feature has led to the
extensive use of silicon in industry. However, the scaling down required for new high
performance devices considerably alters the properties of the silicon dioxide insulating layers,
and leads to gate leakage current by tunnelling through the gate dielectric. Further decreasing
the size of integrated circuits requires the development of new insulating layers, thus
challenging the leading position of silicon among the available semiconducting materials. In
this context, germanium appears to be a good candidate to replace silicon owing to its better
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intrinsic properties, its higher carrier mobilities, and its narrower band gap, as the main
motivation for using only silicon is discarded by the scaling down. Unfortunately, the
Ge/GeO2 interface is far from being as good as Si/SiO2. Indeed, this interface is very defective
in terms of regularity, but also in terms of composition. Schmeisser has shown that four
different oxidation states are involved in the oxide layer1. Furthermore, these species are
neither insulating nor stable. For instance, GeO2 is water soluble and is a poor dielectric2.
Consequently, the oxide layer must be removed in order to achieve Ge-based devices. But,
due to the fast reoxidation of Ge, the surface has to be passivated before subsequent
deposition of any high- dielectric material.
Different methods have been investigated to remove the oxide from Ge surfaces. The most
popular are those involving wet chemistry treatments providing hydrogen- or halogenpassivated surfaces. Because of the nature of the oxide layer, the cleaning of Ge substrates
remains complex. For instance, HF cleaning was reported to completely remove oxide, but
suboxide may still remain present 2-8. Oxide-free surfaces have, however, been obtained by
HBr or HCl treatments, providing halogen-terminated surfaces that are more stable than
hydrogen-terminated ones3, 5, 7, 9-12. Other wet chemistry treatments were also reported,
including NH4OH-based treatments that minimize the carbon contamination13-15 or (NH4)2S
treatments that provide S-terminated surfaces7, 16. All these treatments efficiently remove
oxide, but they do not remove the carbon contamination. Full carbon removal can only be
achieved when the oxide is thermally eliminated in ultra-high vacuum17-20. This thermal
desorption provides smooth oxide- and carbon-free surfaces, but this technique is hard to
adapt to industrial processes. Another key parameter for further use in nano electronics is the
roughness of the surface: the cleaning procedure should lead to smooth surfaces; this is
achieved by cyclic oxidation/etching process, but the resulting surface state strongly depends
on the choice of the oxidizing agent and the etchant and on their concentrations. Finally, wet
chemistry treatments have to be followed by post-functionalization in order to better cover the
surface as Cl- and H-passivated surfaces have been reported to be stable only for few hours3,
5, 10, 21, 22
.
During the past decade, different functionalization methods of Ge surfaces have been studied.
The first organic functionalization of Ge surfaces was reported by Cullen in 1962 using
Grignard reagents to introduce ethyl groups on Cl-terminated surfaces23. Then,
hydrogermylation of alkenes was introduced on H-terminated surfaces yielding strongly
bound organic monolayers5, 24. Almost at the same time, Maboudian reported the formation of
self-assembled monolayers of alkanethiolates at H-terminated Ge surfaces5, 25. Because Hterminated surfaces have a low stability, the functionalization of halide-terminated surfaces
was also studied as alternative process. Bent reported in 2009 the formation of SAMs at
halide-terminated surfaces12, 26. Although these methods provide stable passivating layers, the
one obtained through hydrogermylation or with Grignard reagents providing more stable films
than the formation of SAMs from alkanethiolates5, 27, 28, they all have number of drawbacks
such as long reaction times (from 6 h to several days), harsh conditions (more than 200C for
hydrogermylation24) or incompatibility with various organic functionalities (especially
Grignard reagents which are very reactive).
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In this context, the functionalization via diazonium salts grafting appears attractive. These
reagents are easily synthesized starting from the corresponding amines and are known to be
readily grafted through chemical or electrochemical reduction as well as, in some cases,
spontaneous grafting. For instance, attachment of aryl ligands via electrochemistry has been
studied on carbon29-32, gold33-35, iron36-38 or oxide surfaces39, 40. Grafting of diazonium salts by
chemical reduction has been achieved with hypophosphorous acid41-46 or ascorbic acid47, 48.
Finally, spontaneous grafting has been reported on carbon49-55, metals49, 50, 55-59, and
semiconductors60 like Si61-63 or GaAs64. Although the mechanism of the spontaneous grafting
remains strongly discussed, a wide variety of substrates has been modified in this way. Very
recently, Holmes et al. reported the spontaneous modification of Ge nanowires with
arenediazonium salts65.
To our knowledge, bulk Ge surface modification has not been published yet. Furthermore,
except Holmes and co-workers work on Ge nanowires, no investigation of the reactivity of
arenediazonium salts with Ge surfaces has yet been proposed. In this paper, we report the
spontaneous grafting of an extended range of diazonium salts at room temperature and with
very short reaction times onto Cl-terminated Ge surfaces. As the surface state is a key
parameter for further use in nanoelectronics, we also discuss some preparation methods in
regards to the roughness of the final oxide-free surface. The morphology of the final grafted
films was investigated with X-ray photoelectron spectroscopy (XPS) and atomic force
microscopy (AFM). We also explored the effects of different factors: temperature, grafting
time, influence of ring substituents. A mechanism for the spontaneous grafting of diazonium
salts on Ge surfaces is also discussed. The absolute coverage and the stability of the films
were also studied and found to be comparable to thiol-based passivation. Thus, diazonium
salts grafting could be the first step of a robust passivation process of Ge surfaces.
EXPERIMENTAL
Germanium surfaces (Undoped Ge(100) wafers, 550 m thickness, 1-30 .cm-1 resistivity)
were purchased from Neyco. All chemicals were purchased from Sigma Aldrich and used as
received. Prior to use, solvents and water were degassed with nitrogen. Piranha solution was
prepared by mixing 3 volumes of sulfuric acid with 1 volume of 30% H2O2 (caution: piranha
solution is an extremely strong oxidant and should be handled very carefully).
Procedure for sample cleaning. In general, germanium surfaces were first oxidized with
30% H2O2 for 5 min to remove carbon contamination. Then, after rinsing with deionized
water, they were dipped in 10% HCl for 10 min. These oxidation-rinsing-etching cycles were
repeated three times. The halide terminated surfaces were then blown dry with N2 and readily
used for functionalization. Other treatments will be detailed later in the text. This method
provided Ge(100) - 2x1 reconstructed surfaces (See LEED pattern in Supporting
Information).
Procedure for SAM formation. Halide-passivated samples were dipped in degassed 10-3M
solutions of alkanethiols in ethanol. The solutions were freshly prepared in a glove box. The
samples were immersed in the solution for 72 h in closed tubes. After SAM formation, the
samples were rinsed with ethanol and dried under vacuum.
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III. Chemical grafting of diazonium salts on germanium


Procedure for diazotization of anilines. The non-commercially available diazonium salts
were prepared from the corresponding amines according to literature procedures66. In a typical
synthesis, 3 equivalents of BF3.OEt2 were added to a solution of the aniline derivate in 20 mL
of THF at -40 C. The mixture was stirred for 20 min and then 3 equivalents of butyl nitrite
(BuONO) were added drop wise. The mixture was stirred for 10 min and then warmed to
room temperature and poured in ether to precipitate the diazonium salt. The salt was filtered
and washed with ether. The different diazonium salts were stored at -18 C prior to use.
Synthesis of benzenediazonium tetrafluoroborate 67. 200 mg (2.15 mmol) of aniline were
converted to benzenediazonium salt following the procedure described above. 360 mg of a
light pink powder were obtained (87 % yield). 1H NMR (400 MHz, CD3CN, ): 7.40 (m, 2H); 7.54

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(m, 3H). IR: 2302 cm-1 (N=N).

Synthesis of 4-cyanobenzenediazonium tetrafluoroborate (CN-BD). 254 mg (2.15 mmol) of 4aminobenzonitrile were converted to 4-cyanobenzenediazonium salt following the procedure
described above. 390 mg of an orange powder were obtained (84 % yield). 1H NMR (400
MHz, CD3CN, ): 8.25 (d, J= 8.8 Hz, 2H); 8.62 (d, J= 8.8 Hz, 2H). IR: 2290 cm -1 (N=N);
2240 cm-1 (CN).
Synthesis of 4-dimethylaminobenzenediazonium tetrafluoroborate (NMe2-BD). 292 mg (2.15
mmol)
of
4N,
N-dimethylaminophenylamine
were
converted
to
4dimethylaminobenzenediazonium salts following the procedure described above. 430 mg of a
green powder were obtained (85 % yield). 1H NMR (400 MHz, CD3CN, ): 3.26 (s, 6H); 6.93
(d, J= 9.6 Hz, 2H); 7.99 (d, J= 9.6 Hz, 2H). IR: 2248 cm-1 (N=N).
Synthesis of 4-trifluoromethylbenzenediazonium tetrafluoroborate (CF3-BD). 346 mg (2.15
mmol) of 4-trifluoromethylaniline were converted to 4-trifluoromethylbenzenediazonium salt
following the procedure described above. 500 mg of a white powder were obtained (89 %
yield). 1H NMR (400 MHz, CD3CN, ): 8.23 (d, J= 8.8 Hz, 2H); 8.69 (d, J= 8.8 Hz, 2H). IR:
2306 cm-1 (N=N).
Synthesis of 4-heptadecafluorooctylbenzenediazonium tetrafluoroborate (C8F17-BD). 1.1 g
(2.15
mmol)
of
4-heptadecafluorooctylaniline
were
converted
to
4heptadecafluorooctylbenzenediazonium salt following the procedure described above. 1.02 g
of a white powder were obtained (78 % yield). 1H NMR (400 MHz, CD3CN, ): 7.73 (m, 2H);
8.42 (m, 2H). IR: 2308 cm-1 (N=N).
Synthesis of 4-(p-nitrophenyl)azobenzenediazonium tetrafluoroborate (DO-BD). 520 mg (2.15
mmol)
of
4-[(4-nitrophenyl)diazenyl]aniline
were
converted
to
4-(pnitrophenyl)azobenzenediazonium salt following the procedure described above. 586 mg of a
dark red powder were obtained (80 % yield). 1H NMR (400 MHz, CD3CN, ): 8.19 (d, J= 8.8
Hz, 2H); 8.31 (d, J= 8.8 Hz, 2H); 8.46 (d, J= 8.8 Hz, 2H); 8.68 (d, J= 8.8 Hz, 2H). IR: 2290
cm-1 (N=N); 1527 cm-1 (NO2); 1350 cm-1 (NO2).
Procedure for spontaneous diazonium salts grafting. After preparation of the halideterminated surface, the samples were dipped in a degassed 5.10-3M solution of diazonium salt
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III. Chemical grafting of diazonium salts on germanium


in acetonitrile. We used grafting times ranging from 5 min to 60 min and a reaction
temperature between -18 C and 80 C. Some experiments were carried out in the dark to
probe light influence. However, there was no difference whether the experiments were
conducted in light or in the dark. After functionalization, the samples were dipped in
acetonitrile and soaked to remove physisorbed products. The samples were then rinsed with
acetonitrile and blown dried with N2.

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Furthermore, even if the studies were performed in acetonitrile, it is possible to graft


diazonium salts on Ge surfaces by adding the salt on the substrate immersed in the last HCl
etching solution.
Characterization. X-ray photoemission spectroscopy (XPS) analyses were performed with a
Kratos Axis Ultra DLD using a high-resolution monochromatic Al-K line X-ray source at
1486.6 eV. Fixed analyser pass energy of 20 eV was used for core level scans. Survey spectra
were captured at pass energy of 160 eV. The photoelectron take-off angle was always normal
to the surface, which provided an integrated sampling depth of approximately 15 nm. A
survey spectrum (Survey spectra are shown in Supporting Information) and core-level spectra
of C1s (282 - 291 eV), O1s (526 - 538 eV), N1s (396 - 409 eV), Ge 2p (1215-1225 eV) and
Ge 3d (25-35 eV) regions were systematically recorded. In some cases, Br 3d (62-74 eV), F
1s (675-689 eV) or Cl 2p (188-204 eV) were recorded. All spectra were referenced with an
external gold substrate with a binding energy of 84.0 eV for Au 4f. Data were treated with
Avantage software. Germanium substrates were imaged by AFM in contact mode with a
Molecular Imaging PicoSPMLe commercial AFM microscope (PicoScan 2100 controller,
Scientec, France) using a commercial pyramidal Si tip (mounted on 225 m long single-beam
cantilever with a resonance frequency of approximately 75 kHz and a spring constant of about
3 N.m-1). The scan rate was in the range of 1.20 Hz with a scanning density of 512 lines per
frame. The AFM was mounted on a floating table to achieve vibration insulation during
investigations. The RMS roughness values of the scans were calculated using the Gwyddion
2.19 program covered by GNU General Public License. Differential scanning calorimetry
experiments were performed on a Setaram DSC 131. FT-IR spectra were recorded on a
Bruker Alpha. The LEED patterns were recorded on a VG Rear View LEED.
Figure 1 illustrates the diazonium salts used in this study: benzenediazonium
tetrafluoroborate,
4-cyanobenzenediazonium
tetrafluoroborate
(CN-BD),
4nitrobenzenediazonium
tetrafluoroborate
(NBD),
4-methoxybenzenediazonium
tetrafluoroborate (OMe-BD), 4-dimethylaminobenzenediazonium tetrafluoroborate (NMe2BD),
4-trifluoromethylbenzenediazonium
tetrafluoroborate
(CF3-BD),
4heptadecafluorooctylbenzenediazonium
tetrafluoroborate
(C8F17-BD),
and
4-(pnitrophenyl)azobenzenediazonium tetrafluoroborate (DO-BD, diazonium salt derived from
Disperse Orange 3). All these diazonium salts except BD presents characteristic groups that
are easily detected by XPS. Furthermore, different electronic effects are expected from the
various para-located substituents68 (see figure 1) and different steric properties which will be
compared here.

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III. Chemical grafting of diazonium salts on germanium


CN

NO2

NO2

N2+ BF4-

(BD)

N2+ BF4-

(CN-BD)

N2+ BF4-

(NBD)

Electron withdrawing
Mesomeric withdrawing

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N
OMe

NMe2

CF3

C8F17

N2+ BF4-

N2+ BF4-

N2+ BF4-

N2+ BF4-

N2+ BF4-

(OMe-BD)

(NMe2-BD)

(CF3-BD)

Electron withdrawing
Mesomeric donating

(C8F17-BD)

(DO-BD)

Electron withdrawing

Figure 1. Diazonium salts used for Ge functionalization and the electronic effects of groups
in para-position compared to benzenediazonium 67.
RESULTS AND DISCUSSION
1. Preparation of Germanium substrates.
Prior to functionalization, the thick oxide layer (Fig. S1, see Supporting Information in
Appendix II) that contains defects that could alter the Ge properties for further use must be
removed from the Ge surface. This step is very important as it will determine the roughness of
the resulting surface. Indeed, the roughness is a key parameter, as well for SAM formation,
for passivation, but also for use in electronics at nanoscale. Thus, the surfaces must be as
smooth as possible. A lot of recent works dealt with Ge etching, but relatively few discussed
the roughness obtained after treatment. Here, we studied different methods in regards with the
quality of the resulting surface. The surfaces were studied by XPS and AFM to determine the
best way to prepare our sample.
As already reported in literature, hydrohalogenic acids are known to efficiently remove oxides
from Ge surfaces, but they do not alter the surface identically. We studied HF, HCl and HBr
treatments along with H2O2 in a cyclic oxidation-rinsing-etching procedure7, 10-12. The Ge
surfaces obtained by this way were studied by XPS. The Ge 3d and Ge 2p spectra (Fig. S2)
confirmed that the etching partially removed the native oxide, but XPS spectra still exhibited
germanium oxide, meaning either a non-complete removal of oxide or a fast reoxidation of
the surface. As the reoxidation process could possibly alter the roughness, we chose to readily
protect our freshly etched substrates with a SAM of nonanethiol that allowed us to study both
the efficiency of the etching and its impact on the roughness of the sample without affecting
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III. Chemical grafting of diazonium salts on germanium


directly its roughness. After protection by a SAM, the efficiency of hydrohalogenic acidsbased etching was confirmed, as no trace of Ge oxides were detected by XPS (Fig. S3). The
presence of the SAM was also confirmed by XPS as the S 2p and the C 1s spectra exhibit the
presence of both sulfur and aliphatic carbon (Fig. S3). Thus, the C 1s spectrum also shows an
important carbon contamination of the surface which is in accordance with previously
reported surface treatments. From both protected and unprotected substrates prepared with the
same etching procedure, we estimated the quantitative contribution of the SAM to the XPS C
1s peak to be approximately 6000 counts. This value is in accordance with the recorded
intensity of the S 2p spectra. Residual carbon contamination (given in Table 1) was obtained
by subtracting 6000 counts to the C 1s peak intensity. To eliminate or reduce contamination,
few methods are available (for example with NH4OH or with previous treatment in piranha),
but they did not provide, in our case, better results, with or without the SAM protection. The
measured carbon contamination is due to the very reactive surfaces obtained after etching that
were readily recontamined during transfer to XPS. Other smoother treatments were also
investigated, both in organic and aqueous media. Pure water was tested, as it dissolves GeO2.
GeO is however not water soluble and using only water to remove oxide is not satisfactory.
For the same reasons, etching in 10 % KBr did not completely remove oxides, but treatment
with 10 % NH4Cl provided good results except for the carbon contamination. To conclude on
the oxide removal, the best results were obtained with a cyclic oxidation- rinsing- etching
procedure with H2O2 and HCl.
The analysis of the resulting roughness after treatment allowed discarding many of the abovelisted methods. For instance, a piranha exposure for 30 s dramatically damaged the Ge
surfaces leading to surface roughness of 25.5 nm presenting massive plots, while the pristine
Ge surfaces had a roughness around 0.3 nm. Among H2O2- hydrohalogenic acids cyclic
procedures, the one involving HCl provided the best results in terms of final roughness, while
HBr and HF treatments were found to be more detrimental for the surface. These results are
illustrated on Figure 2.

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III. Chemical grafting of diazonium salts on germanium

(a) RMS : 0.21 nm

(b) RMS : 25.5 nm

(c) RMS : 4.01 nm

(d) RMS : 0.47


nm

Figure 2. AFM images of as received Ge (a), piranha treated Ge, showing huge damage of the
surface (b), H2O2 (30%)/HBr (10%) cyclic procedure treated Ge, showing a smoother surface
(c) and H2O2 (30%)/HCl (10%) cyclic procedure treated Ge showing the smoothest surface
obtained(d). The differences in the vertical scales are directly related with the very large
variations in roughness between the four images
Table 1 summarizes the results obtained with the different etching methods in terms of
roughness and carbon contamination.
Table 1. Roughness and carbon contamination obtained for as received Ge and for Ge treated
with a piranha and H2O2/HBr cyclic procedure, b H2O2/HBr cyclic procedure, c H2O2/HCl
cyclic procedure, d 30% NH4Cl for 30 min, e H2O2/NH4OH cyclic procedure, f DI water for 30
min or g 30% KBr for 30 min. The H2O2/HCl cyclic procedure provides the best results both
in terms of roughness and carbon contamination.
Pristine
0.21

piranhaa
25.5

HBrb
4.01

HClc
0.47

NH4Cld
4.30

NH4OHe
10

H2Of
0.41

KBrg
1.40

Roughness
(nm)
Carbon
4942
17554
3200
2738
3344
4181
3742
3722
contamination
(counts)
To conclude with the preparation of oxide-free Ge smooth surfaces with a low C
contamination, the best results were obtained with a cyclic procedure involving 30 % H2O2
and 10 % HCl. This strategy was used for all the experiments involving the grafting of
diazonium salts.

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2. Grafting of diazonium salts.


