Polymer Electronics

Polymer Electronics –
A Flexible Technology
Editors: Frances Gardiner

Eleanor Carter
Polymer Electronics –
A Flexible Technology
Editors:
Frances Gardiner
Eleanor Carter
iSmithers – A Smithers Group Company
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
First Published in 2009 by
iSmithers
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©2009, Smithers Rapra
All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
Every effort has been made to contact copyright holders of any material reproduced
within the text and the authors and publishers apologise if
any have been overlooked.
ISBN (Hard-backed): 978-1-84735-421-1

ISBN (Soft-backed): 978-1-84735-422-8
e-book: 978-1-84735-423-5
Typeset by Argil Services

Indexed by Argil Services
Printed and bound by Lightning Source
C
ontents
1 Roadmap for Organic and Printed Electronics ................................................1
1.1 Introduction ..........................................................................................1
1.2 Applications ..........................................................................................2
1.3 Organic Electronics Association (OE-A) Roadmap for Organic

Electronics Applications ........................................................................3
1.3.1 Technology................................................................................4
1.3.2 Materials...................................................................................4
1.3.3 rinting and Patterning Techniques .............................................6
1.3.4 Devices......................................................................................7
1.4 Principle Challenges/Red Brick Walls .....................................................8
1.5 Summary and Outlook ........................................................................10
1.6 Global Network for an Emerging Industry ..........................................10
2 Technical Issues in Printed Electrodes for All-Printed Thin-Film Transistor

Applications 13
2.1 Introduction ........................................................................................13
2.2 Surface Roughness of Printed Electrodes .............................................14
2.3 Edge Waviness in Printed Electrodes ....................................................15
2.4 Solution-Process Organic TFT .............................................................17
2.5 Conclusion ..........................................................................................18
2.6 Acknowledgement ...............................................................................18
iii
Polymer Electronics – A Flexible Technology
3 All-Printed Flexible Organic Light-emitting Diodes .......................................21
Introduction 21
Roll-to-Roll Printing......................................................................................21
Gravure Printing of Poly(3,4-ethylenediocythiophene):poly(styrene sulfonate)

and Pentafluorobenzenethiol .........................................................................24
Screen Printing of Aluminium Cathode .........................................................25
Characteristics of All-Printed OLEDS............................................................26
Roll-to-Roll Printed OLED Demonstrators ...................................................27
Summary 28
Acknowledgement .........................................................................................28
4 Roadmap for Organic and Printed Electronics ..............................................31
Introduction 31
4.1 Process Modelling and Simulation of Ink Jet Printing ..........................32
4.2 Characterisation of PEDOT-PSS Inks and Products .............................36
4.3 Characterisation of Carbon Nanotube - PEDOT:PSS

Nanocomposite Products .....................................................................37
4.4 Electrospinning of Carbon Nanotube Inks ...........................................40
4.5 Conclusions .........................................................................................41
5 Highly Conductive Plastics – Custom-formulated Functional Materials

for Injection Mouldable Electronic Applications ...........................................43
5.1 Introduction ........................................................................................43
5.2 Characteristics of the Hybrid Compound Within the Injection

Moulding Process ................................................................................45
5.2.1 The Cavity Filling ...................................................................45
5.2.2 The Morphological Structure ..................................................46
5.2.3 Dependence of the Conductivity on Geometry, Material and
Process Condition ...................................................................47
iv
Contents
5.2.4 Temperature Dependency on the Conductivity ........................50

5.2.5 Electromagnetic Shielding Effectiveness ..................................51
5.2.6 Injection Moulding of Conductor Paths ..................................52
5.3 Conclusions and Outlook ....................................................................54
Acknowledgements........................................................................................55
6 Additives in Polymer Electronics ...................................................................57
6.1 Introduction ........................................................................................57
6.2 Degradation and Stabilisation of Polymer ............................................57
6.3 Stabilisers for Polymer Electronics .......................................................60
6.4 Functional Additives for Polymer Electronics ......................................63
7 A Facile Route to Organic Nanocomposite Dispersions of Polyaniline – single

Wall Carbon Nanotubes ................................................................................67
7.1 Introduction ........................................................................................67
7.2 Materials .............................................................................................68
7.3 Experimental Section ...........................................................................68

7.3.1 Scheme - 1 Polyaniline Synthesis [17] ......................................68
7.3.2 Scheme - 2 Organic Dispersions of PANI ................................68
7.3.3 Scheme - 3 Exfoliation of Single Wall Carbon Nanotubes .......69
7.3.4 Scheme - 4 Organic ‘Nanocomposite’ Dispersions of PANI-
SWNT 69
7.4 Characterisation ..................................................................................70
7.5 Results and Discussions .......................................................................70

7.5.1 Phase Inversion Phenomenon ..................................................70
7.5.2 FT-IR Spectroscopy .................................................................70
7.5.3 UV-Vis Spectroscopy ...............................................................72
7.5.4 Four-probe Conductivity .........................................................73
7.6 Conclusions .........................................................................................73
v
7.7 Acknowledgements ..............................................................................74
8 Preparation and Characterisation of Novel Electrical Conductive Rubber

Blends 77
8.1 Introduction ........................................................................................77
8.2 Experimental .......................................................................................77

8.2.1 Chemicals and Raw Materials.................................................77
8.2.2 Synthesis of PANI.DBSA and Blends Preparation ....................77
8.3 Characterisation of NBR-PAni.DBSA Blends .......................................78
8.3.1 Methods of Characterisation...................................................78
8.3.2 Calculation of Solubility Parameter Values..............................78
8.3.3 Morphological Studies (Optical Microscopy and TEM) ..........78
8.3.4 FT-IR Spectroscopy .................................................................80
8.3.5 DSC Thermal Analysis ............................................................81
8.3.6 Electrical Conductivity Determination ....................................81
8.4 Conclusion ..........................................................................................85
Acknowledgements........................................................................................85
9 Solar Textiles 87
9.1 Introduction ........................................................................................87
9.2 Why Textiles? ......................................................................................88
9.3 Solar Cells ...........................................................................................88
9.4 Technological Specifications.................................................................89
9.5 Suitable Textile Constructions .............................................................90

9.5.1 Fibres ......................................................................................90
9.5.2 Fabrics ....................................................................................91
9.6 Electrical Conductivity ........................................................................91
9.7 The Future ...........................................................................................93
vi
Contents
10 Flexible Sensor Array for a Robotic Fingertip Using Organic Thin Film Tran-
sistors (OTFT) with Minimum Interconnects and Improved Noise Tolerance 95
10.1 Introduction ........................................................................................95
10.2 General Description of the System .......................................................96
10.3 Operation Mechanism .........................................................................96
10.4 Robotic Finger Tip Specifications.........................................................97
10.5 System Design ......................................................................................97

10.5.1 OTFT Devices .........................................................................97
10.5.2 Sensor Array ...........................................................................98
10.5.3 Active Matrix Addressing Electronics .....................................98
10.5.4 Astable Multivibrator .............................................................99
10.6 Important Design Features .................................................................101
Conclusion 102
11 An Organic Thin Film Transistor Pixel Circuit for Active-Matrix Organic

Light
Emitting Diode Flat Panel Display ...............................................................105
11.1 Introduction ......................................................................................105
11.2 Pixel Circuits Designs ........................................................................106
11.3 The Voltage Programming Pixel Circuit .............................................107
11.4 Simulation Results .............................................................................108

11.4.1 OTFT model .........................................................................110
11.4.2 OLED model.........................................................................110
11.4.3 The results of the voltage programming circuit .....................110
11.5 Conclusion ........................................................................................113
12 Intelligent Packaging for the Food Industry .................................................117
12.1 Introduction ......................................................................................117
12.2 RFID and Packaging Connection - The Age of Connectivity ..............119
vii
12.3 TTI and Other Solutions - The Viewpoint of Food Industries ............123
12.4 New Proposals - The Consumer’s Viewpoint .....................................127
12.5 Food Companies Under Attack - Sabotage and Class Actions ............130
12.6 Conclusions .......................................................................................130
Abbreviations .....................................................................................................133
Index ..................................................................................................................137
viii
C
ontributors
Kok Chong Yong
Advanced Rubber Technology Unit, Rubber Research Institute of Malaysia (RRIM),

Malaysian Rubber Board, 47000 Sungai Buloh, Selangor, Malaysia
Seungjun Chung
Seoul National University, Department of Electrical Engineering and Computer

Science
Kwanak-Ro 599 Shillim-9-Dong, Kwanak-Gu, Seoul 151-744, Korea
Jan Fragner
Institute of Plastics Processing at RWTH Aachen University (IKV), Pontstrasse 49,

Aachen, D-52062, Germany
Daisuke Fujiki
Ciba Inc, R1038.4.07, Basel, CH-4002, Switzerland
Klaus Hecker
PolyIC GmbH & Co. KG, Tucherstrasse 2, 90763 Fürth, Germany
Yongtaek Hong

Science
Jaewook Jeong

Science
ix
Jinwoo Kim

Science
Darek Korzec
The German University in Cairo, 15th Moustafa el Maghraby-el, nozha Heliopolise,

Eygpt
Constantina Lekakou
Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, Surrey

GU2 7XH, UK
Arto Maaninen
VTT Technical Research Centre of Finland, Kaitoväylä 1, FI-90571 Oulu, Finland
Tiina Maaninen
Ahmed Maitouk
Faculty of Electrical and Electronics Engineering, German University in Cairo
7, Rabaa al Istethnary buildings, Nozha St – Nasr, Egypt
Robert Mather
Power Textiles Limited, Upland House, Ettrick Road, Selkirk, EH14 4AS, UK
Walter Michaeli

Wolfgang Mildner
PolyIC GmbH & Co. KG, Tucherstrasse 2, 90763 Fürth, Germany
x
Contributors
Mohamed Montasser
Electrical and Electronics Engineering Department, The German University in Cairo,

15th Moustafa el Maghraby-el, nozha Heliopolise, Eygpt
Pradipta Nayak

Science
Salvatore Parisi
Department of Hygiene, Preventive Medicine and Public Health ‘R. DeBlasi’,
University of Messina, Via Roccazzo, 25-90135, Palermo, Sicily, Italy
Tobias Pfefferkorn

Sanjay Rastogi
Department of Materials, University of Loughborough, Loughborough, LE11 3TU,

UK
Dimitris Schoinas

GU2 7XH, UK
Markus Tuomikoski
Sainath Vaidya
Department of Materials, University of Loughborough, Loughborough, LE11 3TU,

UK
Marja Välimäki
xi
John Watts

GU2 7XH, UK
John Wilson
Power Textiles Limited, Upland House, Ettrick Road, Selkirk, EH14 4AS, UK
Peter Wilson

GU2 7XH, UK
xii
Preface
P
reface
The worldwide market for polymer electronic products has been estimated to be
worth up to £15 billion by 2015 and the opportunity for new markets could be as
high as £125 billion by 2025.”
The rapid development of polymer electronics has revealed the possibility for
transforming the electronics market by offering lighter, flexible and more cost effective
alternatives to conventional materials and products. With applications ranging from
printed, flexible conductors and novel semiconductor components to intelligent labels,
large area displays and solar panels, products that were previously unimaginable are
now beginning to be commercialised.
Smithers Rapra is pleased to announce its first Polymer Electronics conference,

designed to inform researchers, material suppliers, component fabricators and
electronics manufacturers of the latest research and developments in this dynamic
and rapidly evolving field.
With a prestigious panel of speakers presenting on a wide range of polymer electronics

and related technology topics, this conference will bring together senior delegates
from across the world to discuss the technologies and opportunities at the heart of
polymer electronics.
The conference offers two full days of application focussed technical papers detailing
current and future developments in the fast-moving polymer electronics industry: it
is a must for forward thinking companies wishing to participate in this predicted
£125 billion market.
Who Should Attend:
The conference will particularly appeal to those with the following roles:
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1
Roadmap for Organic and
Printed Electronics
Wolfgang Mildner and Klaus Hecker
1.1 Introduction
The key trends that will drive modern societies in the next decades are:
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Roadmap for Organic and Printed Electronics
1.3 Organic Electronics Association (OE-A) Roadmap for Organic

Electronics Applications
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1.3.1 Technology
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1.3.2 Materials
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1.3.3 Printing and Patterning Techniques
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Table 1.1 Key parameters for several printing technologies

Printing Speed (m2/s) Resolution Film thickness Viscosity
Method (μm) (μm) (Pa-s)
iÝ £ä Óäxä ä°xÊÊÓ ä°äxä°x
À>ÛÕÀi £ä Óäxä ä°xÊÊÓ ä°äxä°Ó
"vvÃiÌ Óä £x ä°xÊÊÓ Îä£ää
-VÀii Ê£ä nä£ää xÊÊÓx ä°xxä
iÌ ä°£ Óä ä°£ÊqÊä°x ä°ääÓä°äÓx
Source: OE-A; Printed Electronics Consulting, in ‘Organic Electronics
Technology’, VDMA, 2006; Fraunhofer IZM, ‘Abschlussbericht zum Projekt
PropolyTec’, 2006.
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1.3.4 Devices
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1.4 Principle Challenges/Red Brick Walls
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12
2
Technical Issues in Printed Electrodes
for All-Printed Thin-Film Transistor
Applications
Yongtaek Hong, Jaewook Jeong, Seungjun Chung, Jinwoo Kim,

and Pradipta K Nayak
2.1 Introduction
Direct-printing of functional layers of solution-process thin-film devices has recently

been a hot topic in rugged, disposable, large-area, printed, and flexible electronics
applications. Several direct printing methods such as screen printing, microcontact
printing, gravure printing, imprinting, laser assisted patterning, and inkjet printing have
been considered as the next-generation patterning methods because they can provide
high-throughput, low-cost, low-temperature manufacturing capabilities [1-5].
For all-printed thin film transistors (TFT), various organic and inorganic metal
electrode materials, such as conductive polymer, carbon nanotube (CNT), organic
metal compound, or metal nano-particles, have been used as gate and source/drain
electrodes [6-11] in a combination with inkjet- and laser-based printing methods.
One of the immediate applications for all-printed TFT would be flexible or rugged
display backplane and disposable radio frequency identification (RFID) tags. In
addition, printed metal electrodes and TFT have also been used to fabricate passive
circuit components, power transmission sheets and sensors for ambient electronics
and electronic skin [12-13].
When a narrow line is patterned by printing-based methods, rough surfaces, coffee

rings, and/or the creation of wavy edges along the printed lines are frequently observed.
Rough surface and coffee ring effects of printed gate electrodes are directly related to
gate leakage current, thus current on/off ratio, of the fabricated TFT. If edge waviness
of the printed electrodes exists in source/drain (S/D) electrodes, current flow variation
and possible changes in operation stability are to be expected. Ink and printing
process conditions, especially for inkjet printing methods, must be well controlled to
suppress these undesirable structural effects due to the relatively large ink drop size
for narrow line patterning. Even in the laser-printing method where a few micron-
size beam spots are used, edge waviness can be obtained if the overlap between laser
13
beam spots is not well optimised [14]. Therefore, in this paper, technical issues of
the printed electrodes for all-printed TFT applications, including surface roughness
and edge waviness, are addressed.
2.2 Surface Roughness of Printed Electrodes
An inkjet printer from DIMATIX Corporation (DMP-2800 series) and silver ink
from INKTEC Corporation (IJ-TEC-010) have been used to print silver electrodes
on various substrates. When the width of the printed electrodes was in the range of
several hundred micrometers, it was possible to suppress the surface roughness of
the printed electrodes to a level similar to that of comparable thermally evaporated
electrodes. A surface roughness of about 2.2-2.4 nm in root-mean-square (RMS) and
19-20 nm in peak-to-valley values was obtained from both printed and evaporated
silver electrodes. If the line width of the printed silver electrode was reduced to
some tens of micrometers, it was found that the surface roughness increased to
approximately 5 nm in RMS and 29 nm in peak-to-valley values, respectively. The
atomic force microscope (AFM) images are shown in Figure 2.1. The AFM images
were measured by using the non-contact mode at a rate of 1 Hz for a scan area of
10 s 10 μm2. Although surface roughness increased, if an organic dielectric layer
was used on the printed electrodes, surface roughness was further reduced due to
the planarisation capability of the organic dielectric layers. It was observed that, for
wide silver electrodes, surface roughness was reduced to about 1.5 nm in RMS and
10 nm in peak-to-valley values when a poly(4-vinylphenol) (PVP) layer was spin-
coated onto the electrodes.
Figure 2.1 Microscope and atomic force microscopy images of the printed
silver electrodes
14
Technical Issues in Printed Electrodes for All-Printed
Thin-Film Transistor Applications
Sheet resistance of the printed silver electrode also increased from 0.2-0.4 ohm/
square to 0.6-0.8 ohm/square when the line width was reduced, which correspond
to approximately 4-5 s 10-6 ohm-cm and 16-20 s 10-6 ohm-cm, respectively. The
20 Mm diameter nozzle used in this investigation gave a typical ink drop size on
substrates of approximately 50 Mm. This gave a smaller potential line width than
is obtained from current processes suggesting that if the nozzle size can be reduced,
narrow line widths are achievable. However, for inkjet printing, it can be difficult
to obtain sufficiently narrow lines and to ensure a high enough aspect ratio at the
same time. If the aspect ratio is not high enough, resistance of the printed line will
be high and current flow capacity through the lines will be significantly reduced.
2.3 Edge Waviness in Printed Electrodes
Edges of the printed narrow lines frequently show irregular wavy patterns depending
on the material and printing process conditions. Extra care should be taken during
the inkjet-printing process, since the properties of inks, such as concentration and
viscosity, change with time. Figure 2.2 shows examples of printed silver electrodes
with wavy edges. Edge waviness can be modeled and numerically analyzed [15]. If
S/D electrodes of TFT have wavy edges, TFT performance and operation stability
can be significantly affected. The ATLAS 3D device simulator (Silvaco Inc.) was
used to simulate this S/D edge waviness effect. Peak-to-peak magnitude of the wavy
patterns in S/D electrodes had the most significant effects on the TFT performance
variations. In addition to performance variation, the effects of the overlap between
gate and S/D electrodes on TFT performances were also analysed. It was assumed
that gate and S/D electrodes had flat and wavy edges, respectively. Due to highly
localised electric field distribution along the edges of the wavy patterns, as shown
Figure 2.2 Examples of edge waviness in printed silver electrodes
15
Figure 2.3 Current density distribution of TFT with flat gate and wavy S/D
electrodes in (a) lateral and (a) vertical direction with respect to channel. Dotted
white and red lines show defined effective channel length and flat edge of the gate
electrodes. GO means gate overlap
in Figure 2.3, overlap smaller than peak-to-peak magnitude of the wavy patterns
provided sufficiently low contact resistance as long as the overlap was larger
than characteristic lengths of TFT. The characteristic lengths of TFT are typically
determined by current spreading under the S/D electrodes, which is a function of
channel resistance and parasitic resistance of the TFT. Therefore, there exits an
optimised gate overlap for given TFT structure from the viewpoint of reducing
parasitic resistance. Although the characteristic length concept was used for typical
TFT with flat edges in the S/D electrodes, similar analysis can be applied to the TFT
with wavy S/D electrodes. However, in this case, due to the current localisation
effect, current spreading occurs along the peak region of the wavy patterns, leading
to variation in characteristic length according to the waviness parameters, such as
peak-to-peak magnitude. The variation of characteristic length can be obtained from
a transmission line method [15] and can be used for optimisation of gate overlap
in the TFT with wavy S/D electrodes.
Hydrogenated amorphous silicon (a-Si:H) TFT were used as test vehicles for the
simulation results. Wavy edges were photolithographically patterned in the S/D
electrodes and TFT performance and operation stability were tested [16]. Stress
bias-dependent operation instability was shown by a-Si:H TFT. Threshold voltage
16
shift was relatively independent of peak-to-peak magnitude of the wavy edges.