As reported by Holmes and coworkers65, Ge nanowires can be functionalized by diazonium
salts. Here we will discuss the grafting of diazonium salts on Ge bulk surfaces and its possible
mechanism. A wider variety of diazonium salts was spontaneously grafted on Ge surfaces,
with no reducing agent and no electrochemistry to induce the grafting. XPS data demonstrate
the presence of grafted material, as the different functional groups borne by the diazonium
salts are easily detected. For instance, F 1s and C 1s spectra showed the presence of CF3-BD
(688.67 eV and 293.21 eV respectively, Fig. S9) and C8F17-BD (689.34 eV and 291.91 eV
(CF2 groups) and 294.20 eV (CF3 group) respectively, Figure 3) on the surfaces69, whereas N
1s spectra confirmed the presence of CN-BD (400.14 eV for the cyano nitrogens, Fig. S5),
DO-BD (406.08 eV for NO2 groups and 400.33 eV for N=N groups, Fig. S11), NMe2-BD
(399.27 eV for NMe2 groups, Fig. S8) and NBD (406.11 eV for NO2 groups, Fig. S6). The
presence of OMe-BD was more difficult to observe as it was only depicted in C 1s spectrum
(286.31 eV for C-O, Fig. S7). Contrary to spontaneously grafted films on gold surfaces from
diazonium salts that exhibit the presence of azo bridges, similar films on Ge surfaces do not
present such features except for BD (399.50 eV), NBD (around 400 eV as well reported in
literature, this peak arises either from a reduced form of nitro group or from the presence of
azo groups within the film70-74) and OMe-BD (399.32 eV). The absence of a peak
corresponding to the diazonium group (around 402 eV75) and the absence of azo bridges in
most of the cases suggest that the diazonium salts were actually reduced and that, in some
cases, it is possible to form azobenzene moieties inside the film. This latter phenomenon arose
only when the diazonium salt is not sterically hindered and is somehow activated by electron
donating mesomeric effects. Finally, because of the low difference in electronegativity
between aromatic carbon and Ge surface atoms, the interfacial Ge-C bond was observed
neither in Ge core levels spectra nor in C 1s spectra. We assume that such a bond is, however,
present within the film, but it could not be detected by XPS.

Figure 3. C 1s XPS core level spectrum of functionalized Ge after immersion in a 0.005 M


solution of C8F17-BD in acetonitrile at room temperature for 15 min. The spectrum exhibits
the features of the fluorinated chain (CF2 and CF3 groups) as well as the aromatic ring (Carom),
thus confirming the grafting. The presence of a C-O and a COO peak is probably due to
remaining carbon contamination at Ge surfaces prior to functionalization.
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III. Chemical grafting of diazonium salts on germanium


Regarding the grafting conditions, no heating was needed to achieve the grafting on Ge bulk
surfaces, contrary to Ge nanowires for which heating is often required as observed by Holmes
et al.. Furthermore, only 15 to 20 minutes are enough to graft bulk surfaces, when few hours
to a day are required to functionalize the Ge nanowires. Finally, the spontaneous grafted films
on bulk Ge surfaces exhibit a good stability towards reoxidation of the substrate. The obtained
results are similar to those obtained with alkanethiolate SAMs76(Fig. S12). Reoxidation of Ge
surfaces occurred after few days of air exposure and damaged the films. Indeed, Ge 3d and 2p
XPS spectra showed an important reoxidation of the Ge surface, while C 1s, F 1s and N 1s
spectra indicated a loss of organic material. Thus, diazonium salts can be used as a primer
layer that must be post-functionalized to achieve an efficient passivation of Ge surfaces. We
will now study the different parameters playing a role in the grafting process.

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3. Parametrical study
For the studies in temperature and reaction time, CN-BD was chosen for several reasons.
First, the CN group is easily detected in XPS and not affected by the X-ray beam (as nitro
groups are). Second, surfaces grafted with CN-BD, fluorinated BD (CF3- and C8F17-BD) or
BD did not show fast reoxidation, contrary to surfaces grafted with NBD or DO-BD that
presented a quite large amount of oxide (presumably arising from an oxidation of the surface
by the nitro groups). OMe-BD and BD were eliminated due to the presence of azo bridges
within the films thus leading to a mixed mechanism of grafting. Then, we chose to eliminate
fluorinated BD as fluorine could prevent radical species from grafting on already attached
fluorinated aryls.
3.1 Influence of temperature. Functionalization reactions were carried out at different
temperatures ranging from -18 C to 80 C to investigate the possible reduction of the
diazonium salts by the Ge surface and the eventual role of thermal activation on that process.
All the diazoniums salts used in the present study thermally decompose at temperatures
ranging from 88.8 C 67 to 156 C (NBD), as demonstrated by DSC studies in the solid state.
The temperature has an influence on the efficiency of the grafting, particularly with
diazonium salts more difficult to reduce (those containing an electron donating group in paraposition for example)65, 77. In our case with Ge surfaces, at room temperature, all the
diazonium salts were reactive and grafted, thus suggesting that the reduction was easier than
on Ge nanowires on which only C8F17-BD was grafted at room temperature. Furthermore, at 18 C, C8F17-BD and CN-BD were also reactive. The full study in temperature with CN-BD
showed two different behaviours, one at low temperature and one at high temperature with a
switching temperature around 30 C. The grafted layer at high temperature is either thicker or
has a higher density as depicted on Figure 4. The relative intensity of the N 1s peak
corresponding to the NC group is about five times larger above 40 C than below.

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III. Chemical grafting of diazonium salts on germanium

Figure 4. N 1s XPS core level spectra of functionalized Ge with CN-BD (0.005 M in


acetonitrile) after 15 min of immersion at different temperatures from -18 C to 80 C. 2
different regimes are depicted, one at low temperature with a moderate grafting rate, one at
higher temperature (above 40 C) with a higher grafting rate.
To understand this phenomenon, we performed DSC on CN-BD. In the solid state, CN-BD
decomposes at 114.8 C (position of the maximum) which is far too high to explain our
observations. Thus, we managed to do a DSC in acetonitrile solution. The latter DSC exhibits
a large exothermic peak at 69.5 C beginning around 50 C. Diazonium salts are thus quite
stable in the solid state, but they are far less stable in solution (for instance, NBD decomposed
at 156 C in the solid state and from 45 C only in water solution). This low stability in
solution can explain the increase in grafting, but also the two different plateaus observed in
XPS studies. These results demonstrate that (i) Ge itself is able to reduce diazonium salts until
saturation of the surface and, (ii) the thermal decomposition of diazonium salts produces aryl
cations that can graft on a previously grafted layer and lead to more grafted material and to an
increase of the N 1s peak. Finally, regarding the surface state, samples grafted below 40 C
presented a smooth and quite regular surface only exhibiting small plots. On the opposite,
samples grafted above 40C showed a rougher surface with big massive clusters and a very
irregular surface beyond the clusters (Fig. 5).

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III. Chemical grafting of diazonium salts on germanium

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F)

Figure 5. AFM images of Ge surfaces grafted with CN-BD at -18C (A) (Rq= 1.26 nm), 0C
(B) (Rq= 2.05 nm), 25C (C) (Rq= 1.43 nm), 40C (D) (Rq= 1.47 nm), 60C (E) (Rq= 6.88
nm) and 80C (F) (Rq= 5.00 nm).
3.2 Influence of the reaction time. As Ge surfaces are very sensitive substrates towards
reoxidation, we studied the influence of the grafting time on the surface to determine the
optimal reaction time. As observed with XPS on the N 1s NC signal (Figure 6), the grafting
rate quickly increases with the reaction time to reach a maximum between 10 and 15 minutes,
then decreases quickly after 15-20 minutes of grafting: the N 1s peak loses 80 % of its
intensity between 15 and 30 minutes of grafting.

76

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III. Chemical grafting of diazonium salts on germanium

Figure 6. N 1s XPS core level spectra of functionalized Ge with CN-BD (0.005 M in


acetonitrile) after immersion at room temperature for grafting times ranging from 5 to 60 min.
A maximum in the grafting rate appears around 10 to 15 min. For shorter or longer grafting
times, the grafting rate is much lower.
This can be explained by a reoxidation process (by remaining O2) occurring in solution.
Indeed, the Ge surfaces appeared more oxidized with long grafting time. Thus, the Ge
surfaces seem to be first protected by reacting with diazonium salts, but they are surprisingly
further deteriorated by long reaction times allowing reoxidation to occur. We did not observe
any evidence of the interfacial bond, but the binding environment of Ge surface atom was
similar to the one observed in temperature studies except for the presence and the growth of
oxide with increasing the grafting time. These observations are also supported by AFM
studies. The longer the grafting, the rougher and more irregular the surface. While surfaces
protected with short grafting time show regular smooth surfaces, the samples exposed for
more than 20 minutes to diazonium salt solution exhibited irregular surfaces with
accumulations and holes (Fig. 7).

77

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III. Chemical grafting of diazonium salts on germanium

Figure 7. AFM images of Ge surfaces grafted with CN-BD for 5 min (A) (Rq= 1.58 nm), 10
min (B) (Rq= 1.75 nm), 15 min (C) (Rq= 1.16 nm), 30 min (D) (Rq= 1.64 nm), 45 min (E)
(Rq= 2.28 nm) and 60 min (F) (Rq= 6.10 nm).
3.3 Influence of the group in para-position. Among the salts studied, the most striking
effect was obtained with the fluorinated diazonium salts (CF3- and C8F17-BD). Their grafting
was 5 to 10 times less efficient than the grafting of the other salts (based on the C 1s signal in
XPS). We did not observe any significant difference in the amount of grafted materials among
the other diazonium salts. However, AFM images showed different film morphologies.
Indeed, the grafting of diazonium salts bearing mesomeric withdrawing groups (CN-BD,
NBD) or no mesomeric effect (BD, CF3-BD, C8F17-BD, DO-BD) at the para-position resulted
in homogeneous films with RMS values between 1 and 1.5 nm; on the contrary the grafting of
diazonium salts containing mesomeric donating groups (OMe-BD and NMe2-BD) at the paraposition produced irregular films presenting big clusters of material along with regular
surfaces with RMS values between 4.66 and 8 nm (Figure 8).

78

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III. Chemical grafting of diazonium salts on germanium

Figure 8. AFM images of HCl-treated Ge functionalized with CN-BD (left, RMS: 1.16 nm)
and NMe2-BD (right, RMS: 5.81 nm) after 15 min of immersion at room temperature
in 0.005 M solutions in acetonitrile. Mesomeric effects of the group in para-position
induce the film morphology. Electron withdrawing groups (such as CN) provide more
homogeneous films than electron donating groups (such as NMe2).
The mesomeric donating effect thus seems to favour multilayer formation, but also promotes
azo bridges within the film as observed by XPS. Azo bridges were mainly observed with
OMe-BD (we did not observe azo bridges with NMe2-BD as the azo group peak and the
amine group peak are very close, we observed an azo peak once with BD and once with CNBD) and are presumably formed by azo coupling between the diazonium salt and the grafted
film. Such reactivity could explain the morphology obtained with NMe2-BD and OMe-BD as
the formation of azobenzene is a slow and localized process. So, when azobenzene moieties
are formed within the film, the film is irregular and the surface rougher. On one hand,
sterically hindered diazonium salts (mainly C8F17-BD and CF3-BD) prevent both the growth
of the film and the azo bridges formation, thus leading to a monolayer and a smooth surface
(around 1 nm roughness). On the other hand, the mesomerism of the adsorbate can control the
presence (mesomeric donating groups, OMe-BD and NMe2-BD) or the absence (mesomeric
withdrawing group, CN-BD and NBD or groups with no mesomeric effects, fluorinated BD,
BD and DO-BD) of azo bridges during the growth of the film. Moreover, as the presence of
azo bridges is related to the presence of clusters, the mesomeric effects can also control the
morphology of the film and the roughness of the resulting surface. Indeed, mesomeric
donating groups favour the formation of azobenzene moieties and of irregular films with a
rough surface, mesomeric withdrawing groups or groups with no mesomeric effect lead to
homogeneous films with a smooth surface. Finally, diazonium salts bearing an oxidant group
(such as NBD and DO-BD) grafted on the surface, but also oxidized Ge surface during the
process.
3.4 Binding site and absolute coverage. Besides the density of the grafted layer, one
important parameter controlling the stability of a passivating film is the coverage achieved
during the functionalization. Bent and co-workers showed that an alkanethiolate SAM does
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III. Chemical grafting of diazonium salts on germanium

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not provide full coverage of halide-terminated Ge surfaces as halogen remained on the


surface26. Furthermore, Weiss established very recently that at room temperature, the absolute
coverage of a dodecanethiol SAM on Ge(100)-2x1 reconstructed surfaces is about 50%76, and
could be improved up to 100% by increasing the temperature of functionalization. In our case,
we worked with the same Ge(100)-2x1 reconstructed surface (Fig. S13, LEED pattern) and at
room temperature, thus, we expected thiols to react at a single position of the Ge dimer as
observed by Weiss (50% coverage at room temperature). Indeed, chlorine was still detected
by XPS after functionalization by thiols, but also by diazonium salts. By using a fluorinated
thiol (CF3-(CF2)7-(CH2)2-SH) to form a SAM to be compared with C8F17-BD grafted film, we
estimated the absolute coverage obtained with diazonium salts to be similar to the one with
alkanethiols. Indeed, XPS spectra of the fluorinated SAM and of the C8F17-BD film presented
the same features (Figure 9). We detected the same amount of carbons bound to fluorine (CF2
and CF3 groups) and of fluorine in the SAM and in the film. Moreover, the quantity of
remaining chlorine was similar in both cases.

Figure 9. XPS survey spectra of a CF3-(CF2)7-(CH2)2-SH SAM on HCl treated Ge (left, zoom
on the Cl 2s region in inset) and of functionalized Ge with C8F17-BD (right, zoom on
the Cl 2s region in inset) showing the presence of remaining chlorine at the Ge
surface. The absolute coverage of SAMs and diazonium salts appears similar as the
amounts of remaining chlorine are equivalent in both cases.
As C8F17 is assumed to prevent the multi-layering, the absolute coverage achieved with this
diazonium salt is approximately the same than the one obtained with SAMs (about 50%).
Finally, we still detected a comparable amount of chlorine with all the diazonium salts used
here. Thus, the grafting process results in the formation of a 50% coverage film where, in
average, one position of the Ge dimer is occupied by an aryl ring and the other one remained
occupied by a chlorine atom. Complete coverage of the dimers is prevented by steric
hindrance from the diazonium salts. Indeed, the arenediazoniums are too bulky to graft on
both sites of the dimers. This steric effect was also observed with solvated Grignard reagents
by Holmes and co-workers27. The absolute coverage obtained with Grignard reagents has not
been determined yet, but, as chlorine was still detected in XPS, Holmes et al. assumed a
partial coverage of the Ge surface. Lewis and co-workers also showed that complete coverage
was not achieved with Grignard reagent, as they observed the presence of Ge suboxides after
80

III. Chemical grafting of diazonium salts on germanium


functionalization78. In the case of hydrogermylation, no evaluation of the coverage has been
made, but IR analysis did not show remaining Ge-H24. This reactivity is similar to the one
observed by Loscutoff et al. with isocyanate and isothiocyanate derivatives at Ge(100) 2x1
surfaces where only one of the sites of the dimer pairs is occupied before dissociation 79, 80.
This similar binding can explain the similar stability of the films observed for thiol-based
SAMs and diazonium-based grafted films on Ge.

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4. Process of grafting.
Following our different observations on the influence of the temperature and the grafting
time, the functionalization of Ge surfaces by diazonium salts is self-limitating, suggesting that
Ge itself plays an important role in the process. Moreover, the morphology of the grafted
films which do not contain azo bridges indicates that a dediazoniation took place during the
grafting. Finally, the fact that the functionalization is still observed at low temperature (where
it is unlikely to thermally activate the diazonium salts) gives support to a potential reduction
of the salts by Ge itself. Thus, with all our results, the mechanism involving homolytic
dediazoniation through electron transfer81 from Ge surface is the most likely to occur. Such a
mechanism has already been proposed on H-terminated Ge nanowires as well as on Hterminated Si64, 65. Our observations are consistent with this scenario as at low temperature a
thinner layer is obtained82, 83. The absence of azo bridges even at low temperature is consistent
with a full reduction of diazonium salts by Ge surface as well as the self-limitating process
provides evidence for the involvement of an electron transfer from Ge surface to the
diazonium salt. Finally, the increase in the thickness of the layer with temperature can be
explained by thermal activation of the diazonium salt that produces aryl cations or radicals 84,
85
reactive towards the phenyl layer already grafted. The formation of the film is illustrated on
Figure 10.
R

R
Cl

Cl

Ge

Cl

Cl

Cl

N2+

Cl

Ge

Figure 10. Scheme of the spontaneous grafting of diazonium salts on Cl-terminated


Ge surface and structure of the grafted film obtained.
On the other hand, one could propose a heterolytic dediazoniation yielding to aryl cations that
should be able to graft on the surface. As reported by Ishida et al.86, arenediazonium salts in
acetonitrile solution exposed to heating preferentially decompose in cations through a
heterolytic pathway. However, our observations at -18 C suggest that, even at this
temperature at which the role of thermal activation should be very limited, the dediazoniation
process occurred. Furthermore, our DSC experiment revealed that the decomposition of
81

III. Chemical grafting of diazonium salts on germanium


diazonium salts in acetonitrile solution arose only above 35-40 C, thus excluding the thermal
activation of the salt to be the only source of grafting. Although this mechanism is plausible
and is probably involved in the growth of the film, the low temperature successful grafting
strongly supports the reduction pathway.

5. Comparison with grafting on gold


The diazonium salts were also grafted on gold. Even if gold is not reducing enough to reduce
diazonium salts, a spontaneous grafting was observed. The main difference in the film
morphology lies in the presence of azo bridges within the film but also at the interface
through an Au-N bond as depicted in Fig. 11. This binding mode was never observed with Ge
confirming a different reactivity of the substrates towards diazonium salts. Concomitantly,
azo ridges were very rarely observed with Ge thus further supporting the reduction pathway
proposed.
15800

N 1s

Au-N
N=N / NH2

15600

NO2

15400

CPS

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To conclude on the mechanism, while more experiment would be suitable to eliminate any
ambiguity, we believe that the diazonium salts are reduced by Ge itself, producing aryl
radicals that eventually graft on the surface. The film then grows by addition of extra aryl
radicals on the grafted aryl layer. This process stops when electron transfer is blocked.
Nevertheless, thermal activation can still play a role by producing aryl cations or radicals that
can further react with the grafted layers. This mechanism involves the formation of
germanium surface-based radicals and is expected to be similar to the mechanism on
silicon87, 88. Aryl radicals and germanium radicals are formed during the reduction process
and recombine to produce the grafted film. The growth of the film can be controlled by
introducing sterically hindered groups that prevents multilayering. Azo bridges can be formed
through diazo coupling when using mesomeric donating substituent.

15200

15000

14800
410

408

406

404

402

400

398

396

394

Binding Energy (eV)

Figure 11. XPS N 1s core level spectrum of spontaneously grafted NBD on gold
from a 5.10-3 M solution in water.
Experiments conducted at -18 C in acetonitrile to avoid diazonium salt thermal
decomposition (which in fact occurs at 45 C for NBD in acetonitrile) confirmed the
82

III. Chemical grafting of diazonium salts on germanium


possibility of grafting diazonium salts through Au-N bonds. Indeed, 100 % of the grafted
phenyl rings are linked through this mode both with NBD and CF3-BD as observed from the
areas recorded by XPS (Table 2). This result showed that a simple dipping of gold in a
diazonium salt solution results in the grafting of the salts via a direct Au-N bond.
Table 2. XPS C 1s and N 1s core level areas (a.u.) for grafting of NBD and CF3-BD at -18 C
from 5.10-3 M solution in acetonitrile.

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NBD
CF3-BD

Au-N
351
130

N=N
380
124

NO2 + NH2
310
-

CF3
111

However, when performing experiments at room temperature, even if Au-N bonds and azo
bridges are still observed, an important part (about 50 %) of the phenyl rings are not grafted
through azo bridges. As no C-Au bond was observed, Au-N remains the only interfacial bond
recorded. Nevertheless, an Au-C bond can still be assumed, the non-observation arising from
the slight difference in electronegativity between C and Au thus preventing the observation by
XPS of the Au-C bond (such a bond is probably merged with the main carbon peak). Despite
the unclear binding to gold surface, the result clearly underlines that a dediazoniation
occurred during the grafting, as in the case of germanium. However, whereas this process
arises from the reduction of the diazonium salt by the substrate with germanium, the reduction
must be prevented with gold due to low reducing potential of this metal. Therefore, another
mechanism has to be considered. As stated before in the article, diazonium salts can lose their
N2 part either through a heterolytic pathway yielding to aryl cations or by a homolytic route
leading to aryl radicals. Both species are then able to graft on surfaces and already attached
phenyl moieties. However, in the conditions of grafting employed, the formation of aryl
radicals from diazonium salts is very improbable and was thus discarded.
Combining all these results, a mechanism for the film formation can be proposed. In a first
step, diazonium salts directly graft on the gold surface through Au-N bonds. At the same time,
if the grafting is performed at room temperature, the possibility of attaching aryl cations
through Au-C bonds must also be considered. This leads to a first layer of phenyl moieties
linked by azo bridges or directly on the surface (azo bridges only at low temperature,
presumably both modes at higher temperatures). In a second time, aryl cations and diazonium
salts graft on the previously formed phenyl layer, the latter being attached through azo
coupling. The mechanism is presented on Figure 12.

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III. Chemical grafting of diazonium salts on germanium

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Figure 12. Mechanism of grafting of diazonium salts (represented here with NBD) on gold
surfaces.
To conclude, both germanium and gold are spontaneously grafted by diazonium salts but their
behaviour is different. Where germanium itself reduces diazonium salts to produce aryl
radicals that grafted on the surface through a Ge-C bond and later on the formed phenyl layer,
gold is functionalized directly by diazonium salt through an Au-N bond and by thermally
formed aryl cations through an Au-C bond. The growth of the film on gold occurs through azo
coupling and coupling of aryl cations on already grafted phenyl moieties whereas in the case
of germanium, aryl radicals arising from the reduction of the diazonium salt by the substrate
react with already attached phenyl rings. Gold and germanium showed a very different
behaviour toward spontaneous grafting of diazonium salts mainly due to their very different
reducing potential.
CONCLUSIONS
We investigated preparation and organic functionalization of Ge surfaces by arenediazonium
salts. XPS and AFM results indicate that the preparation of Ge samples is sensitive to the
reactants used in terms of roughness and in terms of oxide removing. As the roughness is a
key parameter for further applications, relatively mild conditions are required to properly
remove oxide from the surface without alteration. A cyclic oxidation rinsing etching
procedure with 30 % H2O2 and 10 % HCl yields oxide-free smooth Cl-terminated surfaces. It
was possible to further functionalize these surfaces with various arenediazonium salts. The
spontaneous reduction of the salts, even at room temperature, gives rise to grafted organic
films on Ge surfaces that were identified by XPS analysis. An AFM and an XPS study
demonstrated that the surface state and the thickness of the layer were dependent on the
temperature, the reaction time and the electronic effects of the substituent borne by the
diazonium salt. At low temperature, the film is grafted through the reduction of diazonium
salts by Ge itself. This process is still involved at higher temperature, but it is coupled with
the thermal activation of the salt. Long grafting times resulted in a poor quality film and in a
reoxidation of the surface, where short reaction times yielded smooth regular surfaces.
Finally, sterically hindered aromatic rings limit the thickness of the layer, and mesomeric
donating groups favoured the formation of azo bridges. Oxidizing substituents lead to a
reoxidation of the surfaces during the grafting. The absolute coverage was determined and
found to be similar to the coverage achieved with thiols (around 50 %). The results described
84

III. Chemical grafting of diazonium salts on germanium


here demonstrate the potential of arenediazonium salts as functionalization agents of Ge
surfaces. Furthermore, the thickness of the film may be controlled by either the nature of the
chosen salt or the grafting conditions. On the other hand, we also demonstrated that the
stability of the protective layer is not good enough for further application in nanoelectronics
and must be enhanced by post-functionalization. Arenediazonium salts are promising as
adhesion layer for forming a protective film on Ge surfaces due to the strong binding
developed, but an additional functionalization step must be carried out to achieve complete
passivation of Ge surfaces.

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ACKNOWLEDGMENTS
We are indebted to the Ministry of Higher Education and Research (MESR) for the Ph. D.
funding of XL. This work has been also financially supported by the Region Ile-de-France in
the framework of CNano IdF through PIGe III-V project. CNano IdF is the nanoscience
competence centre of Paris Region, supported by CNRS, CEA, MESR and Region Ile-deFrance. This work was supported by ANR SAGe III-V (Grant ANR Blanc 2011). Jocelyne
Leroy is thanked for the LEED experiment.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.

D. Schmeisser, R. D. Schnell, A. Bogen, F. J. Himpsel, D. Rieger, G. Landgren and J.


F. Morar, Surf. Sci., 1986, 172, 455-465.
S. Rivillon, Y. J. Chabal, F. Amy and A. Kahn, Appl. Phys. Lett., 2005, 87, 253101253103.
S. Sun, Y. Sun, Z. Liu, D.-I. Lee, S. Peterson and P. Pianetta, Appl. Phys. Lett., 2006,
88, 021903-021903.
Y. F. Lu, Z. H. Mai, W. D. Song and W. K. Chim, Appl. Phys. A: Mater. Sci. Process.,
2000, 70, 403-406.
D. Bodlaki, H. Yamamoto, D. H. Waldeck and E. Borguet, Surf. Sci., 2003, 543, 6374.
D. E. Aspnes and A. A. Studna, Appl. Phys. Lett., 1981, 39, 316-318.
T. Hanrath and B. A. Korgel, J. Am. Chem. Soc., 2004, 126, 15466-15472.
H. C. Choi and J. M. Buriak, Chem. Commun., 2000, 1669-1670.
T. Deegan and G. Hughes, Appl. Surf. Sci., 1998, 123-124, 66-70.
Z. H. Lu, Appl. Phys. Lett., 1996, 68, 520-522.
H. Jagannathan, J. Kim, M. Deal, M. Kelly and Y. Nishi, ECS Trans., 2006, 3, 11751180.
P. Ardalan, C. B. Musgrave and S. F. Bent, Langmuir, 2009, 25, 2013-2025.
T. Akane, J. Tanaka, H. Okumura and S. Matsumoto, Appl. Surf. Sci., 1997, 108, 303305.
H. Okumura, T. Akane and S. Matsumoto, Appl. Surf. Sci., 1998, 125, 125-128.
H. Seo, K. B. Chung, J. P. Long and G. Lucovsky, J. Electrochem. Soc., 2009, 156,
H813-H817.
G. W. Anderson, M. C. Hanf, P. R. Norton, Z. H. Lu and M. J. Graham, Appl. Phys.
Lett., 1995, 66, 1123-1125.
85

III. Chemical grafting of diazonium salts on germanium


17.
18.
19.
20.
21.
22.
23.
24.
25.

tel-00782709, version 1 - 30 Jan 2013

26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.

X. J. Zhang, G. Xue, A. Agarwal, R. Tsu, M. A. Hasan, J. E. Greene and A. Rockett,


J. Vac. Sci. Technol., A, 1993, 11, 2553-2561.
N. A. Tabet, M. A. Salim and A. L. Al-Oteibi, J. Electron Spectrosc. Relat. Phenom.,
1999, 101-103, 233-238.
K. Prabhakaran, F. Maeda, Y. Watanabe and T. Ogino, Appl. Phys. Lett., 2000, 76,
2244-2246.
K. Prabhakaran and T. Ogino, Surf. Sci., 1995, 325, 263-271.
B. P. Swain, H. Takato, Z. Liu and I. Sakata, Sol. Energy Mater. Sol. Cells, 2011, 95,
84-88.
K. Park, Y. Lee, J. Lee and S. Lim, Appl. Surf. Sci., 2008, 254, 4828-4832.
G. W. Cullen, J. A. Amick and D. Gerlich, J. Electrochem. Soc., 1962, 109, 124-127.
K. Choi and J. M. Buriak, Langmuir, 2000, 16, 7737-7741.
S. M. Han, W. R. Ashurst, C. Carraro and R. Maboudian, J. Am. Chem. Soc., 2001,
123, 2422-2425.
P. Ardalan, Y. Sun, P. Pianetta, C. B. Musgrave and S. F. Bent, Langmuir, 2010, 26,
8419-8429.
G. Collins, P. Fleming, S. Barth, C. O'Dwyer, J. J. Boland, M. A. Morris and J. D.
Holmes, Chem. Mater., 2010, 22, 6370-6377.
V. C. Holmberg and B. A. Korgel, Chem. Mater., 2010, 22, 3698-3703.
J. L. Bahr, J. Yang, D. V. Kosynkin, M. J. Bronikowski, R. E. Smalley and J. M. Tour,
J. Am. Chem. Soc., 2001, 123, 6536-6542.
J. K. Kariuki and M. T. McDermott, Langmuir, 1999, 15, 6534-6540.
J. J. Gooding, Electroanalysis, 2008, 20, 573-582.
A. J. Downard, Electroanalysis, 2000, 12, 1085-1096.
J. Lyskawa and D. Blanger, Chem. Mater., 2006, 18, 4755-4763.
G. Z. Liu, T. Bocking and J. J. Gooding, J. Electroanal. Chem., 2007, 600, 335-344.
A. Laforgue, T. Addou and D. Blanger, Langmuir, 2005, 21, 6855-6865.
A. Adenier, M.-C. Bernard, M. M. Chehimi, E. Cabet-Deliry, B. Desbat, O.
Fagebaume, J. Pinson and F. Podvorica, J. Am. Chem. Soc., 2001, 123, 4541-4549.
K. Boukerma, M. M. Chehimi, J. Pinson and C. Blomfield, Langmuir, 2003, 19, 63336335.
A. Chauss, M. M. Chehimi, N. Karsi, J. Pinson, F. Podvorica and C. Vautrin-Ul,
Chem. Mater., 2001, 14, 392-400.
S. Maldonado, T. J. Smith, R. D. Williams, S. Morin, E. Barton and K. J. Stevenson,
Langmuir, 2006, 22, 2884-2891.
A. Merson, T. Dittrich, Y. Zidon, J. Rappich and Y. Shapira, Appl. Phys. Lett., 2004,
85, 1075-1076.
P. Abiman, G. G. Wildgoose and R. G. Compton, J. Phys. Org. Chem., 2008, 21, 433439.
C. G. R. Heald, G. G. Wildgoose, L. Jiang, T. G. J. Jones and R. G. Compton,
ChemPhysChem, 2004, 5, 1794-1799.
A. T. Masheter, G. G. Wildgoose, A. Crossley, J. H. Jones and R. G. Compton, J.
Mater. Chem., 2007, 17, 3008-3014.
M. Pandurangappa and T. Ramakrishnappa, Mater. Chem. Phys., 2010, 122, 567-573.
86

III. Chemical grafting of diazonium salts on germanium


45.
46.
47.
48.
49.
50.

tel-00782709, version 1 - 30 Jan 2013

51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.

G. G. Wildgoose, N. S. Lawrence, H. C. Leventis, L. Jiang, T. G. J. Jones and R. G.


Compton, J. Mater. Chem., 2005, 15, 953-959.
G. G. Wildgoose, H. C. Leventis, I. J. Davies, A. Crossley, N. S. Lawrence, L. Jiang,
T. G. J. Jones and R. G. Compton, J. Mater. Chem., 2005, 15, 2375-2382.
C. Galli, Tetrahedron Lett., 1980, 21, 4515-4516.
A. Mesnage, S. Esnouf, P. Jegou, G. Deniau and S. Palacin, Chem. Mater., 2010, 22,
6229-6239.
A. Adenier, N. Barr, E. Cabet-Deliry, A. Chauss, S. Griveau, F. Mercier, J. Pinson
and C. Vautrin-Ul, Surf. Sci., 2006, 600, 4801-4812.
A. Adenier, E. Cabet-Deliry, A. Chauss, S. Griveau, F. Mercier, J. Pinson and C.
Vautrin-Ul, Chem. Mater., 2005, 17, 491-501.
P. Allongue, M. Delamar, B. Desbat, O. Fagebaume, R. Hitmi, J. Pinson and J.-M.
Savant, J. Am. Chem. Soc., 1997, 119, 201-207.
F. Barriere and A. J. Downard, J. Solid State Electrochem., 2008, 12, 1231-1244.
P. A. Brooksby and A. J. Downard, Langmuir, 2004, 20, 5038-5045.
J. R. Lomeda, C. D. Doyle, D. V. Kosynkin, W.-F. Hwang and J. M. Tour, J. Am.
Chem. Soc., 2008, 130, 16201-16206.
J. Lehr, D. J. Garrett, M. G. Paulik, B. S. Flavel, P. A. Brooksby, B. E. Williamson
and A. J. Downard, Anal. Chem., 2010, 82, 7027-7034.
G. Chamoulaud and D. Blanger, J. Phys. Chem. C, 2007, 111, 7501-7507.
C. Combellas, M. Delamar, F. Kanoufi, J. Pinson and F. I. Podvorica, Chem. Mater.,
2005, 17, 3968-3975.
J. Lehr, B. E. Williamson, B. S. Flavel and A. J. Downard, Langmuir, 2009, 25,
13503-13509.
D. M. Shewchuk and M. T. McDermott, Langmuir, 2009, 25, 4556-4563.
J. Charlier, E. Clolus, C. Bureau and S. Palacin, J. Electroanal. Chem., 2009, 625, 97100.
P. Allongue, C. H. de Villeneuve, G. Cherouvrier, R. Cortes and M. C. Bernard, J.
Electroanal. Chem., 2003, 550, 161-174.
P. Allongue, C. H. de Villeneuve, J. Pinson, F. Ozanam, J. N. Chazalviel and X.
Wallart, Electrochim. Acta, 1998, 43, 2791-2798.
R. Haight, L. Sekaric, A. Afzali and D. Newns, Nano Letters, 2009, 9, 3165-3170.
M. P. Stewart, F. Maya, D. V. Kosynkin, S. M. Dirk, J. J. Stapleton, C. L. McGuiness,
D. L. Allara and J. M. Tour, J. Am. Chem. Soc., 2003, 126, 370-378.
G. Collins, P. Fleming, C. O'Dwyer, M. A. Morris and J. D. Holmes, Chem. Mater.,
2011, 23, 1883-1891.
M. Min, G. S. Bang, H. Lee and B.-C. Yu, Chem. Commun., 2010, 46, 5232-5234.
A. Houmam, Chem. Rev., 2008, 108, 2180-2237.
F. Carey and R. Sundberg, in Advanced Organic Chemistry, eds. F. A. Carey and R. J.
Sundberg, Springer US, 2002, pp. 123-185.
Y.-G. Lei, K.-M. Ng, L.-T. Weng, C.-M. Chan and L. Li, Surf. Interface Anal., 2003,
35, 852-855.
V. Mvellec, S. Roussel, L. Tessier, J. Chancolon, M. Mayne-L'Hermite, G. Deniau,
P. Viel and S. Palacin, Chem. Mater., 2007, 19, 6323-6330.
87

III. Chemical grafting of diazonium salts on germanium


71.
72.
73.
74.
75.
76.
77.
78.

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79.
80.
81.
82.
83.
84.
85.
86.
87.
88.

L. Tessier, G. Deniau, B. Charleux and S. Palacin, Chem. Mater., 2009, 21, 42614274.
S. S. C. Yu, E. S. Q. Tan, R. T. Jane and A. J. Downard, Langmuir, 2007, 23, 1107411082.
S. S. C. Yu, E. S. Q. Tan, R. T. Jane and A. J. Downard, Langmuir, 2008, 24, 70387038.
S. Q. Lud, M. Steenackers, R. Jordan, P. Bruno, D. M. Gruen, P. Feulner, J. A.
Garrido and M. Stutzmann, J. Am. Chem. Soc., 2006, 128, 16884-16891.
S. Szunerits and R. Boukherroub, J. Solid State Electrochem., 2008, 12, 1205-1218.
J. N. Hohman, M. Kim, H. R. Bednar, J. A. Lawrence, P. D. McClanahan and P. S.
Weiss, Chem. Sci., 2011, 2, 1334-1343.
C. Galli, Chem. Rev., 1988, 88, 765-792.
D. Knapp, B. S. Brunschwig and N. S. Lewis, J. Phys. Chem. C, 2010, 114, 1230012307.
P. W. Loscutoff, K. T. Wong and S. F. Bent, J. Phys. Chem. C, 2010, 114, 1419314201.
P. W. Loscutoff, K. T. Wong and S. F. Bent, Surf. Sci., 2010, 604, 1791-1799.
H. Zollinger, Angew. Chem., Int. Ed. Engl., 1978, 17, 141-150.
F. Anariba, U. Viswanathan, D. F. Bocian and R. L. McCreery, Anal. Chem., 2006,
78, 3104-3112.
M.-C. Bernard, A. Chauss, E. Cabet-Deliry, M. M. Chehimi, J. Pinson, F. Podvorica
and C. Vautrin-Ul, Chem. Mater., 2003, 15, 3450-3462.
S. Milanesi, M. Fagnoni and A. Albini, Chem. Commun., 2003, 216-217.
S. Milanesi, M. Fagnoni and A. Albini, J. Org. Chem., 2004, 70, 603-610.
K. Ishida, N. Kobori, M. Kobayashi and H. Minato, Bull. Chem. Soc. Jpn., 1970, 43,
285-286.
R. Hunger, W. Jaegermann, A. Merson, Y. Shapira, C. Pettenkofer and J. r. Rappich,
J. Phys. Chem. B, 2006, 110, 15432-15441.
D. Wang and J. M. Buriak, Langmuir, 2006, 22, 6214-6221.