It was also observed that when TFT were stressed in a constant current mode,
the threshold voltage shift demonstrated a large dependency on the peak-to-peak
magnitude variations. This shows that edge waviness will have different effects
for switching and current-driving TFT in terms of the operation stability. The
same analysis can be applied to organic or metal-oxide TFT if their source/drain
electrodes are printed.
2.4 Solution-Process Organic TFT
Inkjet-printed silver electrodes, spin-coated PVP, and spin-coated 6,13-bis

(triisopropylsilylethynyl) pentacene (TIPS-pentacene) were used as gate and S/D
electrodes, gate dielectric layer, and semiconductor layer in solution-process organic
TFT as shown in Figure 2.4. PVP layer (700-800 nm thick) showed a leakage
current of 8-10 nA/cm2 at 0.5 MV/cm and a capacitance of 5-6 nF/cm2 at 1 kHz.
Details of the fabrication process and properties of the printed silver electrodes
and spin-coated PVP insulator have been reported elsewhere [17]. Organic
thin film transistor (OTFT) showed mobility of about 0.07 cm2/Vs, a threshold
voltage of 2.74 V, and on/off current ratio of >103 as shown in Figure 2.5, which
are comparable to other previously reported results [18-21]. When the printing
process and gate dielectric interface are further optimised, better performance is
expected. In addition, printed-version of TIPS-pentacene based TFT showed similar
TFT performances.
Figure 2.4 Schematic description of the fabricated OTFT
17
Figure 2.5 Transfer characteristics of the fabricated OTFT. High gate leakage
current reduced current of/off ratio. (W/L = 1000/40-60 Mm/Mm)
2.5 Conclusion
Technical issues in printed electrodes were briefly reviewed for all-printed TFT
applications. Surface morphology and edge waviness of the printed electrode
should be well controlled to produce uniform and stable TFT behavior and
consistent thin-film device performances. This investigation fabricated solution-
process TIPS-pentacene based TFT with the printed silver electrodes. Solution-
process materials can be readily combined with a low-cost printing process,
which can significantly reduce complexity in the fabrication and manufacturing
process. In addition, these types of solution-process TFT can be fabricated at low
temperatures and they can be also readily implemented on plastic substrates for
flexible electronics applications.
2.6 Acknowledgement
This work was supported by the ‘SystemIC 2010’ project of the Korea Ministry of
Knowledge Economy and the Seoul R&BD Program (CRO70048). Nayak would
like to thank the BK21 project of the Korean Ministry of Education, Science and
Technology (SNU BK21 Research Division for Information Technology). The authors
would like to thank Professor Soon-Ki Kwon at Gyeongsang National University
for providing the TIPS-pentacene material. The authors would also like to thank
Professor Changhee Lee and the OLED Center at Seoul National University for
valuable technical discussions and process facility support, respectively.
18
References
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20
3
All-Printed Flexible Organic
Light-emitting Diodes
Arto Maaninen, Markus Tuomikoski, Marja Välimäki

and Tiina Maaninen
Introduction
Organic electronics has grown into a promising candidate to replace several low end
silicon applications. Printed and organic electronics are expected to become worth
between 250 – 300 billion USD within the next 20 years [1]. To date, fabrication
has been carried out using traditional and expensive batch processes such as the
vacuum evaporation technique. However, the potential application of roll-to-roll
printing represents a new and interesting method for the manufacture of flexible
organic devices [2] that would provide high throughput capability with decreased
fabrication costs.
Printing techniques for roll-to-roll production of organic light-emitting diodes (OLED)

were investigated by the EU funded project; roll-to-roll manufacturing technology
for flexible OLED devices and arbitrary size and shape displays (ROLLED) [3])
under the Sixth EU-Framework Programme. The project objective was to fabricate
an entire OLED structure by using roll-to-roll manufacturing methods and examine
how commercial production could be set up and integrated into an existing printing
process. In order to attain roll-to-roll compatibility, it was essential for all materials,
inks and devices to be suitable for printing.
Roll-to-Roll Printing
In this study, all the printing experiments were carried out using a roll-to-roll
pilot-line production machine, which contains four exchangeable printing units for
reverse and forward gravure, flexography and rotary screen printing techniques. The
printing machine also provided thermal heating units and sensors for controlling the
registration and tension of the web. A photograph of the pilot-line printing machine
is shown in Figure 3.1.
21
Figure 3.1 The photograph of roll-to-roll pilot-line printing machine used for
manufacturing of OLED [3]
The procedure for OLED printing development was carried out in the following way:
1) Developing ink suitable for the printing technique;
2) Printing experiments using lab scale printers with variable printing parameters;
3) Re-formulation of printing inks to optimise film quality and performance;
4) Scaling-up printing inks and fabrication of printing tools for roll-to-roll printing
experiments.
Figure 3.2(a) outlines the gravure printing process in which ink picked up from a
reservoir fills the engraved cells of a rotating gravure cylinder. A doctoring blade
removes any excess ink so that only ink contained within these cells is transferred
onto the surface of the impression roll, which is covered with a flexible substrate.
The thickness and quality of the printed films are determined by parameters such
as the load of the doctoring blade, ink properties, the characteristics of the gravure
cylinder, the pressure between the cylinder and the impression roll, and printing speed.
In this study, the gravure printing technique was used for thin film printing of a hole
injection and green and red light-emitting polymers.
22
All-Printed Flexible Organic Light-emitting Diodes
Figure 3.2 The schemes of (a) gravure printing and (b) rotary screen printing
processes used in the roll-to-roll OLED processing [4]
Screen printing is one of the simplest printing processes and can be used for a number
of applications such as printing textiles, ceramics and electronics. However, print
quality can be affected by factors such as the properties of the ink and substrate, the
type of material used for the stencil and its thickness, the number of mesh openings of
the screen fabric, the properties of the squeegee and printing speed. [5] Rotary screen
printing is carried out at a higher speed than flat screen printing. The screen has a
cylinder shape and the ink is placed inside the cylinder as shown in Figure 3.2(b). The
squeegee, which is also within the cylinder, forces the ink through the openings in the
screen and onto the substrate [6]. In the study, the rotary screen printing technique
was used for printing an insulator, a cathode and electric contacts.
23
Gravure Printing of Poly(3,4-ethylenediocythiophene):poly(styrene

sulfonate) and Pentafluorobenzenethiol
The printability of standard poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)

(PEDOT:PSS) polymer was examined on the top of indium tin oxide (ITO) coated
plastic foil with various gravure printing parameters and ink formulations. The
experiments showed that a modified aqueous PEDOT:PSS solution was necessary
for the gravure printing process. According to printability tests, the addition of the
surfactant Tween®80 enhanced the wetting properties of the ink, as did the addition
of the solvent: isopropyl alcohol. Isopropyl alcohol also influenced the morphology
of the printed structure by altering the fluid, flow and drying properties, of the ink.
A 70 nm thick, smooth and pinhole-free film was successfully printed using a 100
lines/cm and 37 μm cell depth gravure cylinder and modified ink containing 65 wt%
of PEDOT:PSS, 1 wt% Tween®80, and 34 wt% isopropyl alcohol. The PEDOT:PSS
layer was subsequently dried at 110 °C with a web speed of 8 m/min.
The printability of the yellow light-emitting polymer pentafluorobenzenethiol (PFBT)

was examined on the top of printed PEDOT:PSS. The 240 nm thick, smooth and
pinhole-free films were roll-to-roll gravure printed using the mixture of 2.9 wt% of
PFBT in p-xylene without additives. Waviness or interfacial mixing was not observed
after printing and drying at 110 oC with the web speed of 2 m/min. Figure 3.3 (a)
and (b) present the white light interferometer (WLI) 3D surface profiles from gravure
printed PEDOT:PSS and PFBT films on ITO foil.
Figure 3.3 WLI 3D surface profiles of (a) PEDOT: PSS (RMS 16 nm) and (b) PFBT
(RMS 39 nm) polymers
24
Screen Printing of Aluminium Cathode
In the OLED structure, the cathode layer normally consists of vacuum evaporated
low and high work function metals such as calcium and silver, respectively. In this
study, the target was to process a highly conductive cathode from printable metal
ink using a ball milling process [7]. Aluminium was selected for the metal ink
preparation as it has a lower work function (Al 4.2 eV) than silver (Ag 4.6 eV),
which is the more common metal used in conductive pastes for other electronic
applications. After preparation of aluminium ink, the screen printing technique
was selected in order to achieve a thick and opaque layer on top of the OLED
structure. An aluminium layer of around 10 μm thick, and sheet resistance of
0.06 7/sq was successfully screen printed using a 200 lines/cm mesh in an inert
atmosphere to avoid oxidation of aluminium metal particles. An image of the 3D
surface profile and printed aluminium cathode are shown in Figure 3.4(a) and (b).
Further optimisation of the screen printing process will significantly smooth the
aluminium layer [7].
Figure 3.4 (a) WLI 3D surface profile from the edge of screen printed aluminium
cathode, and (b) image of aluminium cathode (after Size)
25
Characteristics of All-Printed OLEDS
The all-printed OLED light sources described previously were characterised in an inert
atmosphere. The devices had a turn-on voltage of approximately 5 V and an average
brightness of 79 cd/m2 was achieved at the voltage of 16 V, as shown in Figure 3.5(a).
Figure 3.5 Brightness (a) and current density (b) versus voltage characteristics of
flexible all-printed OLED with the structure of ITO/PEDOT: PSS/PFBT/aluminium
26
Measuring current density versus voltage characteristics in Figure 3.5(b) illustrates

that there was no leakage of current at low operating voltages, indicating good
compatibility of printed organic and metal structures. However, OLED performance
can be significantly enhanced by adding small amounts of low work function metal
into the aluminium ink.
Roll-to-Roll Printed OLED Demonstrators
The objective was to roll-to-roll manufacture an OLED tamper indicator as a

demonstrator application. The demonstrator consisted of a label with two OLED red
and green light-emitters and a radio-frequency identification (RFID) antenna for the
power supply. The roll-to-roll manufacturing process comprised of printing several
OLED layers on the ITO coated barrier foil, including: PEDOT:PSS, red and green
light-emitters, an insulator, silver electric contacts, an aluminium ink cathode, and an
adhesive glue for laminating the back side barrier foil. The device structure is illustrated
in Figure 3.6(a). Figure 3.6(b) shows the all-printed OLED roll produced using the
roll-to-roll manufacturing process.
The [box] (shown in Figure 3.7) contains an electrical seal in the form of a fuse. If the seal
is broken a red OLED indicator will be light up when the circuit is powered by an external
radio-frequency (RF) field, as illustrated in Figure 3.7(a). Otherwise, if the seal is intact,
a green OLED indicator is light during RF activation, as shown in Figure 3.7(b).
Figure 3.6 (a) The device structure used in the OLED demonstrators and (b) the
photograph of roll-to-roll manufactured OLED foil
27
Figure 3.7 Photographs of the operating (a) red and (b) green OLED indicators
Summary
The study demonstrated the successful roll-to-roll manufacturing of all-printed

flexible OLED, in which the entire OLED stack, including: PEDOT:PSS, green and
red light-emitting polymers, an aluminium ink cathode, insulator and silver electric
contacts were gravure and screen printed onto plastic foil. This shows that roll-to-roll
printing techniques can be used for processing smooth and pinhole-free thin film
polymer layers. Furthermore, the study screen printed homogenous insulator, metal
cathode and electric contact layers for the OLED demonstrators.
Acknowledgement
The European Commission ROLLED Project (FP6-2003-IST-2-004315) is highly

acknowledged for funding the work presented in this paper. We thank ROLLED
partners for their guidance in the demonstrator issues.
References
1. R. Das and P. Harrop in Organic & Printed Electronics Forecasts, Players &
Opportunities, 2007-2027, IDTechEx Ltd., Cambridge, UK, 2007.
28
2. T. Kololuoma, M. Tuomikoski, T. Mäkelä, J. Heilmann, T. Haring,

J. Kallioinen, J. Hagberg, I. Kettunen and H. Kopola in Emerging
Optoelectronic Applications, Eds., G.E. Jabbour and J. T. Rantala, SPIE,
Bellingham, WA, USA, 2004, SPIE Conference Proceedings No.5363, p.77.
3. ROLLED Project Website, http://www.vtt.fi/proj/rolled
4. H. Kipphan, Handbook of Print Media, Springer Verlag, Heidelberg,

Germany, 2001.
5. S.B. Hoff, Screen Printing: A Contemporary Approach, Delmar Publishers,

Albany, NY, USA, 1997.
6. A. Blayo and B. Pineaux in Proceedings of the 2005 Joint Conference on

Smart Objects and Ambient Intelligence: Innovative Context-aware Services -
Usages and Technologies, Grenoble, France, 2005, p.27.
7. T. Maaninen, M. Tuomikoski and A. Maaninen in Proceedings of the 7th

International Meeting on Information Display, Daegu, South Korea, 2007,
p.721
29
30
4
Roadmap for Organic and
Printed Electronics
Peter C. Wilson, Dimitris Schoinas, Constantina Lekakou and John

F. Watts
Introduction
The search for cheaper, lighter, and more flexible electronic devices has caused a
surge of interest in the field of organic polymer electronics. Conducting P-conjugated
polymer films, which possess flexibility, semiconducting electronic properties and
transparency, are opening the door to novel electronic equipment including roll
up screens, photovoltaic coatings and smart windows. Central to this new push
is the ability to use low-cost, precise deposition techniques like inkjet printing and
electrospinning. Further developments, to ensure the electronic stability of the
organic materials over their life cycle, are bringing closer the possibility for mass-
produced, low cost electronics. For example, photovoltaic devices are showing
significant potential to rival current energy sources. In any semiconducting material
application, a transport layer is required to serve as the charge conductor. In many
applications it is important that this layer possesses a high level of transparency. Of
all the options, the use of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
(PEDOT:PSS) is demonstrating the most favourable results, not least due to its high
conductivity (10 S/cm) [1], high work function (~ 5.2 eV) and high mechanical and
thermal resistance.
The primary focus for current investigation is the optimisation of inkjet printed
PEDOT:PSS layers. The two common ink jet printing techniques are thermal ink jet
printing [2], and piezoelectric ink jet printing [3, 4, 5]. Undoped PEDOT can achieve
conductivities of over 200 S/cm [6] although, like most conducting polymers, pure
PEDOT is insoluble in water and hence must be doped with PSS. Analysis of inkjet
printed, spin cast and drop spread deposited PEDOT:PSS layers has shown a phase
separation between the conducting PEDOT and insulating PSS layers. To increase
conductivity, the addition of a polar solvent becomes necessary [7]. The increased
disorder in the morphology leads to an increase in conductivity by a factor of over
10, whilst also increasing the surface tension by 10-20%. Since inkjet printers
31
require fluids with surface tension within the range of 0-70 mN/m, with viscosities
below 20 mPas, it is necessary to employ a surfactant to lower the surface tension
to a more reasonable level. In this paper, it is shown how the optimum dimethyl
sulfoxide (DMSO) concentration results in a surface tension above the upper boundary
of working inkjet requirements. Investigations [8] into further organic solvents
have shown that the addition of ethylene glycol, 2-nitroethanol, methyl sulfoxide
or 1-methyl-2-pyrrolidinone have lead to similar conductivity enhancement. It is
proposed that the driving force behind this is the interaction between the dipole of
the organic compound, and the charges on the PEDOT chain.
Ink jet printing is a drop deposition technique, which results in precise patterns.
Electrospinning, on the other hand, is a fibre deposition technique where a continuous
fibre mat, or fibre assembly, may be deposited to cover a specified area. Electrospun
films are highly porous and it is possible to fabricate them with a preferred fibre
orientation and, hence, anisotropic properties.
4.1 Process Modelling and Simulation of Ink Jet Printing
Table 4.1 presents the dimensionless groups that are important in jet flow and jet
break up times, where Rn is the nozzle radius and Uo is the velocity at the nozzle, R,
μ and S are the density, viscosity and surface tension of the ink.
Table 4.1 Dimensionless groups important in jet flow and jet break-up
RU 0 2 Rn InertiaForces
Reynolds Number (Re) = =
M ViscousForces
MU o ViscousForces
Capillary Number (Ca) = =
S SurfaceTension
2
RU o 2 Rn InertiaForces
Weber No (We) =
S surfaceTension
R ( 2 Rn )
Also Rayleigh time scale for capillary break up (tr) =
S
32
It is considered that the drop formation in the ink jet printing process is e governed
by the timing of the electric pulse. This piezoelectrically controls the ink flow, inertia
forces, viscous forces, surface tension and gravity. The final process model consists of
two, one-dimensional equations originating from the kinematic boundary condition,
the normal and tangential components of the traction boundary condition and the
z-component of the momentum equation, thus:
¥ uu uu ´ u (2 H ) 3 ¨ u ¥ 2 uu ´·
R ¦ u µ S 2 © ¦ MR µ gR
§ ut uz ¶ uz R ª uz § uz ¶¸¹ (4.1)
uR uR 1 uu
u R
ut uz 2 uz (4.2)
where R is the radius of the jet (or drop) at an axial position z, and time t, u is the
axial velocity, g is the gravity and 2H is given by:
1 u 2 R / uz 2
2H
R[1 (uR / uz ) 2 ]1 / 2 [1 (uR / uz ) 2 ]3 / 2 (4.3)
Figure 4.1 Predictions and experiment results of, flow of carbon nanotube –
PEDOT: PSS solution at a constant flow rate of 60 ml/h
33
- 80 0 80
0
- 400
Figure 4.2 Constant flowrate of 43 ml/h: Predictions of drop formation at 80 μs

(dimensions in μm)
Equations 4.1-4.3 describe an ideal constant flow rate problem. The explicit finite
difference technique was applied for the numerical solution of Equations 4.1-4.3.
An experimental study was carried out of the flow of carbon nanotube-PEDOT:PSS
solution (μ 8.8 mPa-s and S = 68 mN/m) through a needle of 60 μm internal diameter
at a constant flow rate to validate the computer simulations. Flow rates of 60 ml/h
resulted in a continuous jet stream, and this was also predicted by the computer
simulation, see Figure 4.1. On the other hand, as the flow rate was lowered below
Wecritical = 15, drop formation occurred. This was also predicted by the computer
simulation as is illustrated in Figure 4.2.
An experimental case-study [9] of ink jet printing was considered to validate the
computer simulations, where R =1000 kg/m3, μ=1.3 mPa-s, S = 60 mN/m, Rn = 20
μm, flowrate = 38.4 ml/h, tpulse = 100 μs. Drop formation and break up were predicted
at about 50 μm distance from the nozzle. The falling droplet grew and evolved to
a cap. The experimental case study showed many similarities, including the droplet
break up time of about 123 μs, which agrees very well with the predictions. However,
the predicted travelled distance is smaller than in the experiment. This is attributed
to the fact that the experiment is not under constant flow rate during the pulse. As a
result, the computer model needs modifications to account for a pressure waveform
at inlet.
34
-80 0 80
0
-50
-100
-150
-200
-250
z
-300
120 μs
-350
-400
-80 0 80
0
-50
-100
-150
-200
-250
z
-300
-350
130 μs
-400
Figure 4.3 Predictions at a constant flowrate of

38.4 ml/h and a pulse time of 100 μs,
and comparison with experiment
35
4.2 Characterisation of PEDOT-PSS Inks and Products
Materials used for the case study included PEDOT:PSS poly(3,4-ethylenedioxythiop

hene):poly(styrenesulfonate) 1.3%wt in water (Sigma Aldrich), Dimethyl Sulfoxide
(Fischer Scientific) and Surfynol (AirProducts). For drop cast conductivity and
surface tension analysis, PEDOT:PSS/DMSO(0-5 wt%) and PEDOT:PSS/DMSO(0-5
wt%)/Surfynol mixtures were prepared at ambient conditions and allowed to mix in
a sonication bath for 24 hours Samples were drop spread onto cleaned glass slides
between the ends of conducting aluminium tapes. All samples were allowed to anneal
in ambient conditions for 30 minutes at 130 oC.
Surface tension was determined via the pendant drop method using a Kruss EasyDrop.
The liquid was suspended from an 1832 μm needle with equatorial and neck diameters
measured for the largest stable drop. The surface tension was calculated using the
relationship:
a 2 g$R
B
S (4.4)
where A is the effective radius of the drop base, g is gravity, R is the density and S is
the surface tension. Similarly:
Ds
S
De (4.5)
where De is the equatorial diameter of the drop, and Ds is the diameter of the drop
at a distance De from the base.
(4.6)
The results in Figure 4.4 demonstrate that surface tension increases when DMSO is
added, which is undesirable in ink jet printing. When 1 wt% Surfynol is added, it
lowers the surface tension below 30 mN/m for 0 – 5 wt% DMSO. Figure 4.5 shows
that for 0 wt% DMSO the addition of 1 wt% Surfynol decreases resistively from
66 k7/ to 52 k7/. It has been shown [6] that the use of a surfactant has a similar
effect on conductivity as the solvent, suggesting that the long chain molecule of the
Surfynol causes a similar disruption to the phase separation, and hence leads to a
greater PEDOT to PSS surface ratio [10]. However, higher concentrations of DMSO
bring down electrical resistivity at a lower rate in the presence of Surfynol. For
example, for 5 wt% DMSO, Ra = 314 7/ with 1% Surfynol and Ra = 81 7/ without
any Surfynol.
36
0.08
0.07
Surface Tension (N/m)