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IV. Electrografting of diazonium salts on


germanium surfaces and grafting of the pushpull systems

IV.1 Electrografting of diazonium salts on Ge..89


IV.1.1 Influence of the group in para-position..95
IV.1.2 Absolute coverage...97
IV.2 Comparison with spontaneous grafting on Ge..98
IV.3 Grafting of the push-pull systems...99
IV.4 Conclusion..105

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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


First described by Elofson1 in 1958 and later popularized by Delamar et al.2,3, the
electrografting of diazonium salts is a widely used process to functionalize a surface. Indeed,
besides their interest in dyes synthesis, diazonium salts can also be reduced to form aryl
radicals able to graft on a large scope of surfaces. In the case of electrografting, the reduction
is performed at the surface of the electrode which is then functionalized by the formed
radicals. Whereas in the chemical grafting process (by using a reducer in solution) the radicals
are produced throughout the solution, their arising close to the surface in the electrografting
prevents most of the reactions in solution (such as radical coupling) from occurring. This
leads to the formation of thicker and/or denser films, the electrode being finally deactivated
by the layer2,4 (no electron can be further transferred to the solution). This could be an
interesting point for passivation and insulation applications. However, electrografting of
diazonium salts presents some drawbacks. First of all, even if the scope is very large, it is
limited to conducting or semi-conducting substrates. Then, the control of the film growth is
often impossible, thus making monolayers very difficult to achieve. Different approaches
were developed to obtain near monolayers instead of multilayers59. Despite these facts, the
electrografting of diazonium salts has been widely studied. Indeed, from conductors to semiconductors, a large variety of substrates have been grafted: metals 1018, semi-conductors such
as Si1922 or AsGa23, carbon materials such as HOPG24,25, graphene2629, glassy carbon4,24,30,31,
carbon fibers3,32, carbon nanotubes33 or diamond3440, oxidized surfaces such as ITO41, SnO242
or TiO243, and even dielectrics like polyethylene44, Teflon45 or SiO244. Nevertheless,
electrografting of diazonium salts has never been applied to germanium.
Regarding the functionalization of surfaces, whereas with simple molecules it has been widely
studied for long, the grafting of push-pull systems, and in particular with control of their
orientation, has been developed only over the last decades. Nevertheless, donor-acceptor
systems have been attached to various substrates via some of the previously described
techniques. Indeed, both covalent and non-covalent interactions between the molecule and the
surface. Depending on the targeted application, different methods are available. For instance,
for second harmonic generation, sulfonylated stilbenes were deposited on a surface through a
Langmuir-Blodgett film46. However, most of the immobilizations were realized with a
covalent bond. Promoting such an interaction often required the modification of the push-pull
system with an anchoring group. Kumar et al.47 introduced an alkanethiol on an azobenzene
moiety to form SAMs on gold and study the photoisomerization of azobenzenes.
Nevertheless, despite a large range of applications, push-pull systems grafting was mostly
studied in organic electronics to create dye-sensitized solar cells, memory devices or
dielectrics. For photovoltaic applications, as the most used substrates are oxides (mainly
TiO2), the donor-acceptor molecules were modified with a carboxylic acid group4850;
whereas, for memories on Si, a diazonium group was introduced5153. Finally, to form
dielectrics based on push-pull systems, Marks and his group developed two approaches: a
non-covalent based on the interaction of pyridine moiety with Si54 or with a carboxylic acid
group55, and a covalent based on organosilanes as anchoring group on siloxane-derived
surfaces5662. These two approaches both allowed a fine control of the dipole orientation
towards the surface but required a cross-linking step to reinforce the structure and only
allowed a layer-by-layer deposition. However, grafting of push-pull systems on a surface has
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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


a wide scope of applications especially in organic electronics. Therefore, techniques are
studied to attach these systems on a surface with controlling the dipole orientation.
In this chapter, in a first part, the electrografting process on germanium will be presented and
discussed in terms of stability of the layer, ease of grafting regarding the group borne in paraposition and morphology of the obtained films. Then, this process will be compared to the
spontaneous grafting described in Chapter III and to the well-studied electrografting of
diazonium salts on gold. Finally, the push-pull systems synthesized in Chapter II will be
grafted on gold and germanium and studied by electrochemistry.

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IV.1 - Electrografting of diazonium salts on Ge


The electrografting process was studied on two different germanium substrates: Ge(100)
wafers (with a resistivity of 1-30 .cm-1) and n-doped Ge(100) wafers (with a resistivity of
0.39-0.45 cm-1) cut in crystals of approximately 1x1 cm. The cyclic etching procedure
described in Chapter III was used both on pristine and n-doped germanium to remove the
native oxide.
Electrografting was performed by cyclic voltammetry between 0.3 V (0 V on Ge to avoid
reoxidation) and -0.6 V or -2 V (to overcome the over potential observed on germanium). All
the diazonium salts studied in the spontaneous grafting described previously were used and
grafted in these conditions. The grafting was confirmed by the cyclic voltammograms (CV)
evolving with the number of cycles. Indeed, the reduction peak observed on the first scan
disappeared through the formation of a thin insulating film on the electrode. Thus, on the
second and the others no reduction peak can be observed. It is worse to note that the current
observed for a similar surface area on undoped Ge were much lower than those on doped Ge
due to the higher resistivity as illustrated on Fig. 1 in the case of C8F17-BD.

Figure 1. CVs of C8F17-BD on n-doped germanium (left) and pristine germanium (right)
Nevertheless, grafting proceeded on both substrates leading to progressive or direct
passivation of the surface regarding the para-group. Except for BD, results obtained on ndoped Ge were similar to those on carbon (2 mm diameters electrodes) and gold (3 mm
diameter electrodes) except for the position of the reduction peak which was shifted towards
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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


more negative values and sometimes regarding the passivation. Indeed, the over potential
induced by germanium prevented the complete passivation of the surface when the reduction
potential of the diazonium salt was not reached. The two peaks observed in the case of gold
for NBD coming from the different crystal facets of the samples63 were never observed on
germanium. Table 1 that presents the different CVs obtained with all the diazonium salts on
the different substrates shows two comportments in function of the used diazonium salt. Full
passivation was achieved at the first cycle for NBD, C8F17-BD and DO-BD since no more
current was detected on the second cycle, whereas the surface was progressively passivated
with the other salts. Surprisingly, for BD, the passivation was not achieved on germanium, the
same effect was observed on gold and carbon, even if, in the latter cases, the reduction peak
was sometimes fully visible.
Table 1. CVs of the diazonium salts on carbon, gold and n-doped germanium

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On carbon

On gold

On n-doped germanium

BD

CN-BD

NBD
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OMe-BD

NMe2-BD

CF3-BD

C8F17-BD

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DO-BD
XPS data confirm the presence of grafted material as observed from the cyclic
voltammograms. Indeed, as previously, the different functional groups were easily detected
by XPS, both on pristine and doped germanium, providing similar signatures like for fluorine
derivative (Fig. 2). Generally, the films grown on pristine Ge were found slightly thicker (or
denser) than their n-doped counterparts (Fig. 2). The covered germanium was less visible in
XPS and the amount of detected carbon more important in the pristine based samples.
However, this effect could also arise from the more oxidized surfaces of the doped
germanium that limited the grafting to oxide-free regions, thus decreasing the amount of
grafted material. Indeed, because of the doping, n-doped germanium is more susceptible to
reoxidation than the already sensitive pristine germanium. Generally the XPS spectra shows
that the n doped germanium substrates are more oxidized than the undoped.

Figure 2. XPS C1s core level spectra of C8F17-BD electrografted on n-doped germanium
(left) and pristine germanium (right).
Regarding the film composition, no remaining diazonium salt was found (no peak around 402
eV), but azo bridges were observed in the case of BD, NBD, OMe-BD, CF3-BD, CN-BD and
C8F17-BD. Due to the presence of an azo bridge within the molecule, no evidence was found
for the presence of azo bridges between the moieties in DO-BD films. However, their
occurrence could not be discarded. Azo bridges were present inside the film in most of the
cases as it has already been observed on other substrates31,6466. Those bridges probably arose
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from the electroreduction of the diazonium salt forming the diazenyl radical which then grafts
on the already attached phenyl rings. The possibility of diazo coupling can also explain the
presence of azo bridges within the film, but, as those bridges were rarely observed in the
spontaneous grafting, the diazo coupling reaction may be prevented by the steric hindrance
and thus not be involved in the film formation. Finally, as in the case of spontaneous grafting,
due to the low difference of electronegativity between aromatic carbon and Ge surface atoms,
the assumed interfacial Ge-C bond was not observed by XPS.
Regarding the robustness of the film, the electrografted films on n-doped Ge surfaces exhibit
a good stability towards reoxidation of the substrate. Indeed, after 63 h of air exposure of a
C8F17-BD derived film, the surface only showed a slight reoxidation as illustrated on Fig. 3 by
the Ge 3d core level spectra. The obtained results are better than those obtained with
spontaneous grafted films in which the reoxidation occurred more quickly. Thus,
electrografting of diazonium salts can be used to achieve an efficient passivation of Ge
surfaces. However, the specific nature of the diazonium salt (containing a long fluorinated
chain acting as O2 barrier) must also been taken into account when considering the stability.
Push-pull systems may not provide such passivating layers.

Figure 3. Ge 3d core level spectra of a C8F17-BD electrografted film after air exposure.
For the mechanism of the film formation, the involvement of spontaneous grafting cannot be
discarded. Indeed, as described before, a simple dipping of a Ge sample in a diazonium salt
solution is enough to graft a thin film on the surface. Therefore before the polarization, the
first layer of the grafted film probably arose from the spontaneous grafting process whereas
the further growth is due to the electrochemical process.
Finally, pushing the potential down to -2 V forced the grafting and the passivation of the
surface after the first cycle (Tab. 2). Indeed, when cycling down to -0.6 V, the over potential
was not overcome for OMe-BD, CF3-BD, BD, CN-BD and NMe2-BD and the passivation not
achieved; whereas, when cycling down to -2 V, the reduction peak appeared and the
passivation was reached after the first cycle. Moreover, even if the passivation was not
observed on gold or carbon, when pushing to -2 V, the passivation was systematically
observed on germanium. Therefore, to obtain passivating thin films on germanium from
diazonium salts, CV between 0 and -2 V is a reliable method and will be used to graft the
push-pull derived salts.
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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


Table 2. CVs of BD, CF3-BD, OMe-BD, CN-BD and NMe2-BD on germanium between 0
and -0.6 V and between 0 and -2 V.
From 0 to -0.6 V

From 0 to -2 V

BD

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CF3-BD

OMe-BD

CN-BD

NMe2-BD

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IV.1.1 - Influence of the group in para-position


The influence of the group in para-position on the electrografting process and the film
morphology was studied by XPS and AFM. However, the first differences were already
observed on the CVs during the electrografting. Indeed, as the group borne by the diazonium
salt directly impacts the reduction potential, we observed these variations on the CVs.
Electron attractor containing salt were reduced at higher potentials (between -0.5 V and 0 V)
than the electron donor containing (under -0.5 V on Ge). Regarding the passivation, when
cycling at -0.6 V, it was not achieved with the electron donor containing salts (including BD)
and progressively with the others; whereas at -2 V, passivation was reached with all the salts.
XPS analyses with an analysis depth of 15 nm confirmed this trend as a wide disparity was
obtained. For instance, BD and NMe2-BD apparently gave very thin films as the germanium
is still very apparent in XPS whereas DO-BD, CN-BD and C8F17-BD led to thicker and/or
denser films as no germanium is detected by XPS. CF3-BD and OMe-BD showed
intermediate results. Surprisingly, the most sterically hindered diazonium salt (C8F17-BD) led
to the formation of the thickest/densest film whereas the less hindered (BD) exhibited the
thinnest film (Fig. 4).

Figure 4. XPS survey and Ge2p core level (inset) spectra of n-doped germanium grafted with
C8F17-BD (left) and BD (right).
Regarding the morphology of the films, once again, the most homogeneous was obtained
with the fluorinated diazonium salt (2.98 nm RMS, Fig. 5, a)), but, this time, BD derived
films also presented a low roughness (3.78 nm RMS, Fig. 5, b)) and a good homogeneity. On
the contrary, the films obtained with the other salts showed roughness between 10.8 and 16.7
nm and presented a very irregular surface with clusters of highly-grafted material and regions
of low grafting (Fig. 5, c)-e)). However, no clear effect of the steric hindrance of the paragroup on the film morphology or on the film thickness was underlined by our results.

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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems

a)

b)

a)

d)

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c)

e)

Figure 5. AFM images of Ge electrografted with a) C8F17-BD, b) BD, c) CF3-BD, d) CN-BD


and e) DO-BD
This tendency was also confirmed by the chemical composition of the films. Azo bridges are
currently observed in grafted films, often being favoured by low steric hindering groups.
However, in the case of electrografting on germanium, this trend was no longer observed as
fluorinated diazonium salts led to formation of films containing azo bridges. If the
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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


observation of azo bridges in BD, NBD, CN-BD and OMe-BD derived films was not
surprising, their occurrence in CF3-BD and moreover in C8F17-BD derived films was not
expected as these groups are sterically much hindered. This suggested that the formation of
azo bridges was no longer governed by the steric effects, but, as the process involved
electroreduction, by the stability of the formed diazenyl radical and its ability to graft on
already attached phenyl layers. Finally, as for the film morphology, no clear effect of the
steric hindrance of the para-group was observed on the occurrence or the absence of azo
bridges. Furthermore, their presence could not be related to the film morphology or the
differences in CVs. The film growth is thus strongly related to the stability of the radical
intermediates. The more stable the aryl radical, the thicker the film. Concomitantly, the more
stable the diazenyl radical, the more azo bridges are present within the film. Attracting
electronic effects of the para-group probably stabilize the radical intermediates, thus leading
to thicker films whereas donating effects destabilize them and led to thinner films. The case of
BD is somehow surprising as the films obtained are very thin even if the CVs showed a
passivation. However, in the case of the other salts, the described effects can be related to the
CVs between 0 and -0.6 V. The CVs are thus related to the density of the film and not directly
to their thickness. The higher thickness of the C8F17-BD derived film can be explained by the
fact that the layer never fully passivated the surface towards electron transfer. The steric
hindrance of the diazonium salt probably prevented the formation of a compact layer, thus
allowing the continuous reduction of the salt in solution. This continuous process induced a
huge provision of quite stable diazenyl and aryl radicals that grafted on the growing layer. A
thicker layer was thus obtained but was probably less dense than the one obtained with less
hindered salts. On the contrary, layers obtained with salts forming less stable radicals were
thinner due to the shorter lifetime of the active species that prevented their grafting on the
surface.
IV.1.2 - Absolute coverage
As in the case of the spontaneous grafting, the coverage is still an important parameter
regarding the stability of the layer. Indeed, the 50% coverage achieved with SAMs must be at
least reached to ensure a good passivation. In the case of the electrografting of diazonium
salts, the absolute coverage was quite difficult to determine. Due to the multilayering, the
method employed for the spontaneous grafting (comparison with a fluorinated SAM) was no
longer possible. However, by studying the remaining chlorine, the coverage could be
estimated. In the case of C8F17-BD, the amount of detected chlorine was equivalent to the one
in spontaneous grafting; therefore, the coverage was estimated at 50%. The less sterically
hindered diazonium salts exhibited lower amount of remaining chlorine, thus providing a
higher absolute coverage (Fig. 6).

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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems

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Figure 6. Survey spectra and zoom on the Cl 2s region (inset) of BD-grafted on n-doped Ge.
These observations are in accordance with the previously discussed CVs. Indeed, when the
surface appeared passivated by CV, the amount of remaining chlorine was very low and, thus,
the absolute coverage was more than 50%. In the contrary, when the passivation was not
reached by CVs, the amount of chlorine was more important and the absolute coverage was
close to 50%. This result further confirms the relation between density and CVs and in
particular the occurrence of passivation on one hand, and the thickness of the film and the
stability of the radicals on the other hand. Indeed, high steric hindrance prevented the full
coverage of the surface, thus preventing the passivation and allowing the growth of the film,
whereas low steric hindrance allowed a higher coverage, thus inducing the passivation and
limiting the film formation.

IV.2 - Comparison with spontaneous grafting on Ge


Compared to the films obtained by spontaneous grafting, those formed by electrografting are
thicker (about 10 nm thick against 1-2 nm) and denser. Indeed, the absolute coverage of
spontaneously grafted films was evaluated at 50% whereas the one of electrografted films
overcame this value. However, the most striking effect of electrografting was the
multilayering obtained even with the fluorinated diazonium salts. Where the growth of the
film was governed by steric and mesomeric effects in spontaneous grafting, it was controlled
by the stability of the formed radicals (and therefore by the attracting effects) in
electrografting. Regarding the film morphology, electrografted films appeared more irregular
than their spontaneously grafted counterparts. This effect probably arose from the fact that
more radicals were produced in the electrografting thus inducing more radical coupling at the
surface, and leading to the formation of regions in which the concentration of radicals was
higher. The films grew from those regions and were therefore more irregular than the
spontaneously grafted films. Finally, contrary to the spontaneous grafting process, azo bridges
were frequently present in electrografting. Once again, when the presence of azobenzene
100

IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


moieties in the film was controlled by the steric effects in the spontaneous process, their
occurrence in electrografting was governed by the stability of the diazenyl radical.

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The electrografting is a faster process than the spontaneous grafting; however, the control of
the film is more difficult. Nevertheless, this control was still achieved with some of salts used,
in particular the most sterically hindered. Indeed, the Ge surface was already passivated after
the first cycle with NBD or CN-BD but this passivation was only achieved after several cycles
with CF3-BD. Therefore by reducing the number of cycles, the thickness of the film could be
controlled. Moreover, another way to partially control the film growth was to change the
lowest potential of the cycling preventing a large reduction of the diazonium salt and thus the
formation of the film. Nevertheless, the steric effects no longer controlled the thickness as the
thickest film was obtained with the bulkiest salt which led to monolayer in the case of
spontaneous grafting.

IV.3 - Grafting of the push-pull systems.


Following the electrografting of the simple salts, the diazonium salt derived push-pull systems
were also electrografted on n-doped germanium and on gold then spontaneously grafted on
Ge. Concomitantly, Ge was also functionalized with the thiols derivatives to form SAMs of
push-pull molecules, whereas TiO2 was functionalized with the carboxylic acid derivatives for
dye-sensitized solar cell. Unfortunately, no energy conversion was observed with the
fabricated cell. The grafting on gold and germanium was studied by XPS and by
electrochemistry. For instance, the azobenzene derivatives were both spontaneously and
electrochemically grafted on germanium (undoped for the spontaneous process, n-doped for
the electrochemical). The spontaneous grafting was performed after etching in a 5.10-3 mol.L-1
solution of the diazonium salt whereas the electrochemical grafting was realized by CV
between 0 and -0.8 V. Even if the fluorine was sometimes difficult to detect, the XPS spectra
confirmed the grafting in both cases. Indeed, C1s core level showed the presence of aliphatic
and aromatic carbons whereas N1s core level demonstrated the presence of the azobenzene
(Fig. 7). Nevertheless, the poor quality of the films (for instance, fluorine was detected in low
quantity for the CF3 derivative in both cases and for C8F17 derivative in the spontaneous
process) coupled with the high sensitivity of germanium prevented further studies. Finally, as
for the other salts, the films were thicker in the electrochemical process as observed from the
amount of carbon or the remaining detectable germanium

101

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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems

Figure 7. XPS survey, C1s, N1s and F1s core level (inset) spectra of CF3 azobenzene grafted
spontaneously on Ge for 15 min (top left), electrochemically by CV between 0 and -0.8 V on
n-doped Ge (bottom left) and C8F17 azobenzene grafted spontaneously on Ge for 15 min (top
right) and electrochemically by CV between 0 and -0.8 V on n-doped Ge (bottom right).
Regarding the stilbazolium thiols derivatives grafted only on undoped germanium from
solutions at 5.103 mol.L-1 in ethanol, sulfur atoms were difficult to detect and the azobenzene
and pyridinium were not observed in the case of the diphenyl derivative but, nevertheless, the
C1s and N1s levels both confirmed the grafting as aromatic carbon, amine, pyridinium and
azobenzene (except for the diphenyl derivative for the last two species) were detected in the
films (Fig. 8). However, due to the sensitivity of germanium and the probable low-quality of
the SAM as observed from XPS spectra, no further study was performed on the samples.

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IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems

Figure 8. XPS survey, C1s, N1s and S2p core level (inset) spectra of NMe2 (top left), NPh2
(top right) and NEtOH2 (bottom) thiol derivatives SAMs on Ge after 72 h.
Concomitantly, the diazonium salt of the dimethyl derivative was spontaneously grafted on
germanium from a 5.10-3 mol.L-1 solution in acetonitrile, providing a thin film on the surface
as illustrated by the XPS spectra (Fig. 9). However, azobenzene and pyridinium were not
detected probably due to the low amount of grafted material, thus not confirming the grafting
of the desired product.

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Figure 9. XPS survey, C1s and N1s core level (inset) spectra of NMe2 diazonium salt
derivatives spontaneously grafted on Ge for 15 min.
Finally, diazonium salt and triazene derivatives were grafted by electrochemistry on
germanium and on gold. However, before the grafting, the triazene and methyl pyridinium
derivatives were studied in acetonitrile solution by electrochemistry to determine the
parameters for the process. CVs of the dimethyl and the diphenyl triazene and methyl
pyridinium derivatives are presented on Fig. 10. Several peaks are visible both in oxidation
and in reduction. The oxidation peak at 0.8 V correspond to the oxidation of the amine moiety
whereas the two reduction peak at -0.8 V and -1.6 V could be attributed to the pyridinium and
the azobenzene moieties; however, further studies are needed to confirm these attributions.

Figure 10. CVs between -2 V and 1 V of diphenyl methyl pyridinium (top left), dimethyl
methyl pyridinium (top right), diphenyl triazene (bottom left), and dimethyl triazene (bottom
right) derivatives.
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Therefore, we also studied the dimethyl pyridine derivative and the Disperse Orange 3 (DO)
to determine the respective position of the pyridinium and the azobenzene on the CVs. Both
CVs, presented on Fig. 11, exhibited the oxidation peak of amines around 0.8 V and a
reversible reduction peak around -1.5 V (-1.6 V for the pyridine dimethyl, -1.25 V for the
DO) corresponding to the azobenzene moiety. The assignation was further confirmed by the
absence of the reduction peak at -0.8 V on both CVs. Therefore, when cycling from 0 V to -2
V, then 1 V and back to 0 V, the methyl pyridinium and the triazene derivatives underwent a
first reversible reduction of the pyridinium moiety, followed by a second reversible reduction
of the azobenzene core and finally an irreversible oxidation of the amine group. The origin of
the two peaks observed between 0 and 0.6 V remains unclear, however, they might arise from
impurities contained in the product as the NMR spectra showed also some impurity of the
compounds.

Figure 11. CVs between -2 V and 1 V of dimethyl pyridine derivative (left) and disperse
orange 3 (right).
Due to the reduction peaks of azobenzene and pyridinium moieties, the derivatives were
grafted by CV between 0 and -0.4 V and between 0 and -1.8 V. The film composition was
relatively similar; however, when cycling down to -1.8 V, the film appeared thicker as
illustrated by the XPS spectra (Fig. 12). Indeed, gold was less visible in the second case and
concomitantly, more carbon and nitrogen were detected. The N1s core level spectra
confirmed the nature of the molecules as amine, azobenzene, and pyridinium were all
detected. Nevertheless, azobenzene moieties were less present when cycling to -1.8 V,
indicating a non-reversible reduction and a loss of material, thus allowing a more important
growth of the film and therefore a thicker layer. Finally, the film was thicker in the case of the
dimethyl derivative as more carbon and nitrogen and less gold were detected by XPS.

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Figure 12. XPS survey, C1s and N1s core level (inset) spectra of NMe2 stilbazolium triazene
derivative electrografted on gold by CV between 0 and -0.8 V (top left) and between 0 and 1.8 (bottom left) and NPh2 stilbazolium triazene derivative electrografted on gold by CV
between 0 and -0.4 V (top right) and between 0 and -1.8 V (bottom right).
This effect was also observed with DO-BD on gold. Indeed, if the film composition was
similar when cycling between 0 and -0.4 V or between 0 and -1.8 V, the latter film were
thicker. Furthermore, cycling the grafted layer in absence of DO-BD down to -1.8 V induced
a loss of material and in particular regarding the C-N bond (on C1s core level spectrum) and
the azobenzene moiety (on N1s spectrum). This further confirmed the partial irreversible
reduction of the azobenzene observed in the case of the push-pull systems. Fig. 13 presents
the different XPS spectra of the grafting of DO-BD on gold under various procedures.

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Figure 13. XPS survey, C1s and N1s core level (inset) spectra of DO-BD electrografted on
gold by CV between 0 and -0.4 V (top left), between 0 and -1.8 V (top right) and between 0
and -0.4 V with further cycling in acetonitrile between 0 and -1.8 V (bottom).
The push-pull systems were thus successfully grafted on gold and germanium. However, the
XPS analyses presented some irregularities (absence of fluorine or azobenzene) which could
be explained by the fragility of the molecules together with their purity. Nevertheless,
multilayers were obtained and will now have to be sent to the electrical characterization.

IV.4 Conclusion
The electrografting of diazonium salt was successfully adapted to germanium (both doped and
undoped) and studied in details. This process provided thicker films than its spontaneous
counterpart, thus being promising for the dielectric applications. The influence of the ring
substituent on the film morphology and thickness was determined and the absolute coverage
evaluated from XPS data. AFM and XPS demonstrated that the surface state and the film
thickness were related to the stability of the intermediate radical and not to the steric
hindrance of the substituent borne by the different salts. The more stable the radicals, the
smoother and thicker the film. The impacts of the doping and of the substrate on the process
were also studied. Germanium presented a higher over-potential than gold or carbon, probably
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due to the involvement of the spontaneous process. Finally, to further demonstrate the
potential of this process for dielectric applications, the push-pull systems were also grafted on
gold and germanium, yielding to thin films. The push-pull systems were also characterized by
CV and exhibited two reduction peaks corresponding to pyridinium and azobenzene moieties
respectively, and an oxidation peak corresponding to the amine group. The grafting
parameters were determined to ensure the formation of a film of push-pull systems. Finally,
the grafted layers exhibited a good stability towards reoxidation of the substrate, better than
their spontaneously grafted counterparts. The electrografting of diazonium salts on
germanium is thus an efficient method to achieve passivation of the surface.

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References
(1)

Elofson, R. M. Can. J. Chem. 1958, 36, 12071210.

(2)

Delamar, M.; Hitmi, R.; Pinson, J.; Saveant, J. M. J. Am. Chem. Soc. 1992, 114, 5883
5884.

(3)

Delamar, M.; Desarmot, G.; Fagebaume, O.; Hitmi, R.; Pinson, J.; Saveant, J. M.
Carbon 1997, 35, 801807.

(4)

Allongue, P.; Delamar, M.; Desbat, B.; Fagebaume, O.; Hitmi, R.; Pinson, J.; Savant,
J.-M. J. Am. Chem. Soc. 1997, 119, 201207.

(5)

Nielsen, L. T.; Vase, K. H.; Dong, M.; Besenbacher, F.; Pedersen, S. U.; Daasbjerg, K.
J. Am. Chem. Soc. 2007, 129, 18881889.

(6)

Malmos, K.; Dong, M.; Pillai, S.; Kingshott, P.; Besenbacher, F.; Pedersen, S. U.;
Daasbjerg, K. J. Am. Chem. Soc. 2009, 131, 49284936.

(7)

Combellas, C.; Kanoufi, F.; Pinson, J.; Podvorica, F. I. J. Am. Chem. Soc. 2008, 130,
85768577.

(8)

Leroux, Y. R.; Fei, H.; Nol, J.-M.; Roux, C.; Hapiot, P. J. Am. Chem. Soc. 2010, 132,
1403914041.

(9)

Allongue, P.; Henry de Villeneuve, C.; Cherouvrier, G.; Cortes, R.; Bernard, M. C. J.
Electroanal. Chem. 2003, 550, 161174.

(10)

Lehr, J.; Williamson, B. E.; Flavel, B. S.; Downard, A. J. Langmuir 2009, 25, 13503
13509.

(11)

Ghilane, J.; Delamar, M.; Guilloux-Viry, M.; Lagrost, C.; Mangeney, C.; Hapiot, P.
Langmuir 2005, 21, 64226429.

(12)

Janin, M.; Ghilane, J.; Randriamahazaka, H.; Lacroix, J.-C. Electrochem. Commun.
2009, 11, 647650.

(13)

Bernard, M.-C.; Chauss, A.; Cabet-Deliry, E.; Chehimi, M. M.; Pinson, J.; Podvorica,
F.; Vautrin-Ul, C. Chem. Mater. 2003, 15, 34503462.

(14)

Hinge, M.; Ceccato, M.; Kingshott, P.; Besenbacher, F.; Pedersen, S. U.; Daasbjerg, K.
New J. Chem. 2009, 33, 24052408.

(15)

Adenier, A.; Bernard, M.-C.; Chehimi, M. M.; Cabet-Deliry, E.; Desbat, B.;
Fagebaume, O.; Pinson, J.; Podvorica, F. J. Am. Chem. Soc. 2001, 123, 45414549.

(16)

Kullapere, M.; Matisen, L.; Saar, A.; Sammelselg, V.; Tammeveski, K. Electrochem.
Commun. 2007, 9, 24122417.

(17)

Mirkhalaf, F.; Paprotny, J.; Schiffrin, D. J. J. Am. Chem. Soc. 2006, 128, 74007401.
109

tel-00782709, version 1 - 30 Jan 2013

IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


(18)

Ghosh, D.; Pradhan, S.; Chen, W.; Chen, S. Chem. Mater. 2008, 20, 12481250.

(19)

Rappich, J.; Hinrichs, K. Electrochem. Commun. 2009, 11, 23162319.

(20)

Henry de Villeneuve, C.; Pinson, J.; Bernard, M. C.; Allongue, P. J. Phys. Chem. B
1997, 101, 24152420.

(21)

Pandey, D.; Zemlyanov, D. Y.; Bevan, K.; Reifenberger, R. G.; Dirk, S. M.; Howell, S.
W.; Wheeler, D. R. Langmuir 2007, 23, 47004708.

(22)

Wang, D.; Buriak, J. M. Langmuir 2006, 22, 62146221.

(23)

Stewart, M. P.; Maya, F.; Kosynkin, D. V.; Dirk, S. M.; Stapleton, J. J.; McGuiness, C.
L.; Allara, D. L.; Tour, J. M. J. Am. Chem. Soc. 2004, 126, 370378.

(24)

Kariuki, J. K.; McDermott, M. T. Langmuir 1999, 15, 65346540.

(25)

Ray, K.; McCreery, R. L. Anal. Chem. 1997, 69, 46804687.

(26)

Lomeda, J. R.; Doyle, C. D.; Kosynkin, D. V.; Hwang, W.-F.; Tour, J. M. J. Am.
Chem. Soc. 2008, 130, 1620116206.

(27)

Sinitskii, A.; Dimiev, A.; Corley, D. A.; Fursina, A. A.; Kosynkin, D. V.; Tour, J. M.
ACS Nano 2010, 4, 19491954.

(28)

Sharma, R.; Baik, J. H.; Perera, C. J.; Strano, M. S. Nano Lett. 2010, 10, 398405.

(29)

Zhu, Y.; Higginbotham, A. L.; Tour, J. M. Chem. Mater. 2009, 21, 52845291.

(30)

Deinhammer, R. S.; Ting, E.-Y.; Porter, M. D. J. Electroanal. Chem. 1993, 362, 295
299.

(31)

Saby, C.; Ortiz, B.; Champagne, G. Y.; Belanger, D. Langmuir 1997, 13, 68056813.

(32)

Barroso-Bujans, F.; Fierro, J. L. G.; Rojas, S.; Sanchez-Cortes, S.; Arroyo, M.; LopezManchado, M. Carbon 2007, 45, 16691678.

(33)

Bahr, J. L.; Yang, J.; Kosynkin, D. V.; Bronikowski, M. J.; Smalley, R. E.; Tour, J. M.
J. Am. Chem. Soc. 2001, 123, 65366542.

(34)

Szunerits, S.; Boukherroub, R. J. Solid State Electrochem. 2007, 12, 12051218.

(35)

Yang, W.; Baker, S. E.; Butler, J. E.; Lee, C.-S.; Russell,, J. N.; Shang, L.; Sun, B.;
Hamers, R. J. Chem. Mater. 2005, 17, 938940.

(36)

Uetsuka, H.; Shin, D.; Tokuda, N.; Saeki, K.; Nebel, C. E. Langmuir 2007, 23, 3466
3472.

(37)

Wang, J.; Firestone, M. A.; Auciello, O.; Carlisle, J. A. Langmuir 2004, 20, 11450
11456.
110

tel-00782709, version 1 - 30 Jan 2013

IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


(38)

Lud, S. Q.; Steenackers, M.; Jordan, R.; Bruno, P.; Gruen, D. M.; Feulner, P.; Garrido,
J. A.; Stutzmann, M. J. Am. Chem. Soc. 2006, 128, 1688416891.

(39)

Mangeney, C.; Qin, Z.; Dahoumane, S. A.; Adenier, A.; Herbst, F.; Boudou, J.-P. P.;
Pinson, J.; Chehimi, M. M. Diamond Relat. Mater. 2008, 17, 18811887.

(40)

Yang, N.; Yu, J.; Uetsuka, H.; Nebel, C. E. Electrochem. Commun. 2009, 11, 2237
2240.

(41)

Maldonado, S.; Smith, T. J.; Williams, R. D.; Morin, S.; Barton, E.; Stevenson, K. J.
Langmuir 2006, 22, 28842891.

(42)

Adenier, A.; Barre, N.; Cabet-Deliry, E.; Chausse, A.; Griveau, S.; Mercier, F.; Pinson,
J.; Vautrin-Ul, C. Surf. Sci. 2006, 600, 48014812.

(43)

Merson, A.; Dittrich, T.; Zidon, Y.; Rappich, J.; Shapira, Y. Appl. Phys. Lett. 2004, 85,
10751076.

(44)

Bureau, C.; Pinson, J. Method for modifying insulating or semi-conductive surfaces,


and resulting products 2007, FR 2892325.

(45)

Combellas, C.; Kanoufi, F. F.; Mazouzi, D.; Thiebault, A.; Bertrand, P.; Medard, N.
Polymer 2003, 44, 1924.

(46)

Desrousseaux, S.; Bennetau, B.; Morand, J.-P.; Mingotaud, C.; Letard, J.-F.; Montant,
S.; Freysz, E. New J. Chem. 2000, 24, 977985.

(47)

Kumar, A. S.; Ye, T.; Takami, T.; Yu, B.-C.; Flatt, A. K.; Tour, J. M.; Weiss, P. S.
Nano Lett. 2008, 8, 16441648.

(48)

Preat, J.; Hagfeldt, A.; Perpte, E. A. Energy Environ. Sci. 2011, 4, 45374549.

(49)

Giribabu, L.; Singh, V. K.; Kumar, C. V.; Soujanya, Y.; Reddy, P. Y.; Kantam, M. L.
Solar Energy 2011, 85, 12041212.

(50)

Giribabu, L.; Vijay Kumar, C.; Gopal Reddy, V.; Yella Reddy, P.; Srinivasa Rao, C.;
Jang, S.-R.; Yum, J.-H.; Nazeeruddin, M. K.; Grtzel, M. Sol. Energy Mater. Sol. Cells
2007, 91, 16111617.

(51)

He, J.; Chen, B.; Flatt, A. K.; Stephenson, J. J.; Doyle, C. D.; Tour, J. M. Nat. Mater.
2006, 5, 6368.

(52)

Aswal, D. K.; Koiry, S. P.; Jousselme, B.; Gupta, S. K.; Palacin, S.; Yakhmi, J. V.
Physica E 2009, 41, 325344.

(53)

Min, M.; Bang, G. S.; Lee, H.; Yu, B.-C. Chem. Commun. 2010, 46, 52325234.

(54)

DiBenedetto, S. A.; Frattarelli, D. L.; Facchetti, A.; Ratner, M. A.; Marks, T. J. J. Am.
Chem. Soc. 2009, 131, 1108011090.

111

tel-00782709, version 1 - 30 Jan 2013

IV. Electrografting of diazonium salts on Ge and grafting of the push-pull systems


(55)

Liu, J.; Buchholz, D. B.; Chang, R. P. H.; Facchetti, A.; Marks, T. J. Adv. Mater. 2010,
22, 23332337.

(56)

Wang, L.; Yoon, M. H.; Lu, G.; Yang, Y.; Facchetti, A.; Marks, T. J. Nat. Mater. 2006,
5, 893900.

(57)

Liu, J.; Hennek, J. W.; Buchholz, D. B.; Ha, Y. G.; Xie, S. J.; Dravid, V. P.; Chang, R.
P. H.; Facchetti, A.; Marks, T. J. Adv. Mater. 2011, 23, 992997.

(58)

Ju, S. H.; Lee, K.; Janes, D. B. Nano Lett. 2005, 5, 22812286.

(59)

Byrne, P. D.; Facchetti, A.; Marks, T. J. Adv. Mater. 2008, 20, 23192324.

(60)

DiBenedetto, S. A.; Paci, I.; Facchetti, A.; Marks, T. J.; Ratner, M. A. J. Phys. Chem. B
2006, 110, 2239422399.

(61)

DiBenedetto, S. A.; Facchetti, A.; Ratner, M. A.; Marks, T. J. Adv. Mater. 2009, 21,
14071433.

(62)

Yoon, M.-H. H.; Facchetti, A.; Marks, T. J. PNAS 2005, 102, 46784682.

(63)

Benedetto, A.; Balog, M.; Viel, P.; Le Derf, F.; Sall, M.; Palacin, S. Electrochim. Acta
2008, 53, 71177122.

(64)

Hurley, B. L.; McCreery, R. L. J. Electrochem. Soc. 2004, 151, B252B259.

(65)

Doppelt, P.; Pinson, J.; Podvorica, F.; Verneyre, S.; Hallais, G. Chem. Mater. 2007, 19,
45704575.

(66)

Toupin, M.; Belanger, D. J. Phys. Chem. C 2007, 111, 53945401.

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compounds

V.1 Grafting of model molecules...112


V.1.1 Grafting on germanium..113
V.1.2 Grafting on gold.114
V.2 Electric measurements on the model molecules grafted on gold...118
V.3 Conclusion122

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V. Grafting and I/V characterization of model compounds


To study the transport properties through a thin (1-30 nm) organic layer, different methods are
available1. The most simple consists in evaporating a metallic layer on top of the organic
layer210. However, short-cuts are often created during the process due to metal diffusion
inside the organic film. Indeed, only 1.2% of the junctions are not short circuits therefore
preventing the reproducible and reliable use of his method. Among the different techniques
developed, methods using a drop of conducting materials were the most employed. The oldest
one is the mercury drop11. However, due to the toxicity of this metal, its use implies safety
handling in a glove box. Furthermore, mercury diffuses through the layer and, in the case of
gold, forms amalgam with the surface. Therefore, this method is progressively replaced by
measurements with a tip of InGa eutectic (25% In-75% Ga)1218. This technique is easier to
settle up, indeed, eutectic is non-toxic and does not form amalgams with gold. Moreover, the
facile modeling of this compound allows forming a tip, thus reducing the contact surface and
the probability of measuring a defect containing zone. Along these macroscopic techniques,
nanoscopic ones were also developed. For instance, STM could be used to measure the
transport properties of SAMs1926. This method presents the advantage of being nondestructive and non-intrusive, therefore avoiding damages on the layer. Furthermore, as the
tip is very thin, only few molecules are measured together. However, even if this technique is
the most widely employed, it presents some drawbacks. First, due to the presence of an air
gap between the tip and the molecule, the variations of apparent height cannot be undoubtedly
attributed to the SAMs. Furthermore, this gap induces low measured current preventing the
characterization of long or insulating molecules. To avoid the existence of a gap, a method
using AFM was developed: conducting AFM with a conductive tip2731. The scope of studied
molecules was extended with this method due to the absence of the gap. However, the tip
being larger than a STM one, defects could be present in the scanned region. All these
techniques allow the study of electric transport through SAMs and will be used here to
characterize the organic layer formed.
In a first time, we will discuss the grafting of the model molecules on both gold and
germanium. Then, the transport properties of the obtained layers on gold will be studied by
In/Ga eutectic tip, STM and conducting AFM.

V.1 Grafting of model molecules


The three thiols derivatives (hexyl and heptyl naphthalenediimide and terthiophene,
respectively C6-naph, C7-naph and 3T) formed SAMs on gold and germanium. As illustrated
on Fig. 1, a different orientation of the aromatic core is expected for C6 and C7-naph due to
the different alkyl chain assuming an Au-S-C angle of 110.