0.06
0.05
0.04
0.03
0.02
0% Surfynol
0.01 1% Surfynol
0
0 1 2 3 4 5 6
DMSO (% wt)
Figure 4.4 Surface tension of

PEDOT:PSS/DMAO solutions, with and without
Surfynol, as a function of DMSO concentration.
1000000
Surface resistivity ( /square)
100000
10000
1000
100 PEDOT / DMSO

10
PEDOT / DMSO / Surf
1
0 1 2 3 4 5 6
DMSO (% wt)
Figure 4.5 Surface resistivity of

PEDOT:PSS/DMSO solutions, without and
with 1 wt% Surfynol, as a function of DMSO concentration.
4.3 Characterisation of Carbon Nanotube - PEDOT:PSS

Nanocomposite Products
An amount of 0.023 g Elicarb multiwall carbon nanotubes (MWNT), supplied by

Thomas Swan Ltd., was added to 25.47 g of 1.3 wt% PEDOT:PSS solution in water.
The mixture was sonicated for 1 hour and it was then subjected to high shear mixing
at 18,000 rpm for 1 hour. The resulting ink had a viscosity of 50 mPa-s. Before further
processing, it was further diluted with de-ionised water by 5:1, yielding a reduced
viscosity of 8.8 mPa-s. The diluted PEDOT:PSS ink had a surface tension of 68.3
mN/m either with or without the prescribed concentration of MWNT.
37
The fabrication method involved drop spreading on a Melinex film substrate. The
drops were produced using a syringe pump at a constant flow rate of 86.5 ml/h, and
a pulse time of 0.6 s. The syringe had a 36 gauge steel needle with a 60 μm inner
diameter, and 180 μm outer diameter. The experimental procedure was repeated for
paper and cardboard substrates. In all cases, printing was carried out incorporating:
1 print pass (1 printed drop), 2 print passes (2 printed drops overlaid), 3 print passes
(3 printed drops overlaid) and 4 print passes (4 printed drops overlaid).
1.E+07
Melinex
Surface resistivity
(Mohm/square)
1.E+05 Paper
1.E+03 Cardboard
1.E+01
1.E-01
1 2 3 4
Number of drops
Figure 4.6 Surface resistivity as a function of the number of printed drops for
different substrates
100
Transparency (%)
80
60
40
20
0
1 2 3 4
Number of drops
Figure 4.7 Transparency as a function of the number of printed drops on Melinex

substrate
38
Figure 4.6 presents measurements of the surface resistivity, Ra, of the products.
Starting from the Melinex substrate, it can be seen that Ra is high. This is due to
(a) the dilution of the MWNT-PEDOT:PSS ink, and, (b) the fact that no DMSO
was used in this experimental section. It can also be seen that the products on the
Melinex substrate exhibited the lowest electrical resistance compared to the paper
and cardboard substrates. This was especially found to be the case for 1 print pass
(1 printed drop only). The reason for this is that paper and cardboard substrates are
highly porous. Therefore, the ink permeates and spreads, where as it stays on the
surface of the Melinex substrate. However, Ra is reduced as the number of printed
drops is increased, which also reduces differences between products with different
substrates. Figure 4.7 presents the transparency of drop prints on the Melinex substrate
for different numbers of print passes. For example, the transparency of a print with
2 printed overlaid drops is 71%, while the value of Ra is fairly close to that of prints
with a higher number of printed overlaid drops (Figure 4.6). Transparency reduces
almost linearly, by approximately 7-9%, for each additional print pass.
(a) (b)
Figure 4.8 Optical micrograph of the border of printed drop on paper substrate:
(a)1 printed drop; (b) 3 printed drops
Figures 4.8 and 4.9 illustrate the microstructure of printed paper and cardboard
substrates. The random fibre structure, with micropores, is evident in both substrates.
The cardboard has larger micropores, facilitating ink impregnation. For both porous
substrates, there is a darker ink ring at the perimeter of the drop.
39
(a) (b)
Figure 4.9 Optical micrograph of the border of printed drop on paper cardboard:
(a) 1 printed drop; (b) 3 printed drops
4.4 Electrospinning of Carbon Nanotube Inks
An amount of 0.032 g of Elicarb MWNT, supplied by Thomas Swan Ltd., was

added to 10 ml of distilled water that contained 0.1 g of dodecylbenzenesulfonate
as a surfactant. The mixture was sonicated for 2 hours. After this, 40 ml of 12%
polyvinyl alcohol (PVA) in water was then added. The mixture was then subjected
to shear mixing at 15,000 rpm for 1 hour. The suspension had a viscosity of
48 mPa-s.
The resultant ink was electrospun from an 18 gauge steel needle at a distance of 150
mm from the ground collector, which was a multiple wire drum rotating at 2 rpm.
The electrospinning took place under a potential of 20 kV, while the MWNT – PVA
ink was fed by a syringe pump at a constant flow rate of 4 ml/h. After 20 min of
electrospinning, a fibrous mat of 300 x 810 mm was fabricated and left to dry for
24 hours.
Figure 4.10a presents an optical micrograph of the fibrous nanocomposite product,

which shows the formation of continuous oriented nanofibres of about 200 nm
diameter (Figure 4.10b). This yielded anisotropic electrical properties for the fibrous
nanocomposite product, with an electrical conductivity of about 400 times higher in
the direction of fibre orientation compared to the in-plane direction perpendicular
to the fibres.
40
(a) (b)
Figure 4.10 Carbon nanotube – PVA nanocomposite fibre assembly deposited on

Melinex substrate by electrospinning: (a) optical micrograph (b) scanning electron
microscope (SEM) micrograph
4.5 Conclusions
The study presents the first results of an investigation on the ink jet printing and
electrospinning of PEDOT:PSS, and related carbon nanotube nanocomposites. A flow
model has been assembled for continuous, and pulse flow, under constant flow rate.
This was successfully validated under constant flow rate conditions. A comparison of
the predictions with the experimental data of a study of piezoelectric ink jet printing
[9] led to the conclusion that the pressure drop term needs to be included in the model
to cater for varying flow rate under a pressure waveform inlet condition. Furthermore,
electric field terms need be included for the modelling of electrospinning. However,
the example of the computer simulation of ink jet printing indicated that a surface
tension below 60 mN/m might be required for the formation of small droplets, since
the predicted drop width of 150 μm for a surface tension of 60 mN/m was rather
large. The surface tension of PEDOT:PSS/DMSO solutions was successfully reduced
from 60-70 mN/m to below 30 mN/m for 1-5 wt% DMSO through the use of 1
wt% Surfynol. The addition of DMSO was essential to lower the surface resistivity
of PEDOT:PSS in the presence of 1 wt% Surfynol, from 52 k7/ (0% DMSO) to 314
7/ (5 wt% DMSO). The addition of MWNT to PEDOT:PSS resulted in increased
surface resistivity.
The carbon nanotube – PEDOT:PSS ink was deposited as printed drops on three
different substrates: Melinex, paper and cardboard. The printed drops on paper and
41
cardboard had higher resistivity than the drop printed on Melinex. This was due to
the high permeability and porosity of paper and cardboard. However, the resistivity
of two overlaid printed drops on paper and cardboard fell substantially to levels
similar to that of the resistivity of two printed drops on Melinex. Therefore, it might
be concluded that two print passes on paper and cardboard are needed to achieve
a reduced resistivity. On the other hand, the transparency of two overlaid drops on
Melinex is 71%, against a 79% transparency of one drop. An electrospinning run
of MWNT – PVA ink resulted in an oriented, continuous, fibre mat deposited on
Melinex. This had an average 200 nm fibre diameter and an electrical conductivity
400 times higher in the direction of the preferred fibre orientation, compared to the
in-plane directi on perpendicular to that preferred fibre orientation.
References
1. BL.Groenendaal, F.Jonas, D.Freitag and H. Pielartzik, Advanced Materials,

2000, 12, 7, 481.
2. B. Ballarin and A. Fraleoni-Morgera, Synthetic Metals, 2004, 146, 201.
3. M.A. Lopez, J.C. Sanchez and M. Estrada in Proceedings of the 7th International
Caribbean Conference on Devices, Circuits and Systems, Cancun, Mexico,
2008, p.165.
4. J. Bharathan and Y. Yang, Applied Physics Letters, 1998, 72, 21, 2660.
5. Z. Liu, Y. Su and K. Varahramyan, Thin Solid Films, 2005, 478, 275.
6. S. Sapp, S. Luebben, Y.B. Losowi, P. Jeppson, D.L. Schulz and A.N. Caruzo,
Applied Physics Letters, 2006, 88, 15.
7. E.Garnett and D.Ginley, Journal of Undergraduate Research, 2005, 5, 24.
8. J. Ouyanga, Q. Xua, C.-W Chua, Y. Yanga, G. Lib and J. Shinarb, Polymer,

2004, 45, 8443.
9. A-S Yang, C-H Cheng and C-T Lin in Proceedings of the Institute of Mechanical
Engineering Part C: Journal of Mechanical Engineering Science, 2006, 220, 4,
435.
10. S.K.M. Jonsson, J. Brigerson and X. Chrispin, Synthetic Metals, 2003, 139, 1.
42
5
Highly Conductive Plastics –
Custom-formulated Functional Materials for
Injection Mouldable Electronic Applications
Walter Michaeli, Tobias Pfefferkorn and Jan Fragner
5.1 Introduction
Electric and electronic products have gained increasing importance in a number of

industries. Becoming ever more complex, they are being used in highly integrated
assembly groups. In addition, there is a growing trend for miniaturisation, particularly
in the fields of electronics, electrical engineering, communications engineering and
automotive engineering [1].
Conductive components in electric and electronic products have to fulfil different

requirements depending on their field of application. For example, a very high
electrical conductivity is needed for plug-in connections, elements in transmission and
engine control systems. Defined ranges of conductivity are required for control units,
sensors and enclosures. For the latter application, electromagnetic shielding is also
of importance. Lower electrical conductivity values are demanded for applications
that have to prevent electrostatic charge.
Polymers are typical insulation materials due to their extremely low electrical
conductivity. Interest in using polymers for other electrical applications has increased
due to advantageous properties such as weight, processibility and resistance to
chemicals. Over the years, thermally and electrically conducting polymers have been
developed by the addition of common fillers such as carbon black, graphite, metallic
fibres, flakes or carbon fibres and, increasingly, nano-fillers such as carbon nano-tubes.
These compounds have already been deployed successfully in a range of antistatic and
electromagnetic shielding applications. In order to ensure a high degree of electrical
conductivity, a high content of conductive fillers is required, which forms a close
percolation network [2, 3].
For each material composition, a compromise has to be found regarding the amount
of filler. Higher filler contents commonly have a negative influence on the mechanical
properties and processability due to the considerable increase in melt viscosity.
43
Concurrently, the wear on machinery and mould is higher than for unfilled polymers.
The material compositions used so far are unable to fulfil the demands of upcoming
component functionality, particularly for thin-walled and miniaturised elements. Hence,
functional components that require high electrical conductivity, are still typically
produced in cost-intensive processing and assembly steps (e.g., insert moulding, hot
stamping or metallising) [2, 4-7].
The filler content, and thus the electrical conductivity, can be increased significantly
without decreasing the processability by using metal alloys that exhibit a low melting
point [8-10]. These metal alloys are liquid in the processing phase and will not solidify
before the cooling phase. This allows the production of complex moulded parts with
definite electrical and thermal properties. As a result, material related disadvantages
are reduced in comparison with highly filled moulding compounds.
The reference material under investigation consists of 15 wt% (56 vol%) polyamide
6 (PA6) (type 6NV12 by A. Schulman Inc, Akron, USA), 33 wt% of a low-melting
tin/zinc alloy with a melting point of 199 °C and 52 wt% of fine copper fibres
(average length: 0.65 mm, diameter: 35 μm), developed in cooperation with Siemens
AG, Germany. This highly filled polymer/metal hybrid material allows passage
conductivities of 105-7 s 106 S/m and conductivities over the wall thickness of 103-105
Figure 5.1 Electrical conductivity in comparison to other materials and

potential applications
44
Highly Conductive Plastics – Custom-formulated Functional Materials
for Injection Mouldable Electronic Applications
S/m [10]. These values are comparable with conductivities of pure metals (Figure 5.1).
Thus, it becomes possible to produce conducting structures and junctions for plug-
in connections and/or cables in a single processing step by means of an injection
moulding process. Time-consuming joining and soldering processes can be avoided.
Figure 5.1 shows some possible applications. Contact pins can be directly integrated
into electrically conducting elements, and electromagnetic shielding, achieving
modules that are more efficient at cooling devices and motors.
5.2 Characteristics of the Hybrid Compound Within the Injection

Moulding Process
5.2.1 The Cavity Filling
The thermoplastic/metal compounds can be processed in conventional single or multi-

component injection moulding processes. Due to the high metal content, the filling and
freezing behaviour of the materials differs from that of unfilled thermoplastics. That is
caused by both the solid and liquid filler. The tests were carried out using an injection
moulding machine of the type Allrounder 320 S 500 - 150 (Arburg GmbH + Co KG,
Lossburg, Germany), which has a screw diameter of 30 mm (L/D = 20). First, the effects
on the flow properties of the new material are discussed, followed by the characterisation
of local filler distribution. Unfilled and low-filled thermoplastics show a typical frontal
flow during filling of the mould. This is typical for viscoelastic fluids, whereby a
parabolic velocity profile is formed over the parts thickness [11, 12]. With increasing
filler content, the velocity profile generally become more block-shaped [13-15]. These
typical flow patterns can be determined by mould filling studies of unfilled PA6 and
material exclusively filled with copper fibres (Figure 5.2). The evenness of the filling is
slightly reduced by copper fibres due to the decreased melt elasticity. The highly filled
thermoplastic/metal compound shows a significantly altered filling behaviour due to
the high filler content of 85 wt%. Beside the significantly reduced melt elasticity of the
compound; the rapid heat flow, increased thermal conductivity and the specific phase
transition of the metal alloy are the main reasons for this behaviour.
45
Figure 5.2 Comparison of mould filling studies of different materials
5.2.2 The Morphological Structure
In addition to the flow behaviour, the morphological structure of the highly filled
compound directly influences the property of the part being produced. The combination
of copper fibres and metal alloys with low melting points forms a dense, three-
dimensional metal network, as can be seen in Figure 5.3. The positive effect of the
metal alloy can be demonstrated in a close up view of a cross section. Due to the fine
dispersion of the alloy, and good affinity of copper fibres and alloy, the distance between
metal particles can be significantly reduced. This explains the high passage conductivity
observed in the range of 106 S/m (Figure 5.3). By contrast, polyamide exclusively filled
with copper fibres achieved conductivity values that were approximately three powers
of ten lower, even when the filling degree was the same.
Figure 5.3 also shows that there is no linear relationship between the quantity of
filler content and conductivity. At a low filler content, the conductivity of the matrix
polymer is dominant. With increasing fibre content, the contacts between the fibres
increase and the specific conductivity escalates in a small window. The critical
concentrations of volume required for this escalation – called the percolation threshold
– range between 20-25 vol% for both the metal/thermoplastic hybrid material,
and the polymer exclusively filled with copper. Above this concentration, the metal
network becomes more dense to an extent where conductivity can be increased only
marginally [3, 16-18].
46
Figure 5.3 Formation of a 3-dimensional network and the improved passage

conductivity (CT = computed tomography)
5.2.3 Dependence of the Conductivity on Geometry, Material and

Process Condition
The measured conductivity is not constant and changes considerably if the resistance
is measured through the interior or over its thickness, thus including the surface.
Figure 5.4 Influence of the geometry (wall thickness) on the conductivity (h = wall
thickness of the plate geometry shown in the figure on the right)
47
This is explained by the surface layer effect. Due to the flow conditions of solid
filled polymers, the surfaces of the injection moulded parts contain hardly any filler
material [17, 19]. This effect can be reduced significantly with a low-melting metal
alloy but cannot be avoided completely. Further on, the conductivity depends on the
flow path due to the flow conditions in the gating system and in the moulded part.
Figure 5.4 shows that the electrical conductivity over the wall thickness rises almost
linearly with increasing flow length, which correlates well with the local density of
the part. Besides the increasing filler content, the outer layer effect is reduced towards
the end of the flow path. The rate of increase varies depending on the geometry, the
composition of the material and the process conditions. With an increasing plate
thickness, the conductivity over the wall thickness shows less dependence on the
part’s position.
Furthermore, the electrical properties can be adjusted by varying the matrix polymer
and the filler distribution. Since the material concept allows for the use of almost any
polymer matrix, the required material properties, for instance a high temperature
resistance, can be provided by the use of polyphenylene sulfide (PPS) as a matrix
polymer. The morphological structure, and thus the measured conductivity over the
thickness, depend on the ratio of the melt temperatures and viscosities of both the
polymer and metal alloy, whereas the passage conductivity is at a similarly high level
of > 4 s105 S/m.
In the case of the polyethylene (PE) matrix, the metal alloy solidifies first leading
to a very even and fine distribution of the metal on the surface as well as in the
interior (Figure 5.5). Therefore, the conductivities measured over the thickness are
Figure 5.5 Influence of various matrix materials on morphological structure and

conductivity (LV = low viscosity and HV = high viscosity)
48
almost constant along the flow path. By contrast the polymer freezes first in the PPS
compound. Thus, the pressure is transmitted by the metal alloy resulting in sizeable
metal alloy agglomerates in the part’s centre and a high amount of the metallic phase
that can be detected near the surface. Due to the big difference between polymer
melting and mould temperature, the free flow cross-section decreases rapidly. This
leads to a higher orientation of the filler material at the surface. The influence of
the shear viscosity is analysed by comparing a low and highly viscous polyamide.
The latter shows very distinctive shear sections in the outer layers leading to
conductivities over the thickness that are strongly dependent on the flow path.
However, the viscosity itself has no significant influence on the distribution of the
metal alloy. Freezing of the polymer at the same time or later than the metal alloy and
a low viscosity of the material can considerably improve the level and homogeneity
of conductivity.
The material properties are not only influenced by the composition of the material but
also by the injection moulding process. Therefore, both the dosing and the injection
parameters were systematically varied in the design of the experiments. The electrical
passage conductivity is nearly constant in a broad process window due to the dense
metallic network, whereas the conductivity measured over the thickness changes
significantly by varying both the dosing and the injection parameters. For example,
Figure 5.6 shows the influence of a low and high injection velocity on conductivity.
Figure 5.6 Influence of the injection velocity on the electrical conductivity over the
wall thickness
49
Figure 5.7 Electrical conductivity in dependence on the part temperature
A lower injection velocity allows a longer filling phase, which reduces the formation
of shear zones and hence improves the conductivity over the wall thickness.
5.2.4 Temperature Dependency on the Conductivity
Up to this point, the material properties have only been discussed at room temperature.
However, in many fields of applications conductive polymers have to fulfil their
functionalities (e.g., electrical conductivity) at elevated temperatures. In certain
situations heating is produced from the outside, such as occur in ‘under the hood’
applications. Material warming can also occur under current load where the material
is used as a conductor path in order to conduct electricity at a reasonably high current.
In this process, the material is heated due to the electrical resistance of the material. It
is important to consider if the conductive network would be damaged locally under
thermal loading. Therefore, the time-dependent passage conductivity was determined
by means of test specimens. The highest values measured at room temperature are
slightly reduced until the glass transition temperature of polyamide (50-60 °C) is
reached (Figure 5.7). Afterwards, the values remain constant at a high level and start
decreasing at approximately 170 °C. The change in conductivity under heating is
reversible, since the initial values are reached again after cooling.
The charging of samples with electric current leads to increasing material temperatures
when choosing either smaller cross sections or higher currents (Figure 5.8). However,
this stabilises after an initial steep increase in temperature. The final temperatures
50
Figure 5.8 Material warming under current load
range between room temperature and approximately 50 °C. Higher temperatures