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V. Grafting and I/V characterization of model compounds

Figure 1. Theoretical orientation of C7-naph (left) and C6-naph (right) SAMs on a gold
surface

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V.1.1 Grafting on germanium


The three SAMs were made from dipping in 10-3 mol.L-1 solutions in a 2:8 mixture of
methylene chloride and ethanol for 24 h on gold and 72 h on germanium. The modified
substrates were characterized by XPS. The S2p and C1s spectra confirmed the grafting (Fig.
2). However, the SAMs were not as closely packed as the alkanethiolates SAMs. Moreover, a
part of the thiols present in the film remained unbound to the substrate (SH peak present in
S2p spectra). Finally, no difference was observed between C6-naph and C7-naph in the SAM
(except a slight larger amount of carbon in the latter case corresponding to the two
supplementary aliphatic carbons in the molecule).

Figure 2. XPS survey, C1s (inset), and S2p (inset) spectra of a C6-naph (top left), C7-naph
(top right) and 3T (bottom) SAM on germanium grown from 10-3 mol.L-1 solutions in a 1:1
mixture of methylene chloride and ethanol for 72 h.
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Concomitantly, the diazonium salt derivative of naphthalenediimide (Naph-BD) was


electrografted by CV from 0 to -0.8 V on n-doped germanium, providing a thick/dense film.
Indeed, Ge2p peak was no longer detected by XPS whereas the Ge3d level showed a slight
oxidation of the surface. C1s and N1s core level spectra confirmed the nature of the organic
layer grafted on the surface (Fig. 3).

Figure 3. XPS survey, C1s (inset) and N1s (inset) spectra of a Naph-BD film electrografted
on germanium by CV between 0 and -0.8 V.
V.1.2 Grafting on gold
The three thiol derivatives were also grafted on gold, providing SAMs after 24 h dipping in
10-3 mol.L-1 solution in a 2:8 mixture of methylene chloride and ethanol. XPS spectra (Fig. 4)
clearly show the presence of the grafted product with less remaining adsorbed product (less
SH detected in S2p spectra) as we obtained similar signatures to those on Ge.

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Figure 4. XPS survey, C1s (inset), and S2p (inset) spectra of a C6-naph (top left), C7-naph
(top right) and 3T (bottom) SAM on gold grown from 10-3 mol.L-1 solutions in a 1:1 mixture
of methylene chloride and ethanol for 24 h.
Adsorption of 3T, C6-naph and C7-naph on gold did not result in a significant perturbation in
binding energy of the Au 4f core level spectra as shown in Fig. 5. However, the total
integrated spectral intensity of the Au 4f peaks decreased compared to the bare gold. This
effect arises from the formation of a quite thick overlayer attenuating the photoelectrons
emitted by gold. Therefore, the attenuation is directly correlated to the thickness of the
organic layer. Here, 3T provided thicker layer than C6-naph and C7-naph, which were
comparable to dodecanethiol SAM.

Figure 5. Au 4f core level spectra of bare gold and octadecanethiol (C18), C6-naph, C7-naph,
and 3T SAMs on gold grown from 10-3 mol.L-1 solutions in a 1:1 mixture of methylene
chloride and ethanol for 24 h.
117

The organization of the SAMs was further studied by IR spectroscopy and by STM. IR
spectra showed the characteristic of a packed monolayer regarding the value of the methylene
antisymetric stretch (Fig. 6)32. Indeed, for C6-naph and 3T, the molecules organized in the
monolayer presented different absorption spectra than those dissolved in solution. For
instance, the intensity of the symmetric ( 2875 cm-1) or anti-symmetric ( 2955 cm-1)
stretching of the CH3 end group increased compare to the CH2 stretching of the aliphatic
chains (Symmetric at 2855 cm-1 and anti-symmetric at 2925 cm-1). This effect arose from
the surface dipole selection rule on surface. The intensity of vibrational modes perpendicular
to the surface is enhanced whereas the vibrational modes parallel to the surface are inhibited.
Therefore, the thiols compounds were grafted almost normal to the surface as this effect was
clearly observed. Moreover, the carbonyl group of C6-naph presented a similar behaviour.
The symmetrical vibration (1705 cm-1) was found more intense in the film whereas the
asymmetrical (1660 cm-1) was more pronounced in solution. Furthermore, even if the effect
is less marked, the terthiophene core (1495 and 1431 cm-1) was also sensitive to the packing
on the surface. Finally, due to the breaking of the symmetry of grafted molecules on gold,
news vibrations modes appeared at 1266 or 1100 cm-1 for 3T and at 1340 cm-1 for C6-naph.
Molecules are thus almost normal to the surface and closely packed.
100
100,50

In CCl4

100,25

90

90

100,00

SAM

NaphSH

80

99,75

75
70

99,50
65
99,25

100,1

Transmittance/%

85

80

3TSH
100,0
70

SAM
99,9

Transmittance/%

Transmittance/%

100

in CCl4

100,2

95

Transmittance/%

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V. Grafting and I/V characterization of model compounds

60

60
55

99,00

50
99,8

50
3500

3000

2500

2000

Wavenumber/cm

1500
-1

1000

3500

3000

2500

2000

Wavenumber/cm

1500

1000

-1

Figure 6. IR spectra of C6-naph (left) and 3T (right) in solution in CCl4 (blue lines) and SAM
on gold (black lines).
The STM images underlined a different behaviour regarding the molecules (Fig. 7). Indeed,
the dodecanethiol SAM presented closely packed molecular domains separated by grain
boundaries in which the molecules arranged in a hexagonal structure with an intermolecular
distance of 5 . If this organization was also observed with 3T, it was no longer present with
C6-naph. However, 3T SAM did not present well-defined grain boundaries but rather
disordered zones. Nevertheless, the 5 intermolecular distance and the hexagonal
arrangement were still observed. Naphthalene derivatives showed no organization, maybe
because of the too bulky aromatic core that could prevent the packing of molecules.

118

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V. Grafting and I/V characterization of model compounds

Figure 7. STM images of dodecanethiol (-0.7 V, 2 pA, a) and b)), 3T (-0.9 V, 20 pA, c) and
d)), and C6-naph (-0.9 V, 2 pA, e) and 20 pA, f)) SAMs on Au(111) evaporated on mica.
Inset of d) is a 4.6x4.2 nm zoom on 3T SAM showing hexagonal molecular arrangement.
To conclude on STM, when applying a pulse voltage between the tip and the surface, it was
possible to eject some molecules of the SAM and therefore to measure the thickness of the
organic layer. As observed from the Au4f attenuation, the 3T SAM was found thicker than the
C6-naph with a thickness comparable to the molecule size (30 and 22 respectively for 3T
and C6-naph).
Finally, 3T and a C6-naph were also characterized by electrochemistry. 3T and C6-naph
molecules without the thiol function were studied in solution whereas 3T and C6-naph SAMs
on gold were also measured. Both compound in solution exhibited two reversible redox
processes (black curves in Fig. 8). These two processes correspond to the injection of two
electrons in the ring due to the withdrawing effect of the carbonyl groups symmetrically
distributed in C6-naph or the removal of two electrons from the electron-rich terthiophene
core. The latter could though polymerize, however, the blocking of the positions prevented
the radical polymerization from occurring. Regarding the grafted molecules, only one
reversible wave remained between -1.45 and 0.45 V vs ferrocene (blue curves in Fig. 8).
Indeed, due to the instability of SAMs towards high reduction potential generating thiolates in
solution (desorption of the SAM) and the possibility of oxidizing the substrate at high
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V. Grafting and I/V characterization of model compounds

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potential, the second reversible wave was not visible. Finally, from the calculated passed
charges during oxidation or reduction of the SAM, the absolute coverage was estimated. 3T
showed a value of 1.3 x 10-10 mol.cm-2 whereas C6-naph presented a coverage of 1.2 x 10-10
mol.cm-2. These coverages are much lower than with alkylthiol (7.6 x 10-10 mol.cm-2) due to
the steric effects induced by the aromatic cores. Therefore, the SAMs obtained with the model
molecules are less compact and less dense than an alkylthiol SAM. However, even if the
molecules were not very closely packed, the aromatic rings of 3T could still interact as the
oxidation peak shifted 95 mV down. Such an interaction was not observed with C6-naph as
the peak showed no shifting.

Figure 8. Cyclic voltammetry on a gold electrode of millimolar solutions (black curves) of


references 3T (left) and C6-naph without thiol function (right) in CH2Cl2-Bu4NPF6 0.1 mol.L
1
at 100 mV.s-1 and of SAMs (blue curves) of 3T (left) and C6-naph (right) on gold in
CH2Cl2-Bu4NPF6 0.1 mol.L1 at 100mV.s-1.

V.2 Electric measurements on the model molecules grafted on gold


Two different types of measurements were performed on the molecules grafted on gold. First,
STM measurements were realized by Lionel Patrone at IM2NP (Universit de Toulon). Then,
conducting AFM experiments were conducted on gold nanoplots33,34 by Stphane Lenfant at
IEMN. Previously in a first time, measurements with a droplet of InGa eutectic (Fig. 9) were
also carried out by Gal Robert at the LEM laboratory of the CEA Saclay.

Figure 9. Formation of an InGa eutectic tip for electrical measurements12.


By the eutectic and STM measurements, the naphthalene derivatives and 3TSH exhibited an
opposite behavior which was consistent with their different nature. Indeed, whereas C6-naph
and C7-naph are n-type organic semiconductors (acceptor ring), 3TSH is a p-type organic
120

V. Grafting and I/V characterization of model compounds

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semiconductor (donor ring). Therefore, under polarization, the naphthalenediimide will rectify
the current under positive bias and 3TSH will present an asymmetric current increase for
positive bias. Measurements confirmed this trend; however, the rectification effect was much
marked with C7-naph than with its C6 counterpart (Fig. 10, rectification ratios of 3 for C6 and
between 5 and 23 depending on the scanning for C7).

Figure 10. InGa eutectic (top) and STM (middle and bottom) measurements of dodecanethiol
(left), 3T (middle), C6-naph (right) and C7-naph (STM only, bottom) SAMs and gold
showing the rectification.
Simple alkanethiolates SAM showed no rectification with a low current level which was
consistent with the insulating properties of these molecules. The current level through the
model molecules was found ten times higher than the one of SAMs, further underlining the
conducting properties of these compounds. Furthermore, these measurements showed that the
organization of the SAM preserved the rectification properties thus opening the way for the
measurement on push-pull systems. Nevertheless, these techniques are long to perform if
statistic is aimed. Moreover, the non-contact mode of STM implies the presence of a thin air
layer that could interfere in the measurement. Therefore, the SAMs were also characterized by
conducting AFM. In this method, the AFM tip is in contact with the organic layer, the
pressure applied being controlled to avoid scratching of the layer. Then, by using a gold

121

V. Grafting and I/V characterization of model compounds


nanoplots network (Fig. 11) and polarizing the substrate, the sample can be scanned and
statistic obtained.

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Figure 11. AFM images of the gold nanoplots network (left) and of a single nanoplot
(right)33.
Indeed, as the nanoplots are made on silicon covered by a thin layer of SiO2, the SAMs were
formed only on the plots. Therefore, the measurements are performed directly on isolated
SAMs of around 80 molecules. By scanning with the AFM tip, all the plots are measured and
a statistic can be made from the obtained images (Fig. 12).

Figure 12. Conducting AFM images of the nanoplots network functionalized with a C6-naph
SAM at a -200 and a 200 mV polarization (top left and right respectively) and the derived
statistic showing the rectification effect (blue bar).
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V. Grafting and I/V characterization of model compounds

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However, in this case, the found rectifications were not as marked as in the STM experiment.
This effect may arise from the fact that less molecules are measured due to the smaller size of
the sample and the tip but also from an interference of the air layer in STM. Furthermore, the
opposite effect observed with 3T and naphthalenes was no longer detected. Indeed, all
rectifications occurred with the same polarization despite the different nature of the
compounds (Fig. 13). However, this statistic must be completed at higher polarizations to be
compared with the STM results.

Figure 13. Plots of the different statistics obtained on C6-naph (top left), C7-naph (top right)
and 3T (bottom) showing the rectification for I<0.
After, measurements of the model molecules, the next step will be to characterize the
diazonium salt derived films. No rectification is expected; however, good insulating
properties (comparable to those of SAMs) are envisaged. These measurements will be
followed by the study of the push-pull systems. This will allow a comparison with the already
published thin film dielectrics. Finally, measurements with the more sensitive germanium
substrate will be carried out to complete this project.

123

V. Grafting and I/V characterization of model compounds

V.3 Conclusion

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The model molecules were successfully grafted on gold and germanium, providing good
quality SAMs for electrical characterization. Preliminary results were obtained on gold with
three different techniques: InGa eutectic, STM and conducting AFM. Naphthalene derivatives
and 3T presented an opposite behavior both with eutectic and STM measurement, showing a
rectification at opposite polarization in accordance with their semiconducting nature.
However, this trend was no longer observed with AFM. Nevertheless, these results showed
that the SAM formation did not alter the electronic properties of the molecules and
furthermore, the attached molecules did not switch under polarization. The extension of these
measurements to diazonium salt derived films will supply more information on the way to the
electrical characterization of the push-pull systems. The first results presented here are
encouraging regarding the possibility of performing such measurements on the push-pull
systems but also in terms of robustness of the layer and prevention of the switching of
molecules. Finally, these techniques will also be adapted to the more sensitive substrate
germanium.

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References
(1)

McCreery, R. L.; Bergren, A. J. Adv. Mater. 2009, 21, 43034322.

(2)

de Boer, B.; Frank, M. M.; Chabal, Y. J.; Jiang, W.; Garfunkel, E.; Bao, Z. Langmuir
2004, 20, 15391542.

(3)

Kim, T.-W.; Wang, G.; Lee, H.; Lee, T. Nanotechnology 2007, 18, 315204.

(4)

Lee, J.-O.; Lientschnig, G.; Wiertz, F.; Struijk, M.; Janssen, R. A. J.; Egberink, R.;
Reinhoudt, D. N.; Hadley, P.; Dekker, C. Nano Lett. 2003, 3, 113117.

(5)

Lee, T.; Wang, W.; Klemic, J. F.; Zhang, J. J.; Su, J.; Reed, M. A. J. Phys. Chem. B
2004, 108, 87428750.

(6)

Yan, H.; Bergren, A. J.; McCreery, R. L. J. Am. Chem. Soc. 2011, 133, 1916819177.

(7)

Seitz, O.; Dai, M.; Aguirre-Tostado, F. S.; Wallace, R. M.; Chabal, Y. J. J. Am. Chem.
Soc. 2009, 131, 1815918167.

(8)

Niskala, J. R.; You, W. J. Am. Chem. Soc. 2009, 131, 1320213203.

(9)

Niskala, J. R.; Rice, W. C.; Bruce, R. C.; Merkel, T. J.; Tsui, F.; You, W. J. Am. Chem.
Soc. 2012, 134, 1207212082.

(10)

Nijhuis, C. A.; Reus, W. F.; Whitesides, G. M. J. Am. Chem. Soc. 2009, 131, 17814
17827.

(11)

Mann, B. J. Appl. Phys. 1971, 42, 4398.

(12)

Chiechi, R. C.; Weiss, E. A.; Dickey, M. D.; Whitesides, G. M. Angewandte Chemie


(International ed. in English) 2008, 47, 142144.

(13)

Dickey, M. D.; Chiechi, R. C.; Larsen, R. J.; Weiss, E. A.; Weitz, D. A.; Whitesides, G.
M. Adv. Funct. Mater. 2008, 18, 10971104.

(14)

Fracasso, D.; Valkenier, H.; Hummelen, J. C.; Solomon, G. C.; Chiechi, R. C. J. Am.
Chem. Soc. 2011, 133, 95569563.

(15)

Meng Chen, X.; Tao Fei, G.; Feng Li, X.; Zheng, K.; De Zhang, L. J. Phys. Chem.
Solids 2010, 71, 918921.

(16)

Nijhuis, C. A.; Reus, W. F.; Barber, J. R.; Whitesides, G. M. J. Phys. Chem. C 2012,
116, 1413914150.

(17)

Thuo, M. M.; Reus, W. F.; Simeone, F. C.; Kim, C.; Schulz, M. D.; Yoon, H. J.;
Whitesides, G. M. J. Am. Chem. Soc. 2012, 134, 1087610884.

(18)

Xu, Q.; Oudalov, N.; Guo, Q.; Jaeger, H. M.; Brown, E. Phys. Fluids 2012, 24,
063101.
125

tel-00782709, version 1 - 30 Jan 2013

V. Grafting and I/V characterization of model compounds


(19)

Mendoza, S. M.; Arfaoui, I.; Zanarini, S.; Paolucci, F.; Rudolf, P. Langmuir 2007, 23,
582588.

(20)

Yang, G.; Liu, G. J. Phys. Chem. B 2003, 107, 87468759.

(21)

Qian, Y.; Yang, G.; Yu, J.; Jung, T. A.; Liu, G. Langmuir 2003, 19, 60566065.

(22)

Esplandiu, M. J.; Carot, M. L.; Cometto, F. P.; Macagno, V. A.; Patrito, E. M. Surf.
Sci. 2006, 600, 155172.

(23)

Poirier, G. E. Chem. Rev. 1997, 97, 11171128.

(24)

Schoenenberger, C.; Jorritsma, J.; Sondag-Huethorst, J. A. M.; Fokkink, L. G. J. J.


Phys. Chem. 1995, 99, 32593271.

(25)

Delamarche, E.; Michel, B.; Gerber, C.; Anselmetti, D.; Guentherodt, H.-J.; Wolf, H.;
Ringsdorf, H. Langmuir 1994, 10, 28692871.

(26)

Delamarche, E.; Michel, B.; Biebuyck, H. A.; Gerber, C. Adv. Mater. 1996, 8, 719
729.

(27)

Wold, D. J.; Frisbie, C. D. J. Am. Chem. Soc. 2001, 123, 55495556.

(28)

Engelkes, V. B.; Beebe, J. M.; Frisbie, C. D. J. Phys. Chem. B 2005, 109, 16801
16810.

(29)

Engelkes, V. B.; Beebe, J. M.; Frisbie, C. D. J. Am. Chem. Soc. 2004, 126, 14287
14296.

(30)

Wang, G.; Kim, T.-W.; Jo, G.; Lee, T. J. Am. Chem. Soc. 2009, 131, 59805985.

(31)

Smaali, K.; Lenfant, S.; Karpe, S.; Oafrain, M.; Blanchard, P.; Deresmes, D.; Godey,
S.; Rochefort, A.; Roncali, J.; Vuillaume, D. ACS Nano 2010, 4, 24112421.

(32)

Porter, M. D.; Bright, T. B.; Allara, D. L.; Chidsey, C. E. D. J. Am. Chem. Soc. 1987,
109, 35593568.

(33)

Clment, N.; Patriarche, G.; Smaali, K.; Vaurette, F.; Nishiguchi, K.; Troadec, D.;
Fujiwara, A.; Vuillaume, D. Small 2011, 7, 26072613.

(34)

Smaali, K.; Clment, N.; Patriarche, G.; Vuillaume, D. ACS Nano 2012, 6, 46394647.

126

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CONCLUSION

Conclusion
The main objective of this work was to create a thin organic film on germanium surfaces in
order to protect and insulate them for application in nanoelectronics. The challenges laid in
the preparation of a smooth surface, the synthesis of push-pull systems, their grafting on the
prepared Ge surfaces and the electrical characterization of the obtained films. The stability of
the films was also evaluated.