can only be reached where a high current is combined with cross-sections under 5
mm2. Thereby, the test specimens could be made to fail when heated strongly. In
order to estimate both the geometry and current load together, the current density is
built showing a linear relationship with the material warming. In addition, sheathed
conductors reached higher end temperatures (approximately 15%) throughout the
tests due to the reduced heat dissipation of plastic sheathing.
5.2.5 Electromagnetic Shielding Effectiveness
In many applications, electrically conductive plastic compounds are also used for
shielding of electromagnetic waves. Electromagnetic compatibility is becoming
increasingly important as electrical systems extend further into daily life. Depending
on the field of application the product must fulfil different kinds of marks, such as the
CE mark [20]. These aims can be facilitated by electromagnetic shielded enclosures.
Plastics cannot alleviate the electromagnetic fields and waves due to their non-magnetic,
insulating physical properties. A good shielding can only be achieved by conductive
polymers, such as those filled with long steel fibres of 20 wt% [20, 21]. The combining
of copper fibres with metal alloy is not only advantageous for electrical conductivity
but also for electromagnetic shielding (Figure 5.9). To show this effect, the shielding of
plates with a wall thickness of 2 mm was measured using transmission-line measuring
equipment. Due to the pronounced metallic network of the hybrid material, a very
51
Figure 5.9 Electromagnetic shielding of conductive polymers
high shielding effectiveness can be reach compared to that obtained with other filled
polymers. The measured values are in the range of the resolution of the equipment and
on the same level as a metallic plate. In addition, the values are practically independent
of the frequency.
As long as the filler content enables a dense, conductive network, the shielding effectiveness
remains at a high level. Despite the lack of homogeneity in the metallic network of
a test place with a wall thickness of 1 mm (Figure 5.4), a shielding effectiveness of
approximately 58 dB can be achieved. Thus, the hybrid material can be considered suitable
for shielding applications and can enable the substitution of metallic plates or coatings.
5.2.6 Injection Moulding of Conductor Paths
High thermal conductivity changes not only the flow behaviour but can also lead
to the premature freezing of the material. As a result, the maximum filling length is
reduced compared to the unfilled matrix polymer. It is often not necessary to take
this behaviour into consideration for the production of shielding housings, and two-
dimensional components with short and medium flow lengths. However, it plays
an important role in the realisation of high flow path/wall thickness ratios. In these
situations it may be necessary to directly manufacture multifunctional electronic
components like electrically conducting structures on electrically insulating polymer
carriers.
52
Figure 5.10 Flow length in dependence on the conductor cross-section and the
mould temperature
Altering the mould temperature can significantly influence the flow and freezing
behaviour of polymer melts in the mould cavity [22]. In order to analyse the influence
of the conductor cross-section on the flow length, conductor parts with different
cross sections were injection moulded on unfilled polymer plates. In addition, the
mould temperature was varied in a wide process window (Figure 5.10). It can be
seen that a flow length of considerably more than 100 mm can be realised for a
cross-section greater than 1 mm² with an oil-heated mould. Conductor cross-section
sizes under 1 mm² only allow a flow length of less than 50 mm. Thus, the limit of
the lowest conductor cross-section size is approximately 1 mm² due to the filler size
used (length of copper fibres L = 0.3-0.8 mm). Furthermore, conductor paths with a
greater height than width offer increased contact area with the mould, and therefore
offer the preferred option. By means of an increased mould temperature of 180 °C
the flow length can also be disproportionately improved.
Especially for the application of the material in conducting and/or shielding structures,
the conductive elements and non-conductive carriers must be integrated in the same
electronic system. In first preliminary tests the bond strength is tested using two-
component tensile bars made of conducting compound and unfilled matrix polymer
PA6. When applying the filled component to the unfilled polymer the stability only
decreases marginally. The two components show good bond strength compared
to conventional highly filled melts. Therefore, the compound is suitable for the
employment in multi-component moulded assemblies.
53
5.3 Conclusions and Outlook
The investigations presented show the high potential of the novel compounds for
the use in moulded parts with high electrical conductivity. The material range
stretches from carbon black compounds to metals and forms the transition between
semiconductors and conductors.
The described thermoplastic/metal hybrid materials have a high potential for being
employed in the production of complex electronic components with very high demands
on the electrical conductivity.
Due to the injection moulding process moulded parts of highly filled material show
a dependence of the distribution and direction of the filler material on the local
position along the flow path and over the part’s thickness. Therefore, in the design of
the moulded part it is important to consider not only global characteristic values but
also the influence of the material composition, the process parameters as well as the
geometries of gating system and cavity. This also makes it possible to systematically
influence morphology and part properties during the compounding and injection
moulding of the polymer/metal hybrid materials.
It can be briefly shown that the matrix polymer can be varied widely in order to adjust
the compound properties for specific applications’ requirements. Thereby, a freezing
of the polymer at the same time or later than the metal alloy and a low viscosity of
the material can considerably improve the level and homogeneity of conductivity.
Moreover, the conductivities of the hybrid material are only slightly influenced by
elevated temperatures. The conductivity is not considerably reduced until the softening
temperature of approximately 200 °C is reached. As long as the cross-section is greater
than 5 mm² at a comparatively low current load of approximately 10 A, the hybrid
material does not heat up critically and can be used for conductor paths. Besides an
outstanding electrical conductivity, an excellent shielding effectiveness is provided by
the hybrid material due to the pronounced metallic network. This allows the material
for being employed in the field of electromagnetic shielding applications.
High filling degrees and high thermal conductivity change the filling and freezing
behavior of the material. This is particularly important for the production of
conducting structures with high flow path/wall thickness ratios and may require an
adjustment of the mould temperature control. First tests already point out that the
minimum cross-section size is approximately 1 mm². Current research projects at the
IKV are aimed at developing mould and process solutions for an optimised material
processing of complex multi-component parts. Thereby, the use of inductive heating
should be investigated at the IKV in order to further increase the flow distances.
54
Acknowledgements
The investigations set out in this report received financial support from the Federal
Ministry of Economics and Technology (BMWi) by the Arbeitsgemeinschaft
Industrieller Forschungsvereinigungen eV (AiF No. 15258 N), to whom we extend
our thanks.
References
1. D. Drummer and R.Dörfler in Spritzgießen 2007, VDI-Verlag, Düsseldorf,

Germany, 2007, p.141-157.
2. H.J. Mair and S. Roth, Elektrisch Leitende Kunststoffe, Carl Hanser

Publishing, Munich, Germany, 1989.
3. A.K. Bledzki, L. Subocz and J. Subocz, Kunststoffe, 1992, 82, 3, 243.
4. B. Pfeiffer in the Proceedings of the OTTI Conference: Elektrisch

Leitfaehige Kunststoffe, Regensburg, Germany, 2006.
5. J. Versieck in the Proceedings of the SPE Annual Technical Conference -

ANTEC, Orlando, FL, USA, 2000, Paper No.290.
6. D.J. Jendritza, Auto & Elektronik, 2002, 3, 12.
7. K. Feldmann, 3D-MID Technologie, Carl Hanser Publishing, Munich,

Germany, 2004.
8. S. Prollius and C. Hopmann, inventors; Foerderung Institut Kunststoff,

assignee; DE 19,962,408, 2001.
9. E. Haberstroh, M. Hoelzel, M. Koch and E. Krampe, Kunststoffe, 2004, 94,

3, 106.
10. W. Michaeli and T. Pfefferkorn, Plastics, Rubber and Composites:

Macromolecular Engineering, 2006, 35, 9, 380.
11. P. Thienel, Der Formfüllvorgang beim Spritzgießen von Thermoplasten,

Rheinisch-Westfälische RWTH Aachen University, 1996. [PhD thesis]
12. G. Menges, W. Michaeli and P. Mohren, Anleitung zum Bau von Spritzgieß-
Werkzeugen, Carl Hanser Verlag, Munich, Germany, 1999.
55
13. R. Schulze-Kadelbach, Fließverhalten Gefüllter Polymerschmelzen,

Rheinisch-Westfälische Technische Hochschule Aachen, 1978. [PhD thesis]
14. P. Barth, Pulvermetallspritzgießen – Ein Beitrag zur Verarbeitung Ultrahoch-

Fefüllter Kunststoffe, Rheinisch-Westfälische Technische Hochschule
Aachen, 1988. [PhD thesis]
15. J.P. Greene and J.O. Wilkes, Polymer Engineering and Science, 1995, 35,
21, 1670.
16. G. Ruschau and R. Newnham, Journal of Composite Materials, 1992, 26,

18, 2727.
17. J.M. Knothe, Elektrische Eigenschaften von Spritzgegossenen

Kunststofformteilen aus Leitfaehigen Compounds, RWTH Aachen University,
Dissertation, 1996. [PhD thesis]
18. W-Z. Cai, S-T. Tu and J-M. Gong, Journal of Composite Materials, 2006, 40,
23, 2131.
19. D.M. Bigg, Advances in Polymer Technology, 1984, 4, 255.
20. U. Leute in the Proceedings of the OTTI Conference: Elektrisch Leitfaehige

Kunststoffe, Regensburg, Germany, 2007.
21. S. Roth, Spritzgegossene Abschirmgehäuse aus Stahlfasergefüllten

Thermoplasten – Materialeigenschaften, Verarbeitung und Gestaltung,
Technical University Chemnitz, 2006. [PhD Thesis]
22. G. Wübken, Einfluss der Verarbeitungsbedingungen auf die innere Struktur

thermoplastischer Spritzgussteile unter besonderer Berücksichtigung der
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56
6
Additives in Polymer Electronics
Daisuke Fujiki
6.1 Introduction
Ciba is global specialty chemicals company. The roots of Ciba date abck to 1758
when JR Geigy Ltd., began trading in chemicals and dyes in Basel, Switzerland. In
1970, Geigy merged with Ciba - a Basel based chemical company founded in 1884 - to
form Ciba Geigy Ltd.,. Ciba Geigy and the pharmaceutical compant Sandoz merged
in 1996 and formed one of the world’s largest life science groups - Novartis. As a
result of this merger, the specialty chemical division were spun off as Ciba Specialty
Chemicals, Inc., in 1997. The company adopted the name Ciba, Inc in 2007. In
April 2009, Ciba was aquired by BASF SE.
Ciba has three segments: Plastic Additives, Coating Effects and a Water and Paper.
The Plastic Additives segment deals with colour and additives for plastics, lubricants
and home & personal care. The Coating Effect segment is dedicated primarily towards
the coating and imaging industries, while the Water and Paper segment provides
solutions for paper and water treatment businesses.
6.2 Degradation and Stabilisation of Polymer
Many kinds of polymers are used in the electronics industries, from polyethylene to
so-called super engineering plastics, such as polyethersulfone or polyimide. Almost all
of them require additives. The reason for this is either to retain intrinsic characteristics
or to extend those characteristics. In order to retain properties, polymers need
process and heat stability, thermal stability or light stability. For the acquisition of
new function, many kinds of functional additives can be added. Metal deactivators,
antistatic agents and flame retardants are just some examples.
Each polymer has different degradation pattern and here shows representative
degradation pattern of polyolefin, the so-called autoxidation cycle (Figure 6.1).
57
Figure 6.1 Degradation and stabilisation of polymer
Polymer is degraded by heat, energy, UV or residues of catalyst and generates alkyl

radicals. This alkyl radical reacts with oxygen and form peroxy radicals. These
peroxy radicals abstract hydrogen from other polymer and forms alkyl radicals and
hydroperoxide. The decomposition of hydroperoxide to alkoxy and hydroxyl radicals
induces additional decomposition of the polymer chain. In order to stop the radical
chain reaction of degradation, stabilisers such as phenolic antioxidant, phosphites,
thioether and hindered amine light stabilisers (HALS) are added.
Figure 6.2 shows some representative processes for degradation and stabilisation
of polymers. Phenolic antioxidants react with peroxy radical and alkoxy radical
by donation of hydrogen. Phosphites and thioether act as reducing agent for
hydroperoxide, which is converted to alcohol. Hydroxylamine, which is a relatively
new stabiliser, acts as hydrogen donor and hydroperoxide decomposer.
As illustrated in Figure 6.3, there are two kind of light stabilisers, HALS and UV
absorbers. HALS react with alkyl radicals and peroxy radicals after activation by
oxygen and light. The radical stabilisation reaction should be cycled as shown.
UV absorbers absorb harmful light and the absorbed energy is converted to harmless
heat. The absorbance of UV absorbers depends on the sample thickness and
concentration. This law is called Beer-Lambert law.
58
Figure 6.2 Process and heat stabilisers
Figure 6.3 Light and heat stabilisers
59
Table 6.1 Harmful wavelength for polymers

Wavelength L and hemolytic bond dissociation energy E (AB mÊUÊ³Ê U®ÊvÊ
some organic molecules
L, nm Bond Bond type Bond energy,
kJ/mol
UV-B 230 –C–C– aromatic 520
290-310 R–O–H alcohol 420-385
290 R–CR2–H prim / sec / tert H 410 / 395 / 385
320 –C–O– ether 365-390
UV-A 240 R–CH2–CH2 aliphatic 335-370
350 CR2–Cl aliphatic chloride 330-350
360 CH2–NR2 amine 330
400 –O–O– peroxide 270
prim: primary, sec: secondary, tert: tertiary
Table 6.1 shows the wavelength that specific bond absorbs, which leads to the
decompostion of the bond. For example, the ether bond absorbs at 320 nm wavelength
and amine absorbs at 360 nm wavelength. This means the UV absorber should absorb
those corresponding wavelengths of light in order to protect the polymer against UV
radiation.
6.3 Stabilisers for Polymer Electronics
Normally UV comes from the sun. The polymers for outdoor applications; here is an
example of photovoltaic module, need protection against UV radiation (Figure 6.4).
In electrical and electronics applications, not only the sun but also the light can be
the source of the UV radiation. For example, the modules in liquid crystal display
(LCD) also need to be protected against UV radiation emitted by the back light. The
fluorescent light possess specific sharp emission of UV radiation and the materials
need protection against it.
For UV management, proper understanding for UV absorbers is necessary. Most UV

absorbers, independent on the type of chromophor, absorb the damaging light and emit
non destructive heat. This is the examples of benzotriazole type of UV absorbers (Figure
6.5). In the market, different kinds of substitution of benzotriazole UV absorbers are
60
Figure 6.4 UV management in polymer electronics
Figure 6.5 Side chain effect on benzotriazole UV absorbers
Figure 6.6 TGA of benzotriazole UV absorbers
available. The reason is different side chains provide different physical influence, such
as volatility, compatibility to the polymer, melting point and others. One example is
thermal gravity analysis (TGA) of UV absorbers (Figure 6.6). All of the UV absorber
have benzotriazole chromophor but different substitutions. This gives molecules of
differing molecular weight. Consequently, they also then have different volatilities. If the
processing temperature is quite high, low volatility UV absorbers should be used.
61
Figure 6.7 Spectra of different UV absorbers
Figure 6.8 Thickness and concentration dependency
62
The chromophor is also an important factor to understand the UV absorber because

different chromophors have different absorption patterns (Figure 6.7). Benzotriazole
type has two peaks around 310 nm and 350 nm. Hydroxyphenyl-triazine has a strong
peak around 270 nm and relatively weak peak around 340 nm. Benzoxazinone has
specific peaks and cyanoacrylate have single peak around 310 nm. Those absorptions
should correspond to the sensitive regions of polymers for better protection.
The performance of UV absorbers follows Beer-Lambert law. It means the absorbance

is proportionate to the extinction coefficient of the UV absorber, concentration and
the sample thickness. Figure 6.8 shows the dependency of thickness and concentration
on transmission. This means that the appropriate concentration should be chosen for
the thickness of the article if whole UV should be cut by the article.
As showed so far, several factors should be considered in order to choose the right
UV absorber. The first factor is the thickness of the article. This determines the
concentration of UV absorber. If the article is quite thin, a UV absorber with high
coefficient is needed. Otherwise too much UV absorber must be added, which leads
to a migration problem if the solubility in the polymer is poor. The second factor is
processing temperature. Each polymer and process has specific processing temperature
and the UV absorber must be stable at the processing temperature. If the UV absorber
is not enough heat stable, volatiles causes several problems. The durability of UV
absorber is also important factor. If the lifetime of the application is one year, most
UV absorbers can do the job. But if the application has over 10 years service time, a
stable UV absorber must be chosen. The last factor is the wavelength that UV absorber
absorbs. Specific wavelength has two meanings. One is to absorb the wavelength of
light that degrades the polymer. For example, polyesters or polycarbonates absorb
around 300 nm and UV absorbers for those polymers should absorb 300 nm in order
to protect polymers. The other purpose is to cut certain wavelengths. If the application
needs to cut 380 nm, the UV absorber should have strong absorbance at 380 nm.
6.4 Functional Additives for Polymer Electronics
So far the retention or stabilisation of polymer characteristics has been discussed. The
last part is functional additives in polymer electronics. In electronics applications,
polymer tends to have contact with metals because metals are used as conductors,
solder, springs, screws and other small parts. If the polymer is in contact with metals,
especially transition metals, the degradation of polymer is accelerated. In that case,
metal deactivation provides the solution.
Standard application of metal deactivator is jacketing of the cable because it contacts

to copper wire. Copper ions can accelerate the degradation by changing valance.
63
Metal deactivators act as electron donors to form a stable complex with copper ions
and the degradation reaction is retarded. Here is an example of adding 0.2% copper
ion and with/without 0.2% IRGANOX® MD 1024 (Figure 6.9). IRGANOX® MD
1024 helps to retain the mechanical properties.
Figure 6.9 Function of metal deactivator
Electricity induces static charge. This causese dust pick up, which interferes with
the calrity, handling problems and electrical discharges which may induce electrical
shocks for fire or dust explosion. Antistatic agents can solkve such an issue.
Classical antistatic agents such as glycerine mono-stearate or amines migrate

to the surface of the polymer and anchor in the polymer while the polar groups
project out of polymer. The polar groups absorb the humidity in the air and form a
conductive path at the surface. The drawbacks are performance over time, thermal
stability, humidity dependency and migration itself, which causes the stickiness of
the film. On the other hand, the discharging mechanism of IRGASTAT® is to build a
conductive network in the polymer matrix and release the charge (Figure 6.10). The
performance is not affected by humidity and the performance lasts a long time until
the network breaks. The benefits are to minimise the risk of fire or explosion and
damage to the product by electrostatic discharge during handling or transportation,
on top of dust pick-up.
64
Figure 6.9 Performance of IRGASTAT®
Figure 6.10 Advantages of MELAPUR® 200
The last topic is halogen free flame retardants. Needless to say, the benefit of flame
retardancy is to minimise the risk of fire accidents. Melamine derivatives are a niche
in the flame retardant market, but have significant advantages in specific polymers.
65
With MELAPUR® technology, UL-94 V-0 with glass fibre reinforced polyamide is
achievable (Figure 6.10). Melamine derivatives influence on heat, oxygen and fuel.
Endothermic decomposition of melamine reduces the heat and nitrogen dilutes the
oxygen and char formation insulates the polymer. Compared to brominated flame
retardants, MELAPUR® 200 shows much less risk for corrosion. Less smoke density
and less toxicity are also benefits against conventional flame retardants.
As a summary, for the best performance of polymer in electronic applications, the

right combination of tailored additives must be optimised for the best protection.
This allows you to differentiate your products.
Further Reading
1. H. Zweilfel, Plastics Additives Handbook, 5th Edition, Hanser Gardner

Publishers, Cincinnati, OH, USA, 2001.
66
7
A Facile Route to Organic Nanocomposite
Dispersions of Polyaniline – single Wall
Carbon Nanotubes
Sainath G. Vaidya and Sanjay Rastogi
7.1 Introduction
Among available conducting polymers, polyaniline (PANI) has been a subject of

interest due to its high conductivity, ease of synthesis, environmental stability,
interesting doping and de-doping characteristics. In general the conducting form
of polyaniline is regarded as intractable in nature, which cannot be processed via
conventional processing routes. This is because emeraldine salt of PANI degrades
before melting and the surface tension is too high to dissolve in available solvents
[1]. It is known that use of functional protonic acids e.g., dodecyl benzenesulfonic
acid (DBSA) facilitates polyaniline processing in a range of organic solvents [2].
Similarly, Han and co-workers [3] used DBSA micellar solution to synthesise
polyaniline with enhanced processibility. Kohut-Svelko and co-workers prepared
polyaniline in presence of non-ionic surfactants in water [4]. The authors reported
that compared to DBSA doped PANI, polymer particle formation is much slower
owing to the lengthening of the induction period. Using micellar solutions of sodium
dodecyl sulfate (SDS) Kim and co-workers obtained polyaniline dispersions with
the particle size of 10-20 nm [5]. It is claimed that electrical properties are affected
by the presence of the SDS micelles and does not depend either upon molecular
weight or morphology. The effect of surfactant anions is also investigated by Cai
and co-workers [6]. The authors reported the preparation of polyaniline film in
presence of sodium dodecylbenzene sulfonate and SDS with higher conductivity
than that of parent polyaniline.
On the other hand carbon nanotubes (CNT) have been the subject of extensive
investigation due to their remarkable properties such as very high aspect ratio,
excellent mechanical, electrical, optical and magnetic properties. To exploit the
properties of carbon nanotubes, efficient exfoliation of the CNT bundles in the
polymer matrix is a prerequisite. There are various methods aimed at efficient
exfoliation of CNT either in polymer or solvent [7-10]. In addition, nanocomposites
67
of polyaniline-single wall carbon nanotubes (SWNT) are pursued with an interest

to use in variety of electronic devices [11-16].
Despite of the advances in preparations, the processing of such nanocomposites still

remains a challenge due to intractability of both PANI as well as SWNT. Up until
now there is no simple route to process such nanocomposite that will facilitate the
use in electronic devices. Here, we used anionic surfactant as a common stabiliser
for polyaniline as well as for SWNT. Based on this work, we report a facile route to
obtain organic nanocomposite dispersions of polyaniline with variable concentrations
of (up to 10 wt%) SWNT. From the processing point of view, this route eliminates
the need for polyaniline to be de-doped followed by dissolution in suitable solvent
and re-doping to regain the conductivity.
7.2 Materials
Highly purified HiPCO single wall carbon nanotubes were purchased from CNI Inc.,
USA. Xylene (in ortho and para forms) was purchased from VWR, UK and used as
obtained. Aniline was purchased from Riedel de Haen, Germany. All other chemicals
were purchased from Sigma Aldrich.
7.3 Experimental Section
7.3.1 Scheme - 1 Polyaniline Synthesis [17]
At room temperature, polyaniline nanofibres are synthesised using interfacial

polymerisation between 1 M HCl in water (25 ml) containing ammonium persulfate
and xylene (25 ml) containing aniline. The molar ratio of aniline to ammonium
persulfate is kept at 4:1. Upon polymerization, xylene containing unreacted aniline
is removed from the top and replaced with an equal volume of xylene.
7.3.2 Scheme - 2 Organic Dispersions of PANI
A portion (1 wt%) of either sodium dodecylbenzenesulfonate (NaDBS) or SDS are

added to the previously mentioned system and rigorously stirred for a minimum of three
hours. The system is then left idle, during which phase inversion occurs (Figure 7.1).
After phase inversion, organic phase containing surfactant modified polyaniline is
taken from the top and washed with excess amount of xylene. Throughout this chapter
the surfactant percentage mentioned is relative to the aqueous phase.
68
A Facile Route to Organic Nanocomposite Dispersions of
Polyaniline–single Wall Carbon Nanotubes
Figure 7.1 Phase inversion phenomenon; from left PANI, as prepared intermediate
state and organic dispersion
7.3.3 Scheme - 3 Exfoliation of Single Wall Carbon Nanotubes
For exfoliation of SWNT, the reported method from the literature is followed [9].
In the first step 0.2 wt% SWNT is dispersed in deionised water containing 1%
anionic surfactant. With the help of ultrasonication and UV-Vis spectroscopy, the
optimum exfoliation of the SWNT is obtained. The final wt% of SWNT in organic
nanocomposite is calculated based on the yield of PANI. The weight % of SWNT
mentioned in this chapter is relative to the yield of PANI.
7.3.4 Scheme - 4 Organic ‘Nanocomposite’ Dispersions of PANI-SWNT
Organic nanocomposite dispersions of PANI-SWNT are prepared by in situ synthesis

of polyaniline as shown in Scheme – 3. Ammonium persulfate is added to aqueous
phase and aniline in xylene is added from the top. After rigorous stirring, the system
is then left idle, during which phase inversion occurs. No traces of SWNT were
observed in the aqueous phase. The nanocomposite dispersion is then taken from
the top and washed with excess amount of xylene. The filtered material is then dried
under dynamic vacuum at 60 oC for more than 24 hours.
69
7.4 Characterisation
Fourier transform infrared (FT-IR) spectra are recorded using a potassium bromide
pellet on Infrared Excalibur instrument. UV-Vis spectroscopy is done on a Hewlett-
Packard 8453 spectrometer. Co-linear four probe conductivity measurements were
performed on the compressed pellets (20 MPa, 10 min) using nanovoltmeter (Keithley
2182A) and programmable current source (Keithley 6220) at room temperature.
7.5 Results and Discussions
7.5.1 Phase Inversion Phenomenon
Figure 7.1 demonstrates the steps in obtaining organic dispersions of PANI.
Interestingly, an addition of surfactant to as synthesised PANI without presence of

organic phase gives viscous gel-like system. Similarly, if an organic solvent is added
to aqueous suspension of surfactant stabilised SWNT, no phase inversion is observed.
It is observed that upon phase inversion (Figure 7.1), the left over aqueous phase was
pink in colour throughout. The pink color arises due to the pernigraniline form of
polyaniline, which is confirmed by UV-Vis spectroscopy and is in accordance with
the observations of other authors [18-20]. Hence it can be said that this facile route
to obtain organic polyaniline dispersion possess self filtering capability.
7.5.2 FT-IR Spectroscopy
Transmission mode FT-IR spectra of PANI, surfactant modified polyaniline and

PANI-surfactant-SWNT is shown in Figure 7.2.
The spectra are normalised with respect to intensity at 1300 cm-1 in neat PANI. The
major peaks in PANI agreed well with the literature [21]. Some similarities are observed
in samples (b) to (e). The peak at 1374 cm-1, which is assigned to quinoid=N-benzene
stretching mode [22] is absent. In addition, quinoid vibration peak at ~1600 cm-1
became broad, which could be resulting from the interaction of the bulky surfactant
headgroups at the quinoid part of polyaniline. It is known that sulfonic acid absorb
strongly in the 1050 and 1200 cm-1 region. Although this region is masked by an
‘electron like band’ of polyaniline, a weak shoulder of symmetric SO2 stretch at 1128
cm-1 is observed in samples (b) to (d) [21]. In sample (e) the electronic like band of
PANI at 1140 cm-1 became broad and shifted to 1116 cm-1. On the other hand no
such shift is observed in nanocomposites prepared using NaDBS [sample (d)] except
that it became broader as compared to sample (b), which contained NaDBS only.
70
Figure 7.2(a) FT-IR spectra of PANI, PANI-Surfactant, PANI-Surfactant-SWNT in

region of 1800-600 cm-1
Figure 7.2(b) FT-IR spectra of PANI, PANI-Surfactant, PANI-Surfactant-SWNT in

region 4000-2800 cm-1
71
Therefore, it can be convincingly deduced that combination of SWNT-SDS perpetuates

more restrictions on electronic like band of PANI as compared to SWNT-NaDBS.
7.5.3 UV-Vis Spectroscopy
UV-Vis spectroscopy can be used to probe the degree of doping in polyaniline [3].
As can be inferred from Figure 7.3, PANI showed only weak polaron (quasiparticle
composed of an electron and its accompanying polarisation field) absorption at ~430
nm while P-P* transition of benzoid segment at 360 nm was absent. It is known that
these two peaks often combine in single distorted peak with local maxima between
360 and 420 nm [3, 5]. Upon addition of either NaDBS or SDS, the polaron band
shifted significantly to 400 nm and became sharp. This observation can be explained
in terms of transformation from compact coil to expanded coil conformation, which
leads to the reduction of P-conjugation defects [3, 23]. With further addition of 2
wt% SWNT the polaron absorption band shifted from 400 nm to 385 nm and new
weak polaron band at ~775 nm is observed. This band is related to the localisation
of the cations on PANI backbone. This band is absent in pristine polyaniline as well
as in surfactant modified polyaniline. Therefore the previous observations show that
complex interactions exist between PANI and SWNT which are further influenced
by the structure of anionic surfactant.
Figure 7.3 Absorbance spectra of PANI, PANI-Surfactant and PANI-SWNT-surfactant
72
7.5.4 Four-probe Conductivity
Four probe conductivity measurements on polyaniline-SWNT pellets are summarised in

Figure 7.4. As observed from UV-Vis spectroscopy, reduction in P-conjugation defects
suggests higher conductivity in surfactant modified polyaniline. Indeed, the conductivity
of PANI-1% NaDBS and PANI-1%SDS is 3.35 S/cm and 5.53 S/cm, respectively.
Figure 7.4 Conductivity of organic nanocomposite dispersions
This result confirms the role of surfactant as an additional dopant to PANI. In

presence of 2% SWNT, the conductivity of the nanocomposite dispersions containing
NaDBS is much higher (11.08 S/cm) compared to its SDS counterpart 8.01 S/cm. It is
known from the literature that both NaDBS and SDS show strong interactions with
SWNT and self organisation on SWNT surface [10, 24]. However, from FT-IR and
UV-spectroscopy, it can be suggested that combination of SWNT-SDS stimulate more
restrictions on chain conformations of PANI as compared to NaDBS counterpart. As
a result, higher conductivity is observed in nanocomposites prepared using NaDBS.
7.6 Conclusions
In conclusion, we have demonstrated a facile route to obtain processable organic

dispersions of polyaniline with and without SWNT. The dispersions are studied with
73
FT-IR and UV-Vis spectroscopy and four-probe conductivity measurements. The role
of surfactants as a secondary dopant as well as effective stabiliser for polyaniline is
recognised. This work is then extended to obtain organic ‘nanocomposite’ dispersions
where it is shown that the anionic surfactants can be successfully used as an ‘interfacial
link’ between polyaniline as well as SWNT. It is observed that SWNT in polyaniline
matrix enhances the conductivity of nanocomposite through complex interactions
in presence of the surfactant. However, the type of anionic surfactant plays a crucial
role to influence the chain conformations of PANI in the presence of SWNT. The
investigation of complex interactions between PANI-Surfactant-SWNT forms the part
of our future work. The nanocomposite dispersion thus obtained is easy to disperse in
a range of polymer matrices through either solution processing or coating route. This
can also be used in coating of the inorganic particles thus facilitating development
of electronic devices.
7.7 Acknowledgements
We gratefully thank Dutch Polymer Institute (DPI) for the financial support for this
work. We are also thankful to Dr. Hari Upadhyaya of CREST (Centre for Renewable
Energy and Systems Technology, Loughborough) and Dr. John.A.E.H.van Haare of
DPI for helpful discussions and comments.
References
1. B. Wessling, Synthetic Metals, 2005, 152, 5.
2. Y. Cao, P. Smith and A.J. Heeger, Synthetic Metals, 1993, 48, 91.
3. M-G. Han, S.K. Cho and S-G. Oh, Synthetic Metals, 2002, 126, 53.
4. N. Kohut-Svelko, S. Reynaud and J. Francois, Synthetic Metals, 2005, 150,

107.
5. B-J. Kim, S-G. Oh and M-G. Han, Synthetic Metals, 2001, 122, 297.
6. L-T. Cai, S-B. Yao and S-M. Zhou, Synthetic Metals, 1997, 88, 209.
7. M.S.P. Shaffer, X.F. Fan and A.H. Windle, Carbon, 1998, 36, 1603.
8. A.R. Bhattacharya, P. Potschke, M. Adbel-Goad and D. Fischer, Chemical

Physics Letters, 2004, 392, 28.
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9. O. Regev, P.N.B. Elkati, J. Loos and C.E. Koning, Advanced Materials, 2004,
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10. O. Mattaredona, H. Rhoads, Z. Li, J.H. Harwell, L. Balzano and D.E.

Resasco, Journal of Physics Chemisty B., 2003, 107, 13, 357.
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12. P.C. Ramamurthy, A.M. Malshe, W.R. Harrell, R.V. Gregory, K. McGuire
and A.M. Rao, Solid- State Electronics, 2004, 48, 2019.
13. S. Lefrant, M. Baibarc, I. Baltog, C. Godon, J.Y. Mevellec, J. Wery, E. Falques,

L. Milhut, H. Aarab and O. Chauvet, Synthetic Metals, 2005, 155, 666.
14. Y. Long, Z. Chen, X. Zhang, J. Zhang and Z. Liu, Applied Physics Letters,
2004, 85, 1796.
15. M.R. Karim, C.J. Lee, Y-T. Park and M.S. Lee, Synthetic Metals, 2005,
151, 131.
16. H. Zengin, W. Zhou, J. Jin, R. Czerw, D.W. Smith, Jr., L. Echegoyen, D.L.
Carroll, S.H. Foulger and J. Ballato, Advanced Materials, 2002, 14, 1480.
17. J. Huang and R.B. Kaner, Journal of the Amerian Chemical Society, 2004,
126, 851.
18. A.G. MacDiarmid, S.K. Manohar, J.G. Masters, Y. Sun and H. Weiss,
Synthetic Metals, 1991, 41-43, 621.
19. K.G. Neoh and E.T. Kang, Synthetic Metals, 1993, 60, 13.
20. H.S. Kolla, S.P. Surwade, Z. Zhang, A.G. MacDiarmid and S.K. Manohar,
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22. M. Trchova, J. Stejskal and J. Prokes, Synthetic Metals, 1999, 101, 840.
23. N. Kuramoto and A. Tomita, Synthetic Metals, 1997, 88, 147.
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Nanoletters, 2003, 3, 269.
75
76
8
Preparation and Characterisation of Novel
Electrical Conductive Rubber Blends
Kok Chong Yong
8.1 Introduction
This chapter describes an efficient method (i.e., solution mixing) for producing
blends with good compatibilities and also high electrical conductivities by
combining poly(butadiene-co-acrylonitrile) NBR [grade with 48 wt% acrylonitrile
(ACN) content, as the rubbery host] with different proportions of polyaniline
dodecylbenzenesulfonate (PAni.DBSA) (as the only electrical conductive filler). In this
method, both NBR and PAni.DBSA are required to be soluble in a common shared
solvent, e.g., chloroform.
8.2 Experimental
8.2.1 Chemicals and Raw Materials
For the PAni.DBSA synthesis, aniline monomer, ammonium persulfate [as the
antioxidant (APS)], HCl solution (as the first doping agent), anhydrous ferric chloride
[(FeCl3) as the catalyst], ammonia solution (as the dedoping agent), DBSA solution
in 2-propanol (as the final doping agent), were used. The NBR with 48 wt% ACN
content was washed with methanol for 24 hours using Soxhlet extraction in order
to remove chemical contaminants [1].
8.2.2 Synthesis of PANI.DBSA and Blends Preparation
The PAni.DBSA with a 42% protonation level on the basis of the S:N atomic ratio
was prepared by the following procedures as described in literature [1]. Masterbatch
solutions of the pure NBR (50 mg NBR/ml solvent) and PAni.DBSA (16.7 mg PAni.
DBSA/ml solvent) in chloroform were prepared and filtered. The pure NBR solution
77
was mixed with the PANI.DBSA solution to obtain the following compositions (wt%
NBR:wt% PANI.DBSA): 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 97.5:2.5 and 99:1.
Each of the blend solutions was magnetically stirred for 24 hours at room temperature
prior to casting in order to enhance its homogeneity [1].
8.3 Characterisation of NBR-PAni.DBSA Blends
8.3.1 Methods of Characterisation
Characterisations of the resulting NBR-PAni.DBSA blends were performed by using:
I. Optical microscope (thickness of each sample, ~3.0 μm and 200 s magnification)

and transmission electron microscope (TEM) (microtome sample, 40,000 ×
magnification) at accelerating voltage, 80 kV [1].
II. FT-IR spectrometer, by casting a thin film (~3.0 μm) on a KBr window [1].
III. Differential scanning calorimeter for 30 to 400 °C analyses (with heating rate
20 °C/min) and -60 to 0 °C analyses (with heating rate 10 °C/min); each sample
sealed with aluminium pan and analysed under a N2 atmosphere [1].
IV. Keithley electrometer to measure the electrical resistances of pure polymers and
their blends cast films (thickness of each sample, ~6.0 μm) on microscope slides
(6.25 cm2 s 0.1 cm), based on the two-probe method [1] and four-probe Van der
Pauw technique [1-2].
8.3.2 Calculation of Solubility Parameter Values
Solubility parameters for pure NBR and PANI.DBSA were estimated by using the molar
attraction constants values, Fi as calculated by Hoy [3]. Chloroform has a solubility
parameter of 19.0 (MJ.m-3)0.5 [1]. The calculated values of solubility parameter for
both NBR 48 wt% ACN and PAni.DBSA were 20.7 and 20.8 (MJ.m-3)0.5, respectively
[1]. The pure NBR (48 wt% ACN) and PAni.DBSA were highly soluble in it.
8.3.3 Morphological Studies (Optical Microscopy and TEM)
Optical micrographs of blends containing 5 and 40 wt% of PANI.DBSA are shown

in Figure 8.1. Two coloured regions were observed, i.e., the bright ones (bright-green
in actual colour) and the dark ones (dark green in actual colour). The bright regions
78
Preparation and Characterisation of Novel Electrical Conductive Rubber Blends
Figure 8.1 Optical Micrograph (200 × magnification) for blends of NBR (48
ACN wt%) - PANI.DBSA containing (a) 5 wt% and (b) 40 wt% of
PANI.DBSA. (Reproduced with permission from K.C. Yong, P.J.S. Foot, H.
Morgan, S. Cook and A.J. Tinker, European Polymer Journal, 2006, 42, 8, 1716,
Figure 2a and 2d. ©2006, Elsevier)
Figure 8.2 TEM (40,000 × magnification) for blends of NBR 41 ACN wt%-
PANI.DBSA containing (a) 5 wt% and (b) 10 wt% of PANI.DBSA. (Reproduced
with permission from K.C. Yong, P.J.S. Foot, H. Morgan, S. Cook and A.J. Tinker,
European Polymer Journal, 2006, 42, 8, 1716, Figure 3. ©2006, Elsevier)
(richer in NBR) are regions with well-blended NBR and PAni.DBSA [1]. The dark
regions (rich in PAni.DBSA) mainly consist of large PAni.DBSA particles and their
agglomerates, resulting from some degree of phase separation [1].
79
Transmission electron micrographs of blends containing 5 wt% (below percolation