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First, concerning the synthesis part, two different types of new push-pull systems as well as a
series of model molecules were synthesized and fully characterized. All the molecules were
functionalized with an anchoring group, either a thiol or a diazonium salt, to be grafted on
surfaces. The donor-acceptor systems presented a high dipolar moment required for the
formation of dielectric layers. Meanwhile, model molecules and a large scope of diazonium
salts were synthesized to study the impact of different parameters on the film formation. The
methods employed for the synthesis of the push-pull systems allow their modification to tune
their properties. Indeed, on the precursor, thiols, diazonium salts and carboxylic acids are
easily introducible with various functionalities without altering the dipolar moment of the
push-pull system.
Regarding the preparation of germanium surfaces, we developed a new etching process based
on a cyclic oxidizing-rinsing-etching procedure involving HCl. This method leaded to very
smooth surfaces without remaining oxide. However, due to the high sensitivity of germanium
towards reoxidation, the surfaces were readily functionalized. Besides the formation of selfassembled monolayers of alkanethiols, we introduced the spontaneous grafting of diazonium
salts on germanium surfaces. This spontaneous process was studied in details and we showed
that germanium itself reduced the diazonium salts to form the film. The impact of different
parameters, temperature and time of reaction, group in para-position, was studied and we thus
developed a process to form stable organic films on germanium by simple dipping for 15
minutes of etched surface in a solution of diazonium salt at room temperature. The absolute
coverage was evaluated at 50% with one site of the reconstructed 2x1 dimer occupied by the
aromatic ring from the diazonium salt and the other by a chlorine atom. Finally, the stability
of such films was found similar to the one of alkanethiol SAMs making the spontaneous
grafting a process of interest for the first step of the protection of germanium before
postfunctionalization.
The development of the spontaneous process was then completed by the study of the
electrochemical grafting of diazonium salt on germanium. The obtained films were found
thicker and denser than their spontaneous counterparts. Furthermore, the stability was
enhanced, particularly with the specifically designed fluorinated diazonium salt. This
electrochemical process was also deeply studied in terms of influence of the substrate (doped
or undoped,Ge, gold, carbon), influence of the group in para-position and influence of the end
potential. Interestingly, a complementary behavior to the spontaneous process was depicted.
This provided two different grafting methods to tune the obtained films regarding the groups
born by the salt or the conditions.
With all the information gathered in the two precedent studies, model molecules and pushpull systems were successfully grafted on gold and germanium with both thiol and diazonium
128

Conclusion

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salt anchoring group. This allowed performing electrical measurements on the obtained layer
with the model molecules. These films were characterized by STM, InGa eutectic and
conducting AFM measurements. A rectification was observed underlining the specific
features of the different molecules. However, these preliminary results will have to be
confirmed on germanium and extended to the push-pull systems. Nevertheless, the organic
thin film passivation of germanium has been achieved with stable layers providing first results
towards the realization of a thin passivating dielectric film on germanium.
In this work, we successfully synthesized new push-pull systems; we prepared smooth oxidefree germanium surfaces and functionalized them with thiols and diazonium salts. The pushpull systems were grafted on germanium and finally, we were able to electrically characterize
the obtained films. Based on these results, the grafted push-pull systems will also be
characterized by STM and conducting AFM and the push-pull systems will be modified to
enhance the dielectric properties of the thin film. This work constitute the first part of the
realization of organic dielectric films on germanium, the next part will be to control the
properties of the synthesized molecules. Furthermore, besides their potential use as dielectric,
these push-pull systems presenting a high dipolar moment are also good candidates as dyes in
organic solar cells. Finally, the development of the diazonium salt grafting, both spontaneous
and electrochemical, opens the way to various functionalization of germanium and therefore
to the development of new devices based on this substrate.

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APPENDIXES

Appendix I

Appendix I: Experimental section


Synthesis of the compounds

Synthesis of the model molecules

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HS

Br

Br

Acetone
+

KPht
reflux

Pht

Br

n= 6; 7

To a solution of dibromoalkane in 30 mL of refluxing acetone was added 0.5 equivalent of


potassium phtalimide over 3 hours. Reaction mixture was then refluxed for 24 hours. The
precipitate of KBr was removed by filtration. The filtrate was concentrated under vacuum and
the crude product was purified on silica gel using a 6:4 mixture of cyclohexane and diethyl
ether as eluent to give a white solid.
n=6: 3.15 mL of 1, 6-dibromohexane (5 g, 20.5 mmol), 1.9 g of KPht (10.25 mmol)
2.9 g (91 % Yield)
1
H NMR (400 MHz, CDCl3, ppm): 7.84 (m, 2H, arom), 7.71 (m, 2H, arom), 3.68 (t, J= 7.2
Hz, 2H, Pht-CH2), 3.39 (t, J= 6.8 Hz, 2H, CH2Br), 1.85 (m, 2H, CH2-CH2Br), 1.69 (q, J= 7.2
Hz, 2H, Pht-CH2-CH2), 1.47 (m, 2H, CH2-C-CBr), 1.37 (m, 2H, Pht-C-C-CH2)
n=7: 3.31 mL of 1, 7-dibromoheptane (5 g, 19.4 mmol), 1.79 g of KPht (9.69 mmol)
2.75 g (87 % Yield)
1
H NMR (400 MHz, CDCl3, ppm): 7.83 (m, 2H, arom), 7.70 (m, 2H, arom), 3.68 (t, J= 7.2
Hz, 2H, Pht-CH2), 3.39 (t, J= 6.8 Hz, 2H, CH2Br), 1.85 (m, 2H, CH2-CH2Br), 1.66 (q, J= 7.2
Hz, 2H, Pht-CH2-CH2), 1.23-1.43 (m, 6H, aliph)

131

Appendix I

Pht

THF

Br

Pht

AcSK
reflux

n
O

n= 6; 7

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To a solution of phtalimide in THF was added 1 equivalent of potassium thioacetate under


argon atmosphere. The reaction mixture was then refluxed for 24 hours. The KBr precipitate
was eliminated by filtration. The filtrate was concentrated under vacuum and the crude
product was purified on silica gel using a 6:4 mixture of cyclohexane and diethyl ether as
eluent to give a yellow solid.
n=6: 2 g of 1-bromo, 6-phtalimidohexane (6.16 mmol), 704 mg of AcSK (6.16 mmol)
1.5 g (80 % Yield)
1
H NMR (400 MHz, CDCl3, ppm): 7.84 (m, 2H, arom), 7.71 (m, 2H, arom), 3.67 (t, J= 7.2
Hz, 2H, Pht-CH2), 2.85 (t, J= 7.2 Hz, 2H, CH2S), 2.32 (s, 3H, CH3), 1.85 (q, J= 7.2 Hz, 2H,
CH2-CH2S), 1.69 (q, J= 7.2 Hz, 2H, Pht-CH2-CH2), 1.47 (m, 2H, CH2-C-CS), 1.37 (m, 2H,
Pht-C-C-CH2)
n=7: 2.2 g of 1-bromo, 7-phtalimidoheptane (6.79 mmol), 0.81 g of AcSK (6.79 mmol)
2 g (92 % Yield)
1
H NMR (400 MHz, CDCl3, ppm): 7.80 (m, 2H, arom), 7.67 (m, 2H, arom), 3.64 (t, J= 7.2
Hz, 2H, Pht-CH2), 2.82 (t, J= 7.2 Hz, 2H, CH2S), 2.28 (s, 3H, CH3), 1.81 (m, 2H, CH2-CH2S),
1.64 (m, 2H, Pht-CH2-CH2), 1.52 (m, 2H, CH2-C-CS), 1.24-1.43 (m, 4H, aliph)

Pht

+ H2NNH2.H2O

EtOH
reflux

H2N

SH

n= 6; 7

To a solution of phtalimidothioacetate in ethanol were added 4 equivalents of hydrazine


monohydrate. The reaction mixture was refluxed overnight. The precipitate was removed by
filtration. The filtrate was concentrated under vacuum. The crude product was then dissolved
in dichloromethane, filtrated and concentrated under vacuum to give product as a yellow oil.
n=6: 1 g of 1- thiacetato, 6-phtalimidohexane (3.28 mmol), 0.41 mL of hydrazine (420 mg,
13.1 mmol)
250 mg (57 % Yield)
1
H NMR (400 MHz, CDCl3, ppm): 2.69 (m, 4H, N-CH2 and CH2S), 1.69 (p, J= 7.4 Hz, 2H,
CH2-C-CS), 1.28-1.52 (m, 6H, aliph).
n=7: 2 g of 1-thiacetato, 7-phtalimidoheptane (6.26 mmol), 0.78 mL of hydrazine (800 mg, 25
mmol)
132

Appendix I
500 mg (56 % Yield)
1
H NMR (400 MHz, CDCl3, ppm): 2.68 (m, 4H, N-CH2 and CH2S), 1.67 (m, 2H, CH2-CCS), 1.26-1.62 (m, 8H, aliph).

H 2N

H 2 O /n-P rO H

50 C
O

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n= 5; 6

To a suspension of naphthalene-1, 4, 5, 8-tetracarboxylic acid dianhydride in 60 mL of a 1:1


mixture of water and n-propanol were added 3.2 equivalents of amine. The mixture was
heated at 50 C for 24 hours. pH was then set to approx. 1 with 20 mL of 2 M HCl. After one
hour stirring, the precipitate was filtered and dissolved in 200 mL of acetic acid and then
refluxed for 2 hours. The mixture was poured in 150 mL of water, the precipitate filtered,
dissolved in chloroform, washed with water, dried over Na2SO4 and concentrated under
vacuum. The product was purified on silica gel using chloroform as eluent to give a light
yellow powder.
n=5: 2 g of dianhydride (7.46 mmol) and 3.2 mL of n-hexylamine (2.42g, 23.86 mmol).
1 g (38 % yield)
1
H NMR (400 MHz, CDCl3, ppm): 8.82 (s, 4H, arom), 4.21 (t, J =7.6 Hz, 2H, NCH2), 1.75
(m, 2H, NCH2-CH2), 1.29-1.48 (m, 6H, aliph), 0.90 (t, J = 7.0 Hz, 3H, CH3)
n=6: 2 g of dianhydride (7.46 mmol) and 3.54 mL of n-heptylamine (2.75g, 23.86 mmol).
1.6 g (59 % yield)
1
H NMR (400 MHz, CDCl3, ppm): 8.82 (s, 4H, arom), 4.20 (t, J =7.6 Hz, 2H, NCH2), 1.75
(m, 2H, NCH2-CH2), 1.23-1.48 (m, 8H, aliph), 0.88 (t, J = 6.8 Hz, 3H, CH3)

H2N

DMF

+
n

SH
n

HS

125C
n

n= 5; 6

A solution of anhydride and thioamine in 10 mL of DMF was first degased for 10 min then
heated at 120 C for 24h. The product was then precipitated in water and purified on Allox
using dichloromethane as eluent.
n= 5: 358 g of anhydride (1.02 mmol) and 136 mg of thioamine (1.02 mmol).
260 mg (55% yield)
133

Appendix I
1

H NMR (400 MHz, CDCl3, ppm): 8.76 (s, 4H, arom), 4.20 (m, 4H, NCH2), 2.67 (m, 2H,
CH2S), 1.74 (m, 4H, NCH2-CH2), 1.27-1.49 (m, 12H, aliph), 0.90 (t, J = 6.8 Hz, 3H, CH3)
n= 6: 740 mg of anhydride (2.04 mmol) and 300 mg of thioamine (2.04 mmol).
654 mg (65% yield)
1
H NMR (400 MHz, CDCl3, ppm): 8.74 (s, 4H, arom), 4.19 (t, J= 7.4 Hz, 4H, NCH2), 2.67
(t, J= 7.4 Hz, 2H, CH2S), 1.74 (m, 4H, NCH2-CH2), 1.23-1.49 (m, 16H, aliph), 0.90 (t, J = 6.8
Hz, 3H, CH3)
SH

n
O

SH

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H2N

DMF
125C

n
SH

n= 5; 6

A solution of dianhydride and thioamine in 10 mL of DMF was first degased for 10 min then
heated at 120 C for 24h. The product was then precipitated in water and purified on silica gel
or Allox using dichloromethane as eluent.
n= 5: 658 g of dianhydride (2.45 mmol) and 654 mg of thioamine (4.91 mmol).
164 mg (13% yield)
1
H NMR (400 MHz, CDCl3, ppm): 8.76 (s, 4H, arom), 4.19 (m, 4H, NCH2), 2.67 (m, 4H,
CH2S), 1.74 (m, 4H, NCH2-CH2), 1.24-1.48 (m, 12H, aliph)
n= 6: 956 mg of anhydride (3.56 mmol) and 1.05 g of thioamine (7.13 mmol).
328 mg (17 % yield)
1
H NMR (400 MHz, CDCl3, ppm): 8.77 (s, 4H, arom), 4.19 (m, 4H, NCH2), 2.67 (m, 4H,
CH2S), 1.75 (m, 4H, NCH2-CH2), 1.22-1.50 (m, 16H, aliph).

134

Appendix I

Br
Br

THF
+ AcSK

S
Br

reflux
O

To a solution of 4 g of 1, 6-dibromohexane (16.4 mmol) in 25 mL of THF were added 3 g of


potassium thioacetate (16.4 mmol) under argon atmosphere. The reaction mixture was then
refluxed for 24 hours. The KBr precipitate was eliminated by filtration. The filtrate was
concentrated under vacuum and the crude product was purified on silica gel using a 6:4
mixture of cyclohexane and diethyl ether as eluent to give 4.28 g of a yellow oil. (>100%,
traces of dibromohexane unreacted)
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H NMR (400 MHz, CDCl3, ppm): 3.40 (t, J= 6.4 Hz, 2H, Br-CH2), 2.85 (t, J= 7.2 Hz, 2H,
CH2S), 2.31 (s, 3H, CH3), 1.86 (m, 2H, CH2-CH2Br), 1.57 (m, 2H, S-CH2-CH2), 1.32-1.49
(m, 4H, aliph).

Diazonium salts preparation


R

THF
+ BF3.OEt2 + n-BuONO
-40C

NH2

BF4-

N+
N

Procedure for diazotization of anilines. The non-commercially available diazonium salts


were prepared from the corresponding amines according to literature procedures. In a typical
synthesis, 3 equivalents of BF3.OEt2 were added to a solution of the aniline derivate in 20 mL
of THF at -40 C. The mixture was stirred for 20 min and then 3 equivalents of butyl nitrite
(BuONO) were added drop wise. The mixture was stirred for 10 min and then warmed to
room temperature and poured in ether to precipitate the diazonium salt. The salt was filtered
and washed with ether. The different diazonium salts were stored at -18 C prior to use.

135

Appendix I
Synthesis of benzenediazonium tetrafluoroborate. 200 mg (2.15 mmol) of aniline were
converted to benzenediazonium salt following the procedure described above. 360 mg of a
light pink powder were obtained (87 % yield). 1H NMR (400 MHz, CD3CN, ): 7.40 (m, 2H); 7.54
(m, 3H). IR: 2302 cm-1 (N=N).

Synthesis of 4-cyanobenzenediazonium tetrafluoroborate (CN-BD). 254 mg (2.15 mmol) of 4aminobenzonitrile were converted to 4-cyanobenzenediazonium salt following the procedure
described above. 390 mg of an orange powder were obtained (84 % yield). 1H NMR (400
MHz, CD3CN, ): 8.25 (d, J= 8.8 Hz, 2H); 8.62 (d, J= 8.8 Hz, 2H). IR: 2290 cm -1 (N=N);

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2240 cm-1 (CN).


Synthesis of 4-dimethylaminobenzenediazonium tetrafluoroborate (NMe2-BD). 292 mg (2.15
mmol)

of

4-

N,

N-dimethylaminophenylamine

were

converted

to

4-

dimethylaminobenzenediazonium salts following the procedure described above. 430 mg of a


green powder were obtained (85 % yield). 1H NMR (400 MHz, CD3CN, ): 3.26 (s, 6H); 6.93
(d, J= 9.6 Hz, 2H); 7.99 (d, J= 9.6 Hz, 2H). IR: 2248 cm-1 (N=N).
Synthesis of 4-trifluoromethylbenzenediazonium tetrafluoroborate (CF3-BD). 346 mg (2.15
mmol) of 4-trifluoromethylaniline were converted to 4-trifluoromethylbenzenediazonium salt
following the procedure described above. 500 mg of a white powder were obtained (89 %
yield). 1H NMR (400 MHz, CD3CN, ): 8.23 (d, J= 8.8 Hz, 2H); 8.69 (d, J= 8.8 Hz, 2H). IR:
2306 cm-1 (N=N).
Synthesis of 4-heptadecafluorooctylbenzenediazonium tetrafluoroborate (C8F17-BD). 1.1 g
(2.15

mmol)

of

4-heptadecafluorooctylaniline

were

converted

to

4-

heptadecafluorooctylbenzenediazonium salt following the procedure described above. 1.02 g


of a white powder were obtained (78 % yield). 1H NMR (400 MHz, CD3CN, ): 7.73 (m, 2H);
8.42 (m, 2H). IR: 2308 cm-1 (N=N).
136

Appendix I
Synthesis of 4-(p-nitrophenyl)azobenzenediazonium tetrafluoroborate (DO-BD). 520 mg (2.15
mmol)

of

4-[(4-nitrophenyl)diazenyl]aniline

were

converted

to

4-(p-

nitrophenyl)azobenzenediazonium salt following the procedure described above. 586 mg of a


dark red powder were obtained (80 % yield). 1H NMR (400 MHz, CD3CN, ): 8.19 (d, J= 8.8
Hz, 2H); 8.31 (d, J= 8.8 Hz, 2H); 8.46 (d, J= 8.8 Hz, 2H); 8.68 (d, J= 8.8 Hz, 2H). IR: 2290
cm-1 (N=N); 1527 cm-1 (NO2); 1350 cm-1 (NO2).
Alternative diazotization method.

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This method was commonly employed with simple aniline derivatives soluble in HBF4 such
as for BD, CN-BD, DO-BD, NMe2-BD and CF3-BD preparation.
To a solution of aniline derivative in 5 mL of HBF4 at 0 C were slowly added 1.1
equivalents of sodium nitrite. After stirring for 15 min at 0 C, the mixture was poured in 150
mL of diethyl ether to precipitate the diazonium salt. The salt was filtered and washed with
diethyl ether. Yields were similar to those reported previously.

Bromotriazene preparation

1.5 g of 4-(2-hydroxyethyl)aniline (10.9 mmol) were placed in 10 mL of 48% HBr. The


mixture was refluxed for 4 h. After cooling, the reaction was poured in diethyl ether. The
white precipitate was filtered and immediately placed in 10 mL of HBF4 at 0 C. 830 mg of
sodium nitrite (12 mmol, 1.1 eq) were slowly added and the mixture was stirred for 15 min at
0 C. The diazonium salt was then precipitated in diethyl ether, filtered and thoroughly
washed with diethyl ether. 2.65 g of a white powder were obtained (85% yield).
1

H NMR (400 MHz, CD3CN, ppm): 8.42 (d, J= 8.8 Hz, 2H, ArH), 7.80 (d, J= 8.8 Hz, 2H,
ArH), 3.74 (t, J= 6.6 Hz, 2H, CH2Br), 3.43 (t, J= 6.6 Hz, 4H, BrCH2CH2).
137

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Appendix I

To a solution of 500 mg of 4-(2-bromoethyl)benzene diazonium tetrafluoroborate (1.68


mmol) in 20 mL of CH2Cl2 at 0 C were slowly added 122 mg of diethylamine (1.68 mmol)
and 230 mg of potassium carbonate (1.68 mmol). The mixture was then stirred at 0 C to
room temperature for 1 h. The inorganic salts were removed by filtration and the solvent
under vacuum to give a yellow oil (380 mg, 80% yield).
1

H NMR (400 MHz, CDCl3, ppm): 7.36 (d, J= 8.4 Hz, 2H, ArH), 7.16 (d, J= 8.4 Hz, 2H,
ArH), 3.75 (q, J= 6.4 Hz, 4H, NCH2), 3.54 (t, J= 7.8 Hz, 2H, CH2Br), 3.14 (t, J= 7.8 Hz, 4H,
BrCH2CH2), 1.26 (t, J= 7.6 Hz, 6H, CH2CH3).