threshold) and 10 wt% (above percolation threshold) of PANI.DBSA are shown in
Figure 8.2. Larger, discrete polyaniline particles are observed in Figure 8.2(a), which
is consistent with the fairly low electrical conductivity of the corresponding blend [1].
In Figure 8.2(b), the PAni.DBSA particles are starting to form conductive pathways,
which is consistent with the much higher conductivity for the related blend [1].
8.3.4 FT-IR Spectroscopy
Examples of FT-IR spectra for pure NBR (48 wt% ACN), PAni.DBSA and their blends
(i.e., with 10 wt% and 40 wt% of PAni.DBSA) are shown in Figure 8.3. All the spectra of
pure materials obtained corresponded well with those found in the literature [1, 4, 5].
Figure 8.3 FT-IR spectra for the pure NBR (48 ACN wt%), PAni.DBSA and
their blends containing 10 wt% and 40 wt% of PAni.DBSA. (Reproduced with
permission from K.C. Yong, P.J.S. Foot, H. Morgan, S. Cook and A.J. Tinker,
European Polymer Journal, 2006, 42, 8, 1716, Figure 4. ©2006, Elsevier)
80
In general, the FT-IR spectra of the blend films are merely superpositions of the
spectra for both polymers with predominance to the richer phase absorption bands
[1]. However, some significant shifts of certain key bands were also successfully
observed, i.e., a decrease from 3447 to 3411 cm-1 for the N-H stretch and an increase
from 1030 to 1080 cm-1 for the S=O stretch (which are solely due to the PAni.DBSA),
attributable to changes in the intermolecular interactions with the NBR [1].
8.3.5 DSC Thermal Analysis
The sub-ambient temperature DSC thermograms (see example, Figure 8.4 and
Table 8.1) of the blends had positive glass transition (Tg) shifts that increased with
the proportion of PANI.DBSA up to 30 wt%, and then decreased when 40 wt% or
more is added (due to more complete phase separation between the two components
at the higher levels of PAni.DBSA) [1].
The above-ambient temperature DSC thermograms for the blends (see Figure 8.5
and Table 8.2) show thermal processes that are combinations of events recorded
for pure NBR and PAni.DBSA, but the events show some temperature shifts relative
to the corresponding processes in the pure polymers [1]. Some indication of the
high-temperature miscibility of PAni.DBSA with NBR in their blends may also be
gained from the onset temperatures of the major exotherm [1]. For high proportions
of PAni.DBSA (40 to 50 wt%), only small shifts in the onset temperature were
observed [1]. The blends containing low to moderate amounts of PANI.DBSA (10
to 30 wt%) showed large shifts in the onset temperature of the major exotherm,
echoing the evidence for better mixing in these blends at room temperature and
below [1].
8.3.6 Electrical Conductivity Determination
Electrical conductivities were calculated from the mean resistance values using the Van
der Pauw Equation (8.1) for the samples measured by the four-probe technique [1].
2ln2
S (8.1)
R1 R2 udf
Where: σ is the electrical conductivity (S/cm), R1 and R2 are the mean values of
measured resistance for a cast blend in its two perpendicular contact configurations
(Ω) d is thickness of the sample (cm), and f is a geometric factor (approximately 1.00
for square-shaped plaques).
81
Figure 8.4 Sub-ambient temperature DSC thermograms for NBR 48 ACN wt%-
PANI.DBSA blends of various compositions (wt% NBR:wt% PANI.DBSA).
(Reproduced with permission from K.C. Yong, P.J.S. Foot, H. Morgan, S. Cook and
A.J. Tinker, European Polymer Journal, 2006, 42, 8, 1716, Figure 6. ©2006, Elsevier)
Table 8.1 The mean glass transition temperature (Tg)

values for NBR-PAni.DBSA blends [1]
Composition
Tg (°C)
(wt% NBR:wt% PAni.DBSA)
Pure NBR -11
90:10 -8
80:20 -8
70:30 -7
60:40 -8
50:50 -8
82
Figure 8.5 Above-ambient temperature DSC thermograms for NBR 48 ACN

wt%-PANI.DBSA blends of various compositions (wt% NBR:wt% PANI.DBSA)
(Reproduced with permission from K.C. Yong, P.J.S. Foot, H. Morgan, S. Cook and
A.J. Tinker, European Polymer Journal, 2006, 42, 8, 1716, Figure 8. ©2006, Elsevier)
Table 8.2 The mean onset temperature values of major exotherms for the above-
ambient DSC thermograms of PAni.DBSA, pure NBR and their blends [1]
Composition Onset Temperature of Major Exotherm
(wt% NBR:wt% PAni.DBSA) (°C)
Pure NBR 331
90:10 263
80:20 240
70:30 222
60:40 246
50:50 229
PAni.DBSA 233
83
Electrical conductivities (< 10-7 S/cm) were also calculated from the mean resistance
values obtained by the two-probe method using Equation 8.2 [1]:
¥ 1 ´¥ L ´
S ¦ µ¦ µ (8.2)
§ R ¶§ A ¶
where: S is the electrical conductivity (S/cm), R is the mean value of measured resistance
(voltage/current) for the cast blend (Ω), L is the measured electrode spacing distance
[cm] and A is the cross-sectional area (cm2) of cast film between the electrodes.
Pure NBR has conductivity in the region of 10-14 S/cm. The PAni.DBSA had an
electrical conductivity of 1.2 ± 0.5 S/cm. The electrical conductivity of all the blends
increased with the proportion of PAni.DBSA. The conductivity percolation threshold
for the blends was estimated by fitting the data from the curve of log blend electrical
conductivity versus PAni.DBSA content (see Figure 8.6) to a simple percolation model
as defined by Equation 8.3 [1, 6-7]:
t

f c f fp (8.3)
where: c is a constant, t is the critical exponent, f is the volume fraction of the

conductive medium and fp is the volume fraction at the percolation threshold. All the
weight fractions referred to previously were converted into volume fractions for this
analysis. The values of t and correlation coefficient (R) for each case were estimated
by fitting the data to a plot of log electrical conductivity (S) versus log (f-fp).
Figure 8.6 Electrical conductivities of NBR 48 ACN wt%-PANI.DBSA blends as

a function of PANI.DBSA content (wt%) [1] (Reproduced with permission from
K.C. Yong, P.J.S. Foot, H. Morgan, S. Cook and A.J. Tinker, European Polymer
Journal, 2006, 42, 8, 1716. ©2006, Elsevier)
84
Reasonably low electrical conductivity percolation threshold, i.e., 6.0 wt%/5.4 volume
% of PANI.DBSA content can evidently be achieved here (with value of t = 3.6 and
R = 0.99 for blends based on NBR 48 ACN wt%).
8.4 Conclusion
NBR-PAni.DBSA blends (48 wt% ACN) with reasonably good compatibility and
useful levels of electrical conductivity (up to 10-2 S/cm) could be produced by solution
mixing [1]. It is also proposed that for an unstrained NBR-PAni.DBSA blend sample
(as discussed in this chapter) the PAni.DBSA fillers in both of the well-blended and
phase-separated-regions are all contributing to the electrical conductivity of the blend,
especially the one that was below the main percolation threshold.
Acknowledgements
The author would like to acknowledge the Malaysian Rubber Board for the financial
support of this project. The author also thanks P. J. S. Foot, H. Morgan, S. Cook,
A. J. Tinker, C. Hull, R. Davies and K. Lawrence for their supervision, support and
assistance in this part of work.
References
1. K.C. Yong, P.J.S. Foot, H. Morgan, S. Cook and A.J. Tinker, European
Polymer Journal, 2006, 42, 8, 1716.
2. L.J. Van der Pauw, Philips Research Reports, 1958, 13, 1.
3. K.L. Hoy, Journal of Paint Technology, 1970, 42, 76.
4. E.L. Tassi and M-A. De Paoli, Polymer, 1992, 33, 11, 2427.
5. H. Morgan, P.J.S. Foot and N.W. Brooks, Journal of Materials Science, 2001,
36, 5369.
6. M.E. Leyva, G.M.O. Barra and B.G. Soares, Synthetic Metals, 2001, 123, 443.
7. D. Stauffer, Introduction to Percolation Theory, Taylor and Francis, London,

UK, 1985.
85
86
9
Solar Textiles
Robert Mather and John Wilson
9.1 Introduction
This Chapter brings together two very important technologies: one old, the other
much newer. The old technology concerns textiles: materials that have been in use
for several thousand years. There are, however, many exciting developments still
occurring in textile processing and application, and indeed this Chapter discusses
such a development. The newer technology concerns sources of energy, alternative
to those predominantly in use today. This is currently a topic of immense importance
and urgency.
It is now almost universally accepted that the dependence on oil worldwide has to
cease within the next few decades. Coal resources are still vast, but there are concerns
about the potentially damaging environmental problems that the extraction and use
of coal entail. Many people are concerned too about nuclear fission as a source of
energy. Controlled nuclear fusion has not yet been achieved. On the other hand, there
are numerous sources of alternative energy: geothermal, wind power, tidal power and
renewable natural products. These sources, taken together, are more than adequate
for the world’s current needs. Their problems are chiefly their uneven distribution
around the world, and also their seasonal or diurnal variations. Many are best utilised
as localised, rather than centralised sources of energy. One particularly important
energy source is sunlight, in that this source is ‘endless’, and through the application
of photovoltaic technology, it can be converted directly to electricity.
This Chapter sets out to make the case for the use of textiles, and the polymeric fibres
that comprise them, as substrates for photovoltaic devices – or solar cells. Apart
from the use of an endless energy source, there are other advantages too: a clean,
silent technology, very small maintenance costs, and an attractive technology for
remote areas where there is no electrical supply from a grid. It could also be a key
technology for quick electrical supply to regions struck by sudden natural disasters,
such as earthquakes, hurricanes and floods.
87
9.2 Why Textiles?
Solar cells are typically sandwiched between glass plates, but glass plates are heavy,
fragile and inflexible. Thus, care has to be taken with their storage, transport and
assembly. For these reasons, there has been increasing attention commercially to the
construction of lighter, flexible cells, which can still maintain the durability required
of them, even in demanding environments. There are now a number of examples of
solar cells embedded onto plastic films. Amongst these examples is the ‘PowerPlastic’,
developed by Konarka Technologies Inc., where organic solar cells are printed or
coated onto a flexible plastic substrate using a roll-to-roll manufacturing process.
Another example is the development by PowerFilm Inc., of a roll-to-roll process for
depositing layers of amorphous silicon onto a polyimide film, backed by a metal
layer. Flexcell Ltd., have developed a process in which a very high frequency plasma
deposition technique is used for the deposition of silicon onto a plastic roll, which
has first been coated with a thin metal layer. In a process developed by Nanosolar
Inc., copper indium gallium selenide ink is printed onto a metal foil.
The successful integration of solar cells on plastics is, without doubt, an important
expansion of photovoltaic technology. Nevertheless, another expansion would be
achieved by the integration of solar cells on textile fabrics, provided the physical and
mechanical properties of the fabrics were not impaired. Textiles have a vast range
of applications and markets, they can be produced by a wide variety of fabrication
processes (weaving, knitting, braiding, felting), and these fabrication processes offer
enormous versatility for tailoring fabric shape and properties. Textile fabrics can,
therefore, be readily installed into structures with complex geometries, a feature that
invites a number of potential applications.
There are already a number of examples of the use of solar cells with textiles. Both
Konarka Technologies Inc., and PowerFilm Inc., have applied their solar plastic
films to textiles. Zabetakis and co-workers have described the design of an awning,
which provides both protection from the sun and converts the incident sunlight into
electricity [1]. A sail has been designed in which flexible solar cells are attached to
the sailcloth [2]. The design allows for the expansion of the sailcloth as wind blows
on it. There is considerable interest too in attaching solar films to apparel.
9.3 Solar Cells
These are essentially large area semiconductor diodes that absorb sunlight to generate
free electrical charges. The photovoltaic effect relies on the in-built electric field that
is produced at the junction between two dissimilar semiconducting layers: the size
of this field determines the voltage that may be produced by the solar cell and it is
88
Solar Textiles
responsible for separating the pairs of positive and negative photogenerated charges.
These are passed to the external electrical load by electrical contacts on the top and
bottom of the cell: one of these contacts is transparent to allow the sunlight to reach
the semiconductor.
The choice of semiconductors is limited by the requirement to match the optical

absorption to the solar spectrum: the semiconductor characteristic that defines this
feature is the bandgap energy, the lowest energy that may be absorbed. If this is too high
(wavelengths towards the ultraviolet (UV)) then most sunlight passes through the cell
without any effect and generates a low current; if it is too low (wavelengths towards
the infrared) then the cell has a weak in-built field and so generates a low voltage.
Fortunately one of the commonest and most developed semiconductors, silicon, is
a reasonable match for sunlight and may be produced in a thin-film form that is an
even better optical absorber than the single-crystal silicon used in microelectronics.
It may also be synthesised in p-type and n-type forms to make up a typical diode.
When these fundamental limits are taken into consideration, the maximum solar
power conversion efficiency for a simple cell with one in-built junction is ~25%.
Triple junction cells have a limiting efficiency of 32% but are more difficult to
manufacture. To attain high conversion efficiency a cell must be designed with trade-
offs between the various conflicting requirements, giving the variety of configurations
and additional layers that are used by different manufacturers. One of the obvious
features is the need to reduce cost without compromising performance: thin-film
cells lie at the low cost end of the range, but have lower efficiencies. Another
consideration is the energy embedded in each cell, because not only is this reflected
in the manufacturing cost but also it determines the energy pay-back period for
a real renewable energy source. Again, most thin-film cells have lower pay-back
periods than do ‘bulk’ crystalline cells.
9.4 Technological Specifications
There are a number of key technological specifications that have to be met, for a solar
textile to prove viable. The performance of the cells must not be compromised by
the textile fabric: in particular, there must be efficient and durable conducting paths
within the fabric to deliver the current from the solar cells. Moreover, the textile is
very likely to contain additives which assist the processing of the fabric, and indeed of
the fibres themselves, and additionally enhance the fabric’s performance as a product.
Not only should the additives not compromise the performance of the solar cells, but
also conversely, the solar cells should not impair the performance of the fabric or
its associated additives. Where solar cells are bonded to a fabric surface, the surface
properties will necessarily be changed. These changes will have implications for the
89
resistance of the fabric surface to abrasion and even to the adverse environments
which the fabric may encounter in use. It is, therefore, essential that a protective
coating is deposited over the solar textile, such as are already used for many textile
fabric applications. Finally, the flexibility of a fabric and its conformability to a desired
shape must not be severely compromised.
One of the most important technological considerations is matching the load to

be powered by the solar textile to the current-voltage characteristics of the solar
cells it contains. The current that can be drawn from the cells is proportional to the
illuminated area. It also depends on the intensity of illumination and the resistance of
the external load [3]. In contrast, the voltage of the cell depends on its construction. On
an open circuit, a cell may produce approximately 0.5 V, but by stacking up to three
cells on top of one another, the voltage is appreciably increased. Nevertheless, when
the cell is connected to the external load, its voltage may be considerably reduced.
Overall, however, the matching of the current-voltage characteristics to the external
load is far less demanding if the area occupied by the cells is sufficiently large, and
hence accessible to sufficient sunlight.
9.5 Suitable Textile Constructions
9.5.1 Fibres
Successful construction of textile fabrics as substrates for the integration of solar

cells has to take into account the type and grade of polymer used, the type of fibre
extruded from it, and subsequent fabric construction. Fibre selection is very much
determined by its ability to withstand successfully the elevated temperatures required
for the deposition of the thin layers comprising a solar cell. Where these temperatures
are as high as 400 oC or more, as in the deposition of many types of solar cell,
selection is restricted to high-performance fibres, such as glass fibres, polyimides,
polybenzimidazoles and polybenzoxazoles, but these types of fibre are expensive.
However, it has been demonstrated that nanocrystalline silicon films can be successfully
laid down at temperatures as low as 200 oC [4, 5], a factor that then broadens fibre
choice to include a range of commodity fibres.
The fibre must also be able to withstand prolonged exposure to sunlight, specifically
irradiation by UV light. The twin considerations of thermomechanical stability up
to 200 °C and resistance to UV radiation do rule out several types of commodity
fibre. These fibres include most natural fibres, as well as commercial polyolefin and
acrylic fibres, all of which melt or begin to decompose below 200 °C. Nevertheless,
polyethylene terephthalate (PET) fibres are potentially suitable substrates: they melt at
260-270 °C and exhibit good stability to UV radiation [6]. They are also commercially
90
Solar Textiles
attractive on account of their widespread use. A huge range of different PET fabrics is
available. They possess good mechanical properties and, with the exception of alkalis,
are resistant to chemical attack. Fabrics made from Nylon 6:6 fibres are also widely
available, although they are prone to degradation in strongly acidic environments.
However, to be sufficiently UV-resistant, they need to contain suitable light-stabilisers,
but it should equally be noted that commercial Nylon 6:6 fabrics are extensively used
in the production of tents, hot-air balloons and parachutes!
Fabrics made of E-glass fibres could also be viable, in that the price of E-glass is
similar to or only slightly higher than that of PET [7]. One advantage could be their
transparency, as with plate glass in conventional solar cells. E-glass fibres are, however,
prone to flexural rupture, and possess poor resistance to environments of extreme pH.
Some other glasses, such as R- and S-glass, which are more stable to these extreme
pHs, are also approximately 6-8 times more expensive [8].
9.5.2 Fabrics
The type of fabric construction is also important, in that it affects the fabric’s physical
and mechanical properties, and its effectiveness as an electrical conductor. Whatever
type of construction is used, it is important that the yarns constituting the fabric are
sufficiently close together. If the fabric is too porous, the thin layers comprising the
solar cells cannot be successfully deposited onto it.
For good electrical conduction, woven fabrics are generally favoured [9, 10], because
they possess the best dimensional stability and can be constructed to render desired
flexibilities and conformations. Furthermore, the yarn paths in woven structures are
well ordered, which permits the design of complex fabric-based electrical circuits [9].
In addition to woven fabrics, embroidered fabrics may also in the future be attractive
options for circuit design, since they too possess ordered yarn paths, but with much
more complex patterns than in woven fabrics. Knitted fabrics, by contrast, do not
retain their shapes so well, and the rupture of a yarn is liable to induce laddering.
These problems are exacerbated if the shape of the fabric is continually changing, as in
apparel usage. Nonwoven fabrics do not, so far, possess the strength and dimensional
stability of woven fabrics; and the scope for construction of electrical circuits in them
is limited, as their yarn paths are highly unoriented.
9.6 Electrical Conductivity
It is evident that, as with any type of solar cell, the top and bottom layers must be
electrically conductive. The transparent top layer will consist of a transparent oxide,
91
such as indium tin oxide or zinc oxide. The bottom layer, formed by the textile fabric,
must also be made conductive, and several strategies are available for achieving this
goal. One approach is to process fibres from electrically conducting polymers. There
has been particular emphasis on the fibre processing of poly-heterocyclic compounds
such as polyaniline, polypyrrole and polythiophene. Conductivities of up to the order
of 100 S/cm have been reported for these polymers [11-13]. For comparison, the
conductivities of copper and graphite are approximately 6 s 105 S/cm and 700 S/cm,
respectively. However, the mechanical properties of these conductive polymers are
often inadequate [14], and they possess limited flexibility [15]. To obviate these
difficulties, some fibre blends with conventional polymers have been produced,
which aim to exploit the desirable properties of both polymeric components. This
approach has enjoyed a measure of success [15], although the conductive polymer has
to withstand the conditions, e.g., elevated temperatures, required for processing the
conventional polymer fibre. However, one report has been published of conducting
fibres arising from the addition of solutions of conducting polymer to strands of
freshly melt extruded synthetic fibre, before the fibre has solidified [13].
Another approach is to incorporate metal filaments during fibre processing, prior to

fabric construction. Whilst conducting fabrics can certainly be achieved by this approach,
it necessitates the production of specially constructed fabrics for supporting the solar
cells rather than the use of fabrics already available on the market. In addition, these
fabrics are generally much stiffer. Nevertheless, a number of electrically conductive
fabrics have been produced, particularly for military use and where safety and security
are important. Deposition of conductive polymers offers another route. The conductive
polymer may, for example, be deposited from a suspension. Alternatively, the conductive
polymer may be formed by bulk polymerisation in the presence of the textile [14]. As
polymerisation proceeds, the resulting polymer is precipitated as an insoluble solid.
The polymer deposited onto the textile surface must adhere to it sufficiently strongly
during the stages of integration of the solar cell and subsequent use [16]. Better control
is achieved if polymerisation occurs on the textile fibre surfaces themselves. A layer of
monomer is first adsorbed onto the fibre surfaces. On exposure to a suitable oxidising
agent, adsorbed monomer is converted to the corresponding polymer [14]. For this
approach to be successful, there must be sufficient adsorption of monomer to the textile
substrate, and the substrate must be resistant to oxidising agent.
The pigmentation of synthetic fibres with carbon black has been practised for a good
number of years. Latterly, its potential for promoting electrical conductivity in fibres
has been explored. Nowadays, there is rapidly growing interest too within the textiles
community in the incorporation of carbon nanotubes into fibres, particularly as a
means of reinforcing them. However, their incorporation at a sufficient level would
also render the fibres electrically conducting, and no doubt this property will be fully
explored over the coming years.
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Solar Textiles
9.7 The Future
The successful integration of solar cells on textiles opens up a whole range of possible
applications. Many of these applications would exploit the light weight, flexibility and
conformability of textile fabrics. For example, they can be placed over curved surfaces
in buildings, and be installed in spaces that would be otherwise inaccessible, such as in
automotive, marine and aerospace equipment. Moreover, textile fabrics can be rolled
up, transported to a desired location and then unrolled at that location. The technology
would, therefore, be valuable to those living in remote areas, and could also be used to
get power quickly to disaster areas, hit by earthquakes, hurricanes, floods or fire.
In the meantime, organic semiconductors are becoming better developed, and these
semiconductors are likely to become increasingly attractive alternatives to inorganic
semiconductors. Many organic semiconductors are polymeric. Their use would
reduce the cost of solar cell deposition. Dye-sensitisation for matching with the
solar spectrum may too one day become a reality, though this day is likely to be far
into the future. Both these developments would assist the future technological and
commercial progress of solar textiles.
References
1. A. Zabetakis, A. Stamelaki and T. Teloniati in Proceedings of a Conference on

Fibrous Assemblies at the Design and Engineering Interface – INTERDEC,
2003, Edinburgh, UK.
2. H-F. Muller, inventor; no assignee; US 6237521, 2001.
3. R.R. Mather and J.I.B. Wilson in Intelligent Textiles and Clothing, Ed., H.R.
Mattila, Woodhead Publishing Limited, Cambridge, UK, 2006, p.206.
4. H. Shirai, Y. Sakuma, Y. Moriya, C. Fukai and H. Ueyama, Japanese Journal

of Applied Physics, 1999, 38, 6629.
5. J. Löffler, C. Devilee, M. Geusebroek, W.J. Soppe and H-J. Muffler in

Proceedings of the 21st European Photovoltaic Solar Energy Conference,
Dresden, Germany, 2006, p.1596.
6. R.W. Moncrieff, Man-made Fibres, 6th Edition, Newnes-Butterworths,

London, UK, 1975.
7. J.W.S. Hearle in High-performance Fibres, Ed., J.W.S. Hearle, Woodhead

Publishing Limited, Cambridge, UK, 2001, p.1.
93
8. F.R. Jones in High-performance Fibres, Ed., J.W.S. Hearle, Woodhead

Publishing Limited, Cambridge, UK, 2001, p.191.
9. M.S. Abdelfattah in Electronics on Unconventional Substrates –

Electrotextiles and Giant-Area Flexible Circuits, Eds., M.S. Shur, P.M. Wilson
and D. Urban, MRS Symposium Proceedings Volume 736, Materials Research
Society, Warrendale, PA, USA, 2003, p.25.
10. E. Bonderover, S.Wagner and Z. Suo in Electronics on Unconventional

Substrates – Electrotextiles and Giant-Area Flexible Circuits, Eds., M.S.
Shur, P.M. Wilson and D. Urban, MRS Symposium Proceedings Volume 736,
Materials Research Society, Warrendale, PA, USA, 2003, p.109.
11. A.G. MacDiarmid and A.J. Epstein, Journal of the Chemical Society, Faraday
Discussions, 1989, 88, 317.
12. J-A. Pomposo, E. Ochoteco, C. Pozo, P-M. Carrasco, H-J. Grande and F-J.
Rodriguez, Polymers for Advanced Technologies, 2006, 17, 26.
13. Chemical Fibres International, 2001, 51, 361.
14. A. Malinauskas, Polymer, 2001, 42, 3957.
15. D. Akbarov, B. Baymuratov, R. Akbarov, P. Westbroek, K. de Clerck and P.

Kiekens, Textile Research Journal, 2005, 75, 197.
16. J.P. Boutrois, R. Jolly and C. Petrescu, Synthetic Metals, 1997, 85, 1405.
94
10
Flexible Sensor Array for a
Robotic Fingertip Using Organic
Thin Film Transistors (OTFT) with
Minimum Interconnects and
Improved Noise Tolerance
Ahmed A. Maatouk and Darek Korzec
10.1 Introduction
Organic technology has quickly developed in the past few years and has been employed
in the manufacturing of several applications such as radio frequency identification
(RFID) tags and thin film transistor (TFT) displays. Mainly because of its simpler
fabrication process and low costs. Recently scientists have developed what is called
artificial skin which mainly relies on organic polymer materials and organic devices
which is OTFT. Due to its high flexibility engineers have been able to develop large
area sensors array in the form of what might be a robot’s skin. This skin would be
able to detect tactile forces and temperature as well as giving the robots the ability
to manipulate objects and physically interact with the surrounding environment.
This could also be promising in the field of medicine to people who have lost limbs
as this new technology could provide some prosthetic limbs. It also could help in the
diagnoses of breast cancer and remotely monitoring patients’ vital signs.
Touch sensing is the ability to detect the force of contact between an object and the
sensing area at a defined point on this object and on the sensor. While tactile sensing is
the ability to detect the mechanical forces directly perpendicular to the surface of the
sensing area. Applications for sensor arrays are not present only in the robotics field
but also in medical fields such as breast manipulation for breast cancer diagnoses and
for monitoring patients’ status. Also in the automotive industry it’s used in defining
tire patterns to enhance tire manufacturing for racing cars and in car seats to monitor
the driver’s comfort and status in order to decrease the probability of car crashes.
There are different technologies available for the development of tactile sensors such as
optical [1], capacitive [2], resistive [3] and micro electro mechanical systems (MEMS)
[4] technologies. Each suffers from a limitation, for example capacitive sensors are
95
very sensitive to any external noise source, optical sensors are highly sensitive to the
deformation of the source as it would cause a change in the light orientation receive
by the optical receiver and last but not least in resistive technologies which mainly
relies on rubber, the rubbery materials get deformed over time with constant usage.
10.2 General Description of the System
These piezoresistive materials are polymeric materials, which are mechanically flexible
and could get tailored to any surface, such a tactile skin would be very thin because
it’s fabricated on a plastic substrate by deposition of thin films. This artificial smart
skin would incorporate its addressing electronics which is designed using flexible
OTFT in this way the number of the interfacing terminals would be decreased to two
terminals, one for the supply voltage while the other is for the output data and the
data would be serially sent to the read out interface. the system under investigation
would send the output signal in the form of an oscillating signal, the frequency of
oscillation of this signal varies with the variation of the applied pressure on the
addressed sensor cell and this would greatly decrease the effect of any external noise
source more than if the output was sent in the form of just a voltage level. In order
to proceed with specifications of the finger-tip sensors array we should first gather
the specifications of a human’s tactile sensors. These data are gathered from [1-9]
and are presented in Table 10.1.
Table 10.1 Specification of a human’s finger-tip

tactile sensors
Frequency Response 0-400 Hz
Response Range 0-100 g/mm2
Sensitivity 0.2 g/mm2
Spatial Resolution 1.8 mm
10.3 Operation Mechanism
The sensor arrays considered in this paper are fabricated using a piezoresistive
material. Piezoresistive materials are materials which exhibit a change in its resistivity
upon an application of a mechanical stress on its surface. This phenomenon is called
piezoresistivity. It has been found that the contact resistance could be described by
the following equation [10]:
96
Flexible Sensor Array for a Robotic Fingertip Using Organic Thin Film
Transistors (OTFT) with Minimum Interconnects and Improved Noise Tolerance
R
Rc t K (10.1)
F
Where Rc is the resistivity of the material and F is the stress force applied while K
is function of the roughness and elasticity of the material [10]. A gauge factor to
characterise the sensitivity of the piezoresistive material to the applied stress force
has been reported [10] which could be described using the following equation:
dSc 1
GFc t (10.2)
dF RK
Where Sc is the electrical conductance of the contact and F is the applied force. It
is shown by the above equation that the material is sensitive to the variation of the
applied stress forces and the lower the material resistivity R (rho) and the roughness
and elastic properties K the higher the sensitivity to such forces.
10.4 Robotic Finger Tip Specifications

In order to start working on the design of the electronic blocks of the system, the
specifications needed for this system to function efficiently for its intended application
need to be set. Based on the criteria found in [6], the specification of the robotic finger
tip’s artificial skin was set, and is found in Table 10.2.
Table 10.2 Robotic fingertip artificial skin specifications

Spatial Resolution 1–2 mm2
Sensitivity 0.01-10 N
Frequency 100 Hz - 10 kHz
Area 20 s 20 mm2
10.5 System Design
10.5.1 OTFT Devices
All the circuits were designed using only a positive channel metal oxide semiconductor
(PMOS) devices as in contrast to their silicon candidates OTFT exhibit high mobility
97
in P-type than in N-type [11]. Also, design techniques for organic circuits that were
presented in [12] were taken into consideration when implementing the circuits. OTFT
with holes’ mobility values up to 15 cm2/V.s were reported [13], therefore, devices
used in this paper are of holes mobility 2 cm2/V.s with on/off ratio 107, Vt = -2.5 V
and maximum drift velocity of 5 s 104 m/s.
10.5.2 Sensor Array
The sensor array under investigation which is presented in [10] consists of two
polyester sheets adhered together with an adhesive at the non sensing areas each sheet
has a deposited 25 Mm Ag-filled conducting polymer lines, upon adhering the two
sheets together they form a grid of lines crossing each other forming the sensor cells at
the point of contact. Such structures of these sensor arrays could be viewed in Figure
10.1(a) while Figure 10.1(b) shows the circuit model of the piezoresistive sensor [10].
The resistance of one sencel (sensor cell) is modelled with a variable resistance that
varies with application of any stress force on the sencel, while the capacitance is due
to the fact that there are two conductors overlapping over each other.
(a) (b)
Figure 10.1 Electric model of a 2 s2 matrix of sencels
10.5.3 Active Matrix Addressing Electronics
The sensor cells are addressed using the active matrix addressing technique, using two
decoders one that acts as a column driver and the other that acts as a row selector.
These two decoders are synchronised using two binary counters one that iterates
98
the select inputs of the column driver decoder having its last bit connected to the
clock input of the second counter which iterates the select inputs of the row selector
decoder. Figure 10.2(a) and (b) shows the output simulation of the primarily designed
decoder that exhibits glitches and the secondary improved one using OTFT devices
both operating at a 20 kHz. Figure 10.3 shows the output simulation of a 3-bit binary
counter using OTFT devices also operating at 20 kHz. It should be noted here that
unlike silicon devices, different paths delays in the 3-bit counter were very significant
even at a frequency of 20 kHz as it was in the order of 2 Ms.
10.5.4 Astable Multivibrator
A multivibrator is a circuit that oscillates between two states, if it’s an astable

multivibrator then it does not settle at any of the two states and keeps on oscillating.
An example of an astable multivibrator circuit is the ring oscillator circuit. The astable
multivibrator is the block responsible for converting our output signal from a voltage
level to a frequency modulated signal. It consists of two inverters connected with
a resistance and capacitance (RC) network. Figure 10.4 shows the configuration of
the multivibrator and its connection with the sensors array, the addressed cell in the
sensors array is the element responsible for modulating the frequency of the output
signal depending on the resistance of the addressed cell which is in turn modulated
by the applied mechanical force. Figure 10.5 shows the output simulation of the
output of the multivibrator running at 100 kHz designed the address of a sensor
cell, using OTFT. Figure 10.6 is the all the blocks integrated together to form the
whole system.
Figure 10.4 The multivibrator consists of a RC network and 2 inverters, while the
frequency modulation of the signal is achieved by the variations in the load of the
first inverter which is the sensor array
99
Figure 10.2 (a) Non-improved output (b) improved output
Figure 10.3 Simulation output of a 3-bit binary counter operating at 20 kHz

using OTFT
100
Figure 10.5 The oscillating output voltage of the astable multivibrator
Figure 10.6 System level design of the finger-tip artificial skin
10.6 Important Design Features

The multivibrator should be sensitive enough to the change in the resistance of
the addressed sensor cell to be able to modulate the frequency of the output signal
significantly with every incremental small change in the applied force. The last sensor
cell to be scanned should have a unique resistivity value so as the read out interface
can mark the end of the scanning frame and the beginning of a new one. Also the
read out interface should be able to mark the start and end of the scanning frame of
each element as it’s only reading the data out and not addressing the sensor cells, so a
time based algorithm to identify each cell should be employed because as mentioned
before the addressing electronics are on the same substrate as the sensor array, and
are not controlled by the read out interface as is usually done.
101
Conclusion
We investigated the design of addressing electronics for an array of sensors by

implementing the circuits for and simulating it on ORCAD Pspice®. Circuits were
implemented using an OTFT model, and the circuits showed good performance
when run at a frequency 20 kHz. OTFT are still in need of major development and
research in order to increase the charges mobility and thus increasing the operation
frequency.
References
1. J.L. Banks, Design and Control of an Anthropomorphic Robotic Finger with

Multi-point Tactile Sensation, Department of Electrical Engineering and
Computer Science, Massachusetts Institute of Technology, Boston, MA, USA,
2001. [MSc thesis]
2. L.K. Baxter, Capacitive Sensors: Design and Applications, IEEE Press,

Piscataway NJ, USA, 1997.
3. T. Someya, T. Sakurai and T. Saketani in the Proceedings of the IEEE

Electron Devices Meeting, 2005, Washington, DC, USA, p.445.
4. F. Jiang, Y. Tai, K. Walsh, T. Tsao, G. Lee and C. Ho in the Proceedings of the

IEEE Tenth Annual International Workshop on Micro Electro Mechanical
Systems - MEMS ‘97, Nagoya, Japan, 1997, p.465.
5. P. Coiffet, Robot Technology – Interaction with the Environment, Volume 2,

Prentice-Hall, Englewood Cliffs, NJ, USA, 1981.
6. Active Touch: the Mechanism of Recognition of Objects by Manipulation,

Ed., G. Gordon, Pergamon, Oxford, UK, 1987.
7. L. Heimer, The Human Brain and Spinal Cord, Springer-Verlag, New York,
NY, USA, 1983.
8. L.L. Langley, I.R. Telford and J.B. Christensen, Dynamic Anatomy and
Physiology: Functional Neuroanatomy and Dissection Guide, McGraw-Hill,
New York, NY, USA, 1974.
9. E.R. Kandel, J.H. Schwartz and T.M. Jessell, Principles of Neural Science, 4th
Edition, The McGraw-Hill Companies, Inc., New York, NY, USA, 2000.
102
10. T.V. Papakostas, J. Lima and M. Lowe in Proceedings of the IEEE Sensors
Meeting, 2002, Volume 2, p.1620.
11. Q. Wu, Zhang and Q. Qiu in Proceedings of the IEEE International

Symposium - Circuits and Systems (ISCAS 2006), 2006, p.1270.
12. C.D. Dimitrakopoulos and D.J. Mascaro, IBM Journal of Resaerch and
Development, 2001, 45,
13. J.N Tegin and J. Wikander, Industrial Robot, 2005, 32, 1, 64.
Further Reading
a) T. Someya, H. Kawaguchi and T. Sakurai in Proceedings of the IEEE

International Solid-State Circuits Conference (ISSCC 2004), San Francisco,
CA, USA, p.288.
b) R.S. Dahiya, and M. Valle, and G. Metta and L. Lorenzelli in Proceedings of

the MRS Fall Meeting, Boston, MA, USA, 2007, Volume 3, p.1.
c) C.M.A Ashruf, Sensors Review, 2002, 22, 4, 322.
d) R.S. Dahiya, M. Valle and G. Metta in Proceedings of PRIME 2007 - 4th

Conference on PhD Research on Microelectronics and Electronics, Istanbul,
Turkey, 2007, p.201.
e) T. Sekitani, Y. Noguchi, U. Zschieschang, H. Klauk and T. Someya,

Proceedings of the National Academy of Sciences, 2008, 105, 13,
f) R.D. Howe, Journal of Advanced Robotics, 2004, 8, 3, 245.
g) V.J. Lumelsky, M.S. Shur and S. Wagner, IEEE Sensors Journal, 2001, 1, 1.
h) R. Brederlow, S. Briole, H. Klauk, M. Halik, U. Zschieschang, G. Schmid,

J-M. Gorriz-Saez, C. Pacha, R. Thewes and W. Weber in Proceedings of the
IEEE Symposium on Computers and Communications, Kemer – Antalya,
Turkey, Session 21/TD: Organic and Nanoscale Technologies, Paper
No.21.6.
i) O. Kerpa, K. Weiss and H. Wörn in Proceedings of the 2003 IEEE/RSJ

International Conference on Intelligent Robots and Systems, Las Vegas, NV,
USA, 2003, Volume 1, p.1.
103
j) N. Wettels, D. Popovic and G.E. Loeb in the Proceedings of the 2nd BioMed -
Frontiers in Biomedical Devices Conference, Irvine, CA, USA, 2007, p.829.
k) P. Dario, R. Lcazzarini and R. Magni in Proceedings of the IEEE 7th