138

Appendix I

Synthesis of push-pull systems


Note: due to the low purity of the final new products (presence of starting material), 13C NMR
and elemental analysis were not performed. Therefore, the products were only characterized
by 1H NMR.
Azobenzene derivatives
NO2
O

K2CO3
I

I
C10H20

DMF
50C

O
C10H20

O2N

NO2

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OH

To a solution of 1.4 g of 4-nitrophenol (10 mmol) in 30 mL of DMF were added 2 g of 1,10diiododecane (5 mmol) and 1.4 g of potassium carbonate (10 mmol). The mixture was stirred
for 24 h at 50 C. Water was then added and the aqueous layer was separated and extracted
with CH2Cl2. The extracts were washed with brine, dried and concentrated under vacuum.
The residue was chromatographed on silica gel using a 6:4 mixture of cyclohexane and
Ch2Cl2 as eluent to give 1.35 g of dimer (66% yield) and 610 mg of monomer (30% yield)
which was converted in dimer using the same protocol.
1

H NMR (400 MHz, CDCl3, ppm): 8.19 (d, J= 9.2 Hz, 4H, ArH, o-NO2), 6.93 (d, J= 9.2 Hz,
4H, ArH, m-NO2), 4.04 (t, J= 6.6 Hz, 4H, CH2O), 1.82 (p, J= 6.8 Hz, 4H, CH2CO), 1.28-1.52
(m, 12H, aliph)

O2N

O
C10H20

hydrazine
Pd/C
NO2

EtOH/DCM
reflux

H2N

O
C10H20

NH2

To a solution of 500 mg (1.2 mmol) of 1,10-bis(4-nitrophenoxy)decane in 20 mL of a 1:1


mixture of CH2Cl2 and EtOH were added 154 mg of hydrazine hydrate (4.8 mmol) and 100
mg of Pd/C. The mixture was refluxed for 24 h. The reaction mixture was then filtered
through cellite and concentrated under vacuum to give 400 mg of the dianiline. (94% yield)
1

H NMR (400 MHz, CDCl3, ppm): 6.73 (d, J= 8.8 Hz, 4H, ArH, o-NH2), 6.63 (d, J= 8.8 Hz,
4H, ArH, m-NH2), 3.87 (t, J= 6.6 Hz, 4H, CH2O), 1.73 (p, J= 7.2 Hz, 4H, CH2CO), 1.23-1.48
(m, 12H, aliph)

139

Appendix I
CnF2n+1

CnF2n+1

+ Oxone

DCM/H2O

NH2
O

n=1, 8

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To a solution of fluoroaniline in 35 mL of methylene chloride were added 3 equivalents of


Oxone in 200 mL of water. The mixture was stirred for 12 h at room temperature. Water was
then added and the aqueous layer was extracted with methylene chloride. The organic layer
was dried and concentrated under vacuum.
n=1: 2 g of 4-trifluoromethylaniline and 11.5 g of Oxone.
635 mg (29%)
1
H NMR (400 MHz, CDCl3, ppm): 8.01 (d, J= 8.4 Hz, 2H, ArH, o-NO), 7.92 (d, J= 8.4 Hz,
2H, ArH, m-NO)
n=8: 2 g of 4-(heptadecafluorooctyl)aniline and 3.6 g of Oxone.
1.2 g (59%)
1
H NMR (400 MHz, CDCl3, ppm): 8.03 (d, J= 8.4 Hz, 2H, ArH, o-NO), 7.90 (d, J= 8.4 Hz,
2H, ArH, m-NO)
O

CnF2n+1
O

O
C10H20

AcOH

H2N

N
N

+
NH2

O
C10H20

NH2

F2n+1Cn

N
O

n=1, 8

To a solution of dianiline in 15 mL of AcOH were added 1.5 equivalents of nitrosobenzene at


room temperature. The mixture was stirred for 36 h. Water was then added; the aqueous layer
was separated and extracted with CH2Cl2. The extracts were washed with brine, dried and
concentrated under vacuum. The residue was purified on silica gel, using a 7:3 mixture of
hexane and ethyl acetate as eluent.
n=1: 200 mg of 4-trifluoromethylnitrosobenzene and 272 mg of dianiline.
250 mg (43%)
1
H NMR (400 MHz, CDCl3, ppm): 8.24 (d, J= 8.4 Hz, 2H, ArH), 8.19 (d, J= 9.2 Hz, 2H,
ArH), 7.76 (d, J= 8.4 Hz, ArH), 6.94 (d, J= 9.2 Hz, 2H, ArH), 6.74 (d, J= 8.8 Hz, 2H, ArH),
6.64 (d, J= 8.8 Hz, 2H, ArH), 4.04 (t, J= 6.4 Hz, 2H, CH2ONN), 3.87 (t, J= 6.6 Hz, 2H,
140

Appendix I
CH2O), 1.82 (p, J= 6.8 Hz, 2H, CH2CONN), 1.74 (p, J= 6.8 Hz, 2H, CH2CO), 1.28-1.52 (m,
12H, aliph)
n=8: 500 mg of 4-(heptadecafluorooctyl)nitrosobenzene and 226 mg of dianiline.
347 mg (67%)
1
H NMR (400 MHz, CDCl3, ppm): 8.19 (d, J= 9.2 Hz, 2H, ArH), 7.34 (d, J= 8.4 Hz, 2H,
ArH), 6.93 (d, J= 9.6 Hz, ArH), 6.74 (d, J= 8.8 Hz, 2H, ArH), 6.71 (d, J= 8.4 Hz, 2H, ArH),
6.64 (d, J= 8.8 Hz, 2H, ArH), 4.04 (t, J= 6.4 Hz, 2H, CH2ONN), 3.87 (t, J= 6.6 Hz, 2H,
CH2O), 1.68-1.96 (m, 4H, CH2CO), 1.28-1.52 (m, 12H, aliph)
Stilbazolium preparation.
NR2

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NR2

N2

NH2

BF4
N

+ NaNO2

HBF4

0C
N

R= CH2CH2OH
R= Me

To a solution of 1 g of 4-aminopyridine (10.6 mmol) in 5 mL of HBF4 at 0 C were slowly


added 910 mg of sodium nitrite (11.3 mmol). The mixture was stirred for 15 min at 0 C. 1
equivalent of aniline derivative were slowly added at 0 C. 20 mL of DI water were added and
the mixture was stirred at room temperature for 1 h. The reaction was then poured in 50 mL of
2M aqueous sodium hydroxide. The resulting precipitate was filtered and the crude solid was
purified on silica gel using first methylene chloride (elimination of unreacted aniline
derivative) then ethyl acetate as eluent.
R= Me. 1.3 g of N,N-dimethylaniline (10.6 mmol).
1.3 g of an orange powder were obtained (54% yield).
1
H NMR (400 MHz, CDCl3, ppm): 8.71 (d, J=5.6 Hz, 2H, CH-N), 7.91 (d, J=8.8 Hz, 2H,
CH-C-CNMe2), 7.63 (d, J= 6 Hz, 2H, CH-C-N), 6.75 (d, J= 9.2 Hz, 2H, CH-CNMe2), 3.12 (s,
6H, CH3).
R= CH2CH2OH. 1.92 g of N-phenyldiethanolamine (10.6 mmol).
850 mg of an orange powder were obtained (28% yield).
1
H NMR (400 MHz, CDCl3, ppm): 8.68 (d, J=6 Hz, 2H, CH-N), 7.87 (d, J=9.2 Hz, 2H, CHC-CNR2), 7.67 (d, J= 6.4 Hz, 2H, CH-C-N), 6.80 (d, J= 9.2 Hz, 2H, CH-CNR2), 3.99 (t, J=
4.8 Hz, 4H, N-CH2), 3.77 (t, J= 4.8 Hz, 4H, O-CH2).
141

Appendix I

Alternative route for the diphenyl derivative

Br

Br

+ Oxone

DCM
H2 O

NH2

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To a solution of 2.5 g of 4-bromoaniline (14.9 mmol) in 35 mL of methylene chloride were


added 17.9 g of Oxone (29.8 mmol) in 45 mL of water. The mixture was stirred for 12 h at
room temperature. Water was then added and the aqueous layer was extracted with methylene
chloride. The organic layer was dried and concentrated under vacuum to give 2.55 g of a
brown solid (92% yield). The crude product was used without further purification.
1

H NMR (400 MHz, CDCl3, ppm): 8.10 (d, J= 8.8 Hz, 2H, ArH), 7.69 (d, J= 8.8 Hz, 2H,
ArH).
Br

NH2

Br

Toluene

NaOHaq

N
N

N
N
O

To a solution of 1 g of 4-nitrosobromobenzene (5.4 mmol) in 20 mL of a 1:1 mixture of


toluene and 50% aqueous sodium hydroxide were added 1.01 g of 4-aminopyridine (10.8
mmol). The mixture was stirred at room temperature for 36 h. Water was then added and the
aqueous layer was extracted with toluene. The organic phases were combined, dried over
sodium sulfate and concentrated under vacuum to give 1.26 g of a brown product (89% yield).
1

H NMR (400 MHz, CDCl3, ppm): 8.81 (d, J= 6 Hz, 2H, ArH), 8.10 (d, J= 8.8 Hz, 2H,
ArH), 7.84 (d, J= 8.4 Hz, 2H, ArH), 7.69 (d, J= 6 Hz, 2H, ArH).
142

Appendix I

Br

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HN

Pd(OAc)2
P(t-Bu)3
t-BuONa
Toluene
Reflux

N
N

In a glove box, a schlenk was charged with 600 mg of 4-[(4-bromophenyl)diazenyl]pyridine


(2.29 mmol) and 387 mg of diphenylamine (2.29 mmol). 20 mL of toluene were added. 15 mg
of palladium(II) acetate (0.07 mmol), 46 mg of tri-tert-butylphosphine (0.23 mmol) and 308
mg of sodium tert-butanolate (3.2 mmol) were added. The mixture was refluxed under argon
for 24 h. Inorganic salts were removed by filtration over cellite. The solvent was then
removed under vacuum. The crude product was purified on silica gel using methylene
chloride (removal of diphenylamine) then ethyl acetate as eluent to give 425 mg of an orange
powder (53% yield).
1

H NMR (400 MHz, CDCl3, ppm): 8.75 (m, 2H, ArH), 7.83 (d, J= 8.8 Hz, 2H, ArH), 7.65
(d, J= 6 Hz, 2H, ArH), 7.34 (t, J= 7.8, 4H, ArH), 7.19 (d, J= 7.6 Hz, 4H, ArH), 7.16 (t, J= 7.2
Hz, 2H, ArH), 7.09 (d, J= 8.8 Hz, 2H, ArH).

143

Appendix I
Diazonium salt derivatives
NR2

NR2

Br
N
N

EtOAc

60C

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NO2

R= CH2CH2OH
R= Me
R= Ph

Br

NO2

To a solution of pyridine azobenzene in ethyl acetate was added 1 equivalent of 4bromomethylnitrobenzene. The mixture was stirred at 60 C for 24 h. The solvent was then
removed under vacuum. Diethyl ether was added and the dark violet precipitate was collected
by filtration to afford product without further purification.
R= CH2CH2OH. 270 mg of 4-[(4-diethanolaminophenyl)diazenyl]pyridine (0.94 mmol) and
204 mg of 4-bromomethylnitrobenzene (0.94 mmol).
Dark violet powder, 365 mg (77% yield).
1
H NMR (400 MHz, CD3CN, ppm): 8.61 (d, J= 7.2 Hz, 2H, CH-N+), 8.28 (d, J= 8.8 Hz, 2H,
CH-C-CNR2), 8.11 (d, J= 8 Hz, 2H, CH-CNO2), 7.62 (d, J= 8.8 Hz, 2H, CH-CNR2), 7.57 (s,
2H, CH-C-N), 7.11 (d, J= 7.6 Hz, 2H, CH-C-CNO2), 5.74 (s, 2H, CH2-N+), 3.83 (s, 8H, NCH2-CH2-OH).
R= Me. 146 mg of 4-[(4-dimethylaminophenyl)diazenyl]pyridine (0.64 mmol) and 139 mg of
4-bromomethylnitrobenzene (0.64 mmol).
Dark violet powder, 128 mg (45% yield).
1
H NMR (400 MHz, CDCl3, ppm): 9.57 (d, J=6 Hz, 2H, CH-N+), 8.19 (d, J= 8.4 Hz, 2H,
CH-CNO2), 8.02 (d, J= 6 Hz, 2H, CH-C-N+),7.96 (d, J= 8.8 Hz, 2H, CH-C-CNO2); 7.91 (d,
J=8.8 Hz, 2H, CH-C-CNMe2), 6.75 (d, J= 9.2 Hz, 2H, CH-CNMe2), 6.56 (s, 2H, CH2-N+);
3.17 (s, 6H, CH3).
R= Ph. 200 mg of 4-[(4-diphenylaminophenyl)diazenyl]pyridine (0.57 mmol) and 123 mg of
4-bromomethylnitrobenzene (0.57 mmol).
Dark violet powder, 305 mg (78% yield).
144

Appendix I
1

H NMR (400 MHz, CDCl3, ppm): 9.61 (d, J= 6.4 Hz, 2H, CH-N+), 8.18 (d, J= 8.4 Hz, 2H,
CH-CNO2), 8.08 (d, J= 6.4 Hz, 2H, CH-C-N+), 7.99 (d, J= 8.8 Hz, 2H, CH-C-CNO2), 7.82 (d,
J= 9.2 Hz, 2H, NN-C-CH), 7.41 (t, J= 8 Hz, 4H, NC-CH), 7.27 (t, J= 8 Hz, 2H, NC-C-CH),
7.24 (d, J= 7.6 Hz, 4H, NC-CH), 6.97 (d, J= 9.2 Hz, 2H, NN-C-C-CH), 6.59 (s, 2H, CH2-N+).

NR2

NR2

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H2 , Pd/C
EtOH

Br

R= CH2CH2OH
R= Me
R= Ph

NO2

Br

NH2

A solution of nitrostilbazolium and Pd/C in ethanol was stirred 2h under 2 bars of dihydrogen
at room temperature. The resulting precipitate was collected. Pd/C was removed by
solubilizing the aminostilbazolium in acetone. The solvent is then removed under vacuum to
afford a dark violet solid. This solid was used directly in diazoniation reaction.

145

Appendix I

Thiol derivatives
NR2

NR2
Br

N
N

EtOAc
N

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60C

Br

SH
N

R= CH2CH2OH
R= Me
R= Ph
SH

To a solution of pyridine azobenzene in ethyl acetate was added 1 equivalent of 6bromohexanethiol. The mixture was stirred at 60 C for 24 h. The solvent was then removed
under vacuum. Diethyl ether was added and the dark violet precipitate was collected by
filtration to afford product without further purification.
R= CH2CH2OH. 187 mg of 4-[(4-diethanolaminophenyl)diazenyl]pyridine (0.65 mmol) and
129 mg of 6-bromohexanethiol (0.65 mmol).
Dark violet powder, 180 mg (57% yield).
1
H NMR (400 MHz, CD3CN, ppm): 8.68 (d, J=6 Hz, 2H, CH-N), 7.87 (d, J=9.2 Hz, 2H,
CH-C-CNR2), 7.67 (d, J= 6.4 Hz, 2H, CH-C-N), 6.80 (d, J= 9.2 Hz, 2H, CH-CNR2), 3.99 (t,
J= 4.8 Hz, 4H, N-CH2), 3.77 (t, J= 4.8 Hz, 4H, O-CH2) 2.57 (m, 4H, N-CH2 and CH2S), 1.281.62 (m, 8H, Haliph).
R= Me. 150 mg of 4-[(4-dimethylaminophenyl)diazenyl]pyridine (0.66 mmol) and 130 mg of
6-bromohexanethiol (xx mmol).
Dark violet powder, 80 mg (29% yield).
1
H NMR (400 MHz, CD3CN, ppm): 8.61 (d, J= 6.4 Hz, 2H, ArH), 7.84 (d, J= 9.2 Hz, 2H,
ArH), 7.67 (d, J= 6 Hz, 2H, ArH), 6.81 (d, J= 9.2 Hz, 2H, ArH), 2.59 (m, 4H, N-CH2 and
CH2S), 1.28-1.62 (m, 8H, Haliph).
146

Appendix I
R= Ph. 200 mg of 4-[(4-diphenylaminophenyl)diazenyl]pyridine (0.57 mmol) and 112 mg of
6-bromohexanethiol (0.57 mmol).
No product obtained.

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Triazene derivatives

To a solution of pyridine azobenzene in ethyl acetate was added 1 equivalent of


bromotriazene. The mixture was stirred at 60 C for 24 h. The solvent was then removed
under vacuum. Diethyl ether was added and the dark violet precipitate was collected by
filtration to afford product without further purification.
R= Me: 75 mg of pyridine azobenzene (0.33 mmol) and 95 mg of bromotriazene (0.33
mmol).
Dark violet powder, 20 mg (12% yield).
R= Ph: 60 mg of pyridine azobenzene (0.17 mmol) and 50 mg of bromotriazene (0.17 mmol).
Dark violet powder, 10 mg (10% yield).

147

Appendix I

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Carboxylic acid derivatives

To a solution of 200 mg of pyridine azobenzene (0.88 mmol) in ethyl acetate were added 135
mg of 2-chloroethanoic acid (0.88 mmol). The mixture was stirred at 60 C for 24 h. The
solvent was then removed under vacuum. Diethyl ether was added and the dark violet
precipitate was collected by filtration to afford product without further purification.
Dark violet powder, 66 mg (20% yield).

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Appendix II

Appendix II: Supporting Information of the article

Supporting Information

Towards organic film passivation of germanium wafers


using diazonium salts: mechanism and ambient stability
Xavier Lefvre, Olivier Segut, Pascale Jgou, Serge Palacin and Bruno Jousselme

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XPS analyses

Figure S1. XPS survey and Ge 2p core level spectra of a pristine Ge surface

Figure S2. XPS survey and Ge 2p core level spectra of a HCl-treated Ge surface
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Appendix II

Figure S3. XPS survey, Ge 2p and S 2p core level spectra of a HCl-treated Ge surface
protected with a SAM of nonanethiol

Figure S4. XPS survey spectrum of a HCl-treated Ge surface functionalized with BD


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Figure S5. XPS survey spectrum of a HCl-treated Ge surface functionalized with CN-BD

Figure S6. XPS survey spectrum of a HCl-treated Ge surface functionalized with NBD

Figure S7. XPS survey spectrum of a HCl-treated Ge surface functionalized with OMe-BD

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Figure S8. XPS survey spectrum of a HCl-treated Ge surface functionalized with NMe2-BD

Figure S9. XPS survey spectrum of a HCl-treated Ge surface functionalized with CF3-BD

Figure S10. XPS survey spectrum of a HCl-treated Ge surface functionalized with C8F17-BD
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Figure S11. XPS survey spectrum of a HCl-treated Ge surface functionalized with DO-BD

Figure S12. XPS survey spectra of a nonathiolate SAM on a HCl-treated Ge surface freshly
prepared (left, black line), after 22 hours at air exposure (30 % reoxidation, left, red line) and
XPS survey spectra of a HCl-treated Ge surface functionalized with CF3-BD freshly prepared
(right, black line), after one week at air exposure (54 % reoxidation, right, red line)

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121 eV

Figure S13. LEED pattern of a HCl-treated Ge surface at 121 eV showing the (100)
orientation and the 2x1 reconstruction.

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