International Symposium on Micro Machine and Human Science, Nagouya,
Japan, 1996, p.91.
104
11
An Organic Thin Film Transistor Pixel
Circuit for Active-Matrix Organic Light
Emitting Diode Flat Panel Display
Mohamed M. Montasser and Darek Korzec
11.1 Introduction
Organic light emitting diode (OLED) displays have promising characteristics that
will make them the dominant technology in the display market in the future. These
characteristics are high efficiency, high contrast ratio, wide viewing angle and low
fabrication cost [1]. However, the challenges in the development of these displays
are the instability of the organic materials, as voltage fluctuations and performance
degradation may occur during the operation of the organic device.
The organic thin film transistor (OTFT) is a thin film transistor which uses an organic
material for its channel instead of a-Si:H or poly-Si. It is also known as an organic
field effect transistor (OFET). The main purpose of fabricating the OTFT was to
realise low cost, large area electronic products such as, high quality, large, flat panel
displays. The OTFT is a low cost fabrication, as the deposition temperature of the
organic materials is very low which allows use of inexpensive substrate materials such
as glass, plastic and foils. There is great interest in OTFT nowadays from researchers,
since the performance of the pentacene TFT has been improved so that it has become
close to the performance of the hydrogenated amorphous silicon, a-Si:H or even better
[2]. Although it became very attractive, it still has problems of instability such as the
threshold voltage shift, and mobility degradation. On the other hand, OLED also
has some limitations such as the formation of dark spots and the OLED luminance
degradation.
In this Chapter, an electronic solution for the instability conditions of the organic
devices is provided. The circuit is an example of the voltage programming technique
for the compensation of the threshold voltage variation and mobility degradation of
the OTFT and the OLED luminance degradation. The circuit is also simulated using
PSPICE (circuit simulation tool) to verify the results.
105
11.2 Pixel Circuits Designs
The pixel circuit is a main part in the OLED flat panel display; it is the circuit that
provides the OLED with sufficient current according to the data current or voltage.
The challenge in the pixel circuit design is to provide high quality picture and to
overcome the problems of the organic devices. Figure 11.1 shows the conventional
active matrix (AM-OLED) pixel circuit; M1 is a switch transistor, M2 is the driver
transistor and Cs is the storage capacitor. Although this pixel circuit has a built
in memory, it suffers from the unstable OTFT conditions such as the threshold
voltage variation and mobility degradation. Therefore, compensation methods
need to be added to the circuit in order to overcome the problems of the organic
transistors. In previous studies [3-5], an optical feedback technique was used in
order to compensate for the decrease of current caused by the instabilities of the
organic devices, however, this technique is inefficient as it uses an organic optical
sensor which adds another source of instability to the whole system. There are
several pixel driving methods that were investigated by previous studies [1, 2,
6]; they were divided between the current and the voltage driving methods. The
current programming scheme can overcome the problems of threshold variation
and mobility degradation of the OTFT however, the current programming method
needs very high addressing speed, also the constant current source is difficult to be
designed for controlling the small current levels. On the other hand, the voltage
driving scheme is very efficient in compensating for the threshold voltage variation
and the mobility degradation of the OTFT, but the voltage driving method become
slow when a large number of gray levels are demanded.
Figure 11.1 The conventional pixel circuit [6]. Reproduced with permission from
W.F. Aerts, S. Verlaak and P. Heremans, IEEE Transactions on Electron Devices,
2002, 49, 2124. ©2002, IEEE
106
An Organic Thin Film Transistor Pixel Circuit for Active-Matrix Organic Light
11.3 The Voltage Programming Pixel Circuit
The voltage programming pixel circuit is the circuit that uses the output voltage
(programming voltage) of the column driver to set the gate voltage of the driver
transistor. The pixel circuit shown in Figure 11.2 is an example of a voltage driven
pixel. This design was presented by Ashtiani and co-workers [1] and was based on
a-Si:H TFT. In this Chapter the same design is developed by using the OTFT for driving
this circuit and the system is converted into a pull-up network as the transistors used
in the design are p-type transistors. The design consists of five p-type OTFT, three
select lines, data line, power supply and an OLED. M1, M3, M4, M5 are switching
transistors, M2 is the driver transistor and C1 is the storage capacitor.
This design is compensating for the threshold voltage variation and the mobility
degradation of the OTFT, and also compensates for OLED luminance degradation.
It operates in three different states; pre-discharging state, compensation state and
driving state. During the pre-discharging period, SEL1 and SEL2 are low therefore
M1, M3 and M5 are ON. Therefore the gate of M2 is discharged to a voltage near to
the power supply VDD (negative supply) and stored in the storage capacitor C1. The
data voltage is chosen to be –VP + VOLEDI, where VP is the programming voltage, and
VOLEDI is the initial ON voltage of the OLED.
During the compensation period, SEL1 goes high and M1 is turned off, therefore C1
charges through M2 until the gate voltage of M2 reaches VOLED+VT2, where VT2 is
the threshold voltage of the driving transistor, and VOLED is the shifted ON voltage
of the OLED. Finally in the driving period, when SEL1 and SEL3 go low and SEL2
goes high, thus M1 and M4 are on. Then the capacitor voltage VC1 is applied to the
gate source of M2, and the current of the driver transistor is supplied to the OLED:
K
I2 (VT 2 VOLED VOLEDI VP VT 2 ) 2
2 (11.1)
K
I2 ($VOLED VP ) 2
2 (11.2)
where K is the trans-conductance and $VOLED is the shift in the OLED voltage.
From (11.2) we can find that the OLED current in independent on the threshold
voltage VT2, and at the same time it is increasing as the $VOLED increases over time.
The OLED current is also dependent on the programming voltage, so the current
range of the OLED is determined by taking a proper value for VP, thus this circuit is
a voltage programming circuit. On the other hand the sensitivity of the IOLED to the
$VOLED is defined as S, where:
107
(11.3)
(11.4)
From Equations (11.2) and (11.4)
(11.5)
From Equation (11.5) the value of the trans-conductance (K) could be calculated and
then the aspect-ratio (W/L) of the driver transistor M2 could be obtained.
OLED
SEL3
M5
VDATA
M4
CI
M2
M3
SEL3
SEL3 M1
VDD
Figure 11.2 The voltage programming circuit
Table 11.1 shows the design parameters of the design. Figure 11.3 shows the timing
diagram of the select signals and the programming voltage.
11.4 Simulation Results
The circuit was simulated using PSPICE to verify the operation of the pixel circuits.
The simulation was based on the following models for the OTFT and OLED.
108
Table 11.1 The design parameters of the voltage programming circuit

Parameter Value
(W/L)1 (μm) 400/5
(W/L)2 (μm) 400/5
(W/L)3 (μm) 100/5
(W/L)4 (μm) 50/5
(W/L)5 (μm) 100/5
C1 (pF) 5
Vsel1 (V) -15 – 15
Vsel2 (V) -15 – 15
Vsel3 (V) -15 – 15
VOLEDI (V) 4
Figure 11.3 The timing diagram of the select signals and the input voltage
109
11.4.1 OTFT model
Since the OTFT is a special type of field effect transistor, then it can be modelled
using a metal oxide semiconductor field effect transistor (MOSFET) model but by
changing the values of some parameters in order to achieve the DC response and to
have the IV curves of the OTFT. In this Chapter the model is taken from [2], this
model is for p-type pentacene transistors. In previous literature, it was found that the
field effect mobility of holes in pentacene is exceeding 1 cm2/V.s, but this model is
based on hole mobility of 0.5 cm2/V.s for practical results [2]. The threshold voltage
is –2.5 V, the maximum drift velocity is 5 x 104 m/s with an on/off ratio of 107. The
dielectric thickness is 0.4 μm, the gate-source and gate-drain overlap capacitance
are 124 pF and the mobility degradation factor is 0.07 V-1. Figure 11.5 shows the IV
characteristics of the OTFT.
11.4.2 OLED model
Figure 11.4 shows the OLED model used in this Chapter. The model consists of a
series resistance and a diode parallel with a capacitor. The capacitor models the total
capacitance of the layers, the series resistance models the total resistance of the device
and the diode models the rectifying nature of the OLED, the model is based on the
model used in [6].
11.4.3 The results of the voltage programming circuit
A set of conditions were used for testing the voltage programming circuit. Figure 11.6
shows the time response of the OLED current with OTFT threshold voltages of –2.5,
–1.5, and –3.5. As shown in the figures, there are slight changes in the OLED current
which will not affect the brightness of the image. The voltage programming circuit
also compensates for the mobility degradation as well as the current programming
circuit - Figure 11.7 shows the OLED current with respect to the mobility degradation.
Furthermore, due to the dependence of the OLED current on the change in the OLED
on voltage, the circuit compensates for the OLED degradation. Figure 11.8 shows
the OLED current with respect to the change in the OLED voltage. As shown in the
figures the OLED current increases by increasing the shift in the OLED voltage which
enhances the lifetime of the display.
110
R1
950
C1 D1
5p n=45.8
Figure 11.4 The OLED model
Figure 11.5 The IV curves of the OTFT
111
V T = -1.5 V V T = -2.5 V
V T = -3.5 V
Figure 11.6 The transient response of the OLED current with respect to the
threshold voltage variation for voltage programming circuit at VT = -2.5V (middle
curve), VT = -1.5V (top curve), VT = -3.5V (bottom curve)
Figure 11.7 The transient response of the OLED current with respect to the
mobility degradation for voltage programming circuit
112
I OLED after a higher

shift in the V OLED
I OLED after the shift

in the V OLED
Figure 11.8 The transient response of the OLED current after the shift in the
OLED voltage. As shown in the figure, the bottom curve is after the shift in the
OLED voltage and the top curve is after a higher shift in the OLED voltage
11.5 Conclusion
In conclusion, this Chapter is about designing a fully organic pixel circuit for AM-
OLED flat panel display. A fully organic means that the circuit consists of organic
transistors (OTFT) and an OLED. The advantage of having a fully organic pixel
circuit is the low cost of fabrication, easy to be fabricated on flexible substrates due
to low temperature fabrication, thus flexible displays are adoptable and this is beside
the high brightness, the great range of colors, the high contrast ratio and the wide
viewing angle of the OLED displays.
However, the organic devices are still unstable and their performance degrades
gradually with time. Therefore, a voltage programming pixel circuit was developed
using OTFT in order to overcome the problems of organic devices and have a fully
organic design. The design was studied and simulated using PSPICE. The design
showed an impressive response with respect to the degradation of the organic devices,
as it provides an electronic solution for these problems. The simulation proofs the
capability of the design in compensating for the threshold voltage variation and
mobility degradation of the OTFT. On the other hand, it compensates for the OLED
luminance degradation and increase the life time of the display.
113
References
1. S.J. Ashtiani, G.C. Reza and N. Arokia, Journal of Display Technology, 2007,
3, 36.
2. M.R. Powell, Integrated Feedback Circuit for Organic LED Display Driver,
Department of Electrical Engineering and Computer Science, Massachusetts
Institute of Technology, Boston, MA, USA, 2004. [MSc Thesis]
3. Y. He, H. Reiji and K. Jerzy, IEEE Transactions on Electron Devices, 2001, 48,
1322.
4. K.S. Lamba, An Integrated Circuit for Feedback Control and Compensation

of an Organic LED Display, Department of Electrical Engineering and
Computer Science, Massachusetts Institute of Technology, Boston, MA, USA,
2006. [MSc Thesis]
5. C-L. Lin and K-C. Liao in Proceedings of the IEEE Conference on Electron
Devices and Solid-State Circuits, IEEE, Taiwan, 2007, p.385.
6. W.F. Aerts, S. Verlaak and P. Heremans, IEEE Transactions on Electron Devices,

2002, 49, 2124.
7. H. Aziz, Z.D. Popovic, N-X. Hu, A-M. Hor and G. Xu, Science, 1999, 283,
1900.
8. G.R. Chaji, C. Ng, A. Nathan, A. Werner, J, Birnstock, O. Schneider and J.

Blochwitz-Nimroth, IEEE Electron Device Letters, 2007, 28, 1108.
9. A. Lin, A Silicon Current Sensing Amplifier and Organic Imager for an Optical
Feedback OLED Display, Massachusetts Institute of Technology, Boston,
MA, USA, 2006. [MSc Thesis]
10. P. Melpignano, A. Baron-Toaldo, V. Biondo, S.Priante, R. Zamboni, M.

Murgia, S. Caria, L. Gregoratti, A. Barinov and M. Kiskinova, Research
Highlights, 95-98.
11. M. Mizukami, N. Hiorhata, T.Iseki, K. Ohtawara, T. Tada, S. Yagyu, T. Abe,

T. Suzuki, Y. Fujisaki, Y, Inoue, S. Tokito and T. Kurita, IEEE Electron
Device Letters, 2006, 27, 249.
12. Ch. Pannemann, T. Diekmann and U. Hilleringmann in Proceedings of an

IEEE Conference on Microelectronics – ICM, Tunisia, 2004, p.76.
114
13. A. Shin, S.J. Hwang, S.W. Yu and M.Y. Sung, Journal of Computers, 2008, 3,
3, 1.
14. S.M. Sze, Semiconductor Devices: Physics and Technology, 2nd Edition, Wiley,
New York, NY, USA, 2001.
115
116
12
Intelligent Packaging for the Food
Industry
Salvatore Parisi
12.1 Introduction
So-called ‘intelligent packaging’, often confused with the better ‘active packaging’, is
singularly differentiated from the other fields of the manufacturing industry. The main
reason for this is the extraordinary growth of the related technology in recent times.
Consequently, there is the concrete possibility of high profits in the future depending
on the predictable request for ‘intelligent’ devices. First of all, some distinction between
the active and intelligent devices has to be made.
Both instruments, generically called ‘smart packaging’, are different from conventional
packages [1]. In detail, the requested function is the capacity to interact with the
product if the device is associated with the packaging. The particular type of interaction
- active mode or passive detection - is the real difference between the two solutions.
This interaction is dependent on the particular exigency of the asking subject with
concern to pharmaceutical companies and food and beverage industries [1]. The
aim of this Chapter is to show the explicit and unknown necessities of the food and
beverage industry.
Basically, the active packaging is able to interact with the inner atmosphere of the
package. The declared aim is the modification of packaged products and related
headspaces by means of antimicrobial and/or antioxidant substances. This alteration
tends to improve the shelf life and other important features (colour, smell, texture).
On the other hand, ‘intelligent packaging’ is designed to collect, store and communicate
particular information about the story of packaged products [1]. In other words,
some kind of external or internal instrument is connected to the package and becomes
able to:
1) Detect storage conditions (temperature, relative humidity) in function of the time

progression, or,
117
2) Make evident the quality decay of the packaged food, or,
3) Detect storage conditions and quality decrement at the same time, and
4) Store all the relevant information and/or modifications.
As a consequence, the previous situation may be expressed as the interaction between

the ‘Food and Package’ system [2] and the aware Consumer [3]. In effect, every food
company should be able to collect, satisfy and anticipate the exigencies of Consumers,
as requested by British Retail Consortium (BRC) and International Food Standard
(IFS) protocols. These requests are often in accord with existing Regulations with
concern to food safety. However, the necessity to foresee the needs of normal people
and sensible consumers is highly recommended because of the risk of expensive and
intricate class actions.
From a general viewpoint, the current ‘intelligent’ solutions can be subdivided in two
categories with concern to food and beverage applications.
The first group is related to all the devices – radio frequency identification (RFID)
tags above all - that are able to record and store important variations of quality and
functional features. In other words, the monitoring activity is linked to the durability
of food commodities and the good storage during all the shelf life. In general terms, the
storage temperature is one of the important parameters that should be monitored. Other
variables are the partial pressure of inner oxygen, the relative humidity, and so on.
The second category of ‘intelligent’ tools are those used to highlight imperceptible
anomalies concerning the storage. In effect, 90% or more of food complaints are
linked to the incorrect storage. So, the monitoring activity should be dedicated to
the measure of storage conditions and Remaining Shelf Life (RSL). This problem is
surely evident when Japanese or South-Korean Retailers import notable quantities
of perishable foods under strict storage conditions (temperature: < –20 °C) because
of the known degradability [4]. It should to be noted that these indicators are easily
understandable by Retailers and normal Consumers without specific training.
The second category of ‘intelligent’ devices can be easily divided in to four subclasses
with concern to the particular use [5]:
a) Temperature indicators
b) Time-temperature indicators (TTI)
c) Leakage indicators
d) Freshness indicators
118
Intelligent Packaging for the Food Industry
These instruments should be:
1) Easily activated
2) Able to exhibit measurable and reproducible variations that are linked to the
remaining quality of foods
3) Absolutely irreversible
In recent times, the world of smart packaging seems to have changed, in comparison
with traditional packaging, because of the enormous contributions of RFID and
other PC-based technologies [1]. Actually, this impetuous evolution is mainly related
to the sub-field of intelligent applications. In effect, new types of microchips have
opened up new possibilities for commercial electronics and wireless technologies. New
approaches have also been used to upgrade or explore other applications for non-food
applications. At the same time, a quantity of possible connections between IT and
other aspects of the social life has been tempted with different results. One of these
attempts has been the development of complicated ‘multi-agent’ networks based on a
number of programs with very low processing capacity. However, the most promising
opportunities are in the food and beverage field, according to Food Retailers [1]. The
declared aim is the reduction of ‘wastage’ by means of the improvement of supply
chains. With regard to logistics, all foodstuffs may be distributed even more quickly
and cost effectively [1]. As a consequence, intelligent packaging sales are predicted to
grow four-fold to reach more than $80 million by 2010 [1] because of the growing
power of retail chains in emerging markets (Asia, Latin America). However, the
incumbent economic crisis and the consequent doubts about the fast expansion of
supermarket chains in emerging countries like China do not allow confirmation of
these predictions, particularly with concern to RFID tags.
For these reasons, a sort of premise about the present situation of Intelligent Packaging
should be necessary.
12.2 RFID and Packaging Connection - The Age of Connectivity
Intelligent monitoring is able to give some information about the presumptive

conditions of packaged foods until the expiration date. Clearly, the most critical
control point (or CCP, in Hazard Analysis and Critical Control Points language
(HACCP)) is represented by refrigerated transports. Thus, the so-called TTI have
been created and continually updated. However, several observers have highlighted
that improvements in supply chain management and innovations in food processing
may reduce or eliminate the necessity of smart packages [1]. This risk has been
119
denied after new developments in RFID technologies; moreover, food retailers tend
to encourage suppliers to boost the efficiency of their stores [1]. In effect, the supply
chain should be seen as a series of intermediate steps from manufacturing to final
distribution and catering services. These steps are generally continuous and carried
out by different operators, but the constant factor is the identity of the product (lot,
batch, expiry date, sell-by-date). Probably, this level of identification is difficult to
enforce on a massive scale.
Anyway, the key factor for the implementation of intelligent packages and RFID
tags is still cost. This assertion was the best argument for use of RFID detractors
until recently. Nowadays, the global lack of liquid assets imposes shared strategies
for the retailers and producers. Otherwise, RFID tags may have serious difficulties
in the food market because of their relatively high cost. Probably, new ‘multi-
factor tags’ (a combination of chemicals, inks and coatings with RFID) may help
to obtain the desired advantages at low cost [1]. With regards to existing devices,
the implementation of new IT systems should correspond to 20-30% of the total
cost [1], while normal tags do not exceed 40 Eurocents (minimum: 5 Eurocents).
On the other hand, the impetuous growth of RFID tags is not comparable with
other Smart applications.
From a technical viewpoint, the RFID is based on three components compressed in

an 1 cm2 adhesive tag:
1) A transponder;
2) An ID code which contains thousands of bits of potential information;
3) A mini-antenna.
In detail, the transponder is a sort of radio transmitter-receiver activated for

transmission by reception of a predetermined signal.
With regard to shapes and dimensions, RFID tags may be produced as adhesive
labels, bottoms or micro-ampules. The final target is the food or pharmaceutical
product, but some in vivo applications have been realised. Anyway, the difference
between different RFID applications is related to the ‘active’ or ‘passive’ role of
tags with regard to the hardware and software tracing system. In effect, ‘active’ tags
are able to detect and record temperature, relative humidity and abnormal shocks
[6]. Successively, these data are transmitted automatically because of the presence
of low batteries or solar micro-cells [7]. In addition, the reader/receiver distance
can be extended to 30 metres (Figure 12.1). These features explain the high costs
($100 per tag).
120
Figure 12.1 Active RFID tags contain small batteries (or solar microcells).
As a consequence, they are able to ‘alert’ receiving and tracing systems
(distance up to 30 m)
On the other hand, ‘passive’ - or battery assisted passive (BAP) - RFID tags are provided
with very low cost batteries (cost: $5) or completely inactive (up to 40 Eurocents). The
difference is the impossibility of activating the reading/receiving system (distance: up
to 10 cm; frequency: 1 Hz, resolution: 100 μm). This apparent limitation is the key of
the success of RFID passive tags (Figure 12.2). Other advantages are:
1) Virtual absence of problems about reading angles.
2) Easy reading during movement.
3) Unlimited durability, except for massive crashes.
4) Possibility of transmission on 865 and 868 MHz (EU, US, etc.).
5) Practical codification, reading and writing standards (Electronic Product Code

(EPC), EU).
6) Possibility of tracing the position and the whole history of food pallets (for ‘n’ units
with 96 bit-RFID tags, the whole pallet represents ‘n s 96’ bits of information).
Other important applications are related to the problem of damage during transport.
It is known that deliveries are critical not only for the storage temperatures but also
121
Figure 12.2 Passive RFID tags are not able to activate the reading/receiving system
(distance: up to 10 cm; frequency: 1 Hz, Resolution; 100 μm). On the other hand,
cost are very low
for possible mechanical shocks [6]. The total cost of claims may be up to 10% of
delivered commodities. So, some operators would like to employ RFID tags with
integrated accelerometers to monitor the shipment step.
With concern to the management of warehouses the so-called ‘First In, First Out’
strategy (FIFO) may be replaced with more practical procedures that are based
on RSL [8]. One of these methods has been already proposed some year ago [7]
with the Products Released on Properties Obviously Selected for Additional Life
(PROPOSAL).
The previously mentioned advantages are not ‘the end of the story’ about RFID tags.
In effect, there are two points that should be considered as inconveniences. Firstly,
food companies are reluctant to employ this technology because of the possible
substitution of RFID software with newer products. So, RFID technology should be
able to manage the information by means of a single writing/receiving protocol that
may be recognised by existing and newer software agents. In addition, this exigency
is strictly linked to the possibility of reading errors and/or data cancellations.
The second problem is related to possible attacks to RFID tags by computer hackers.
So, it is necessary that the electronic devices are provided with protection. This
122
argument is really important with concern to traceability requirements and BRC/IFS

standards about the preservation of food identity (GMO-free or melanin-free products,
etc.). It should be noted that every computer hacker might attack RFID tags in wireless
mode by means of normal mobile networks. This risk can be very high in case of
regional or local RFID networks, managed by private companies. The age of total
connectivity allows this type of actions, thus the problem has to be resolved from
the IT point of view.
This section should not be concluded without some word about new intelligent tracking
solutions, also called nanobarcodes and deoxyribonucleic acid (DNA) codes. The first
technology [9] is related to the possibility of producing particular barcodes on a nano-
scale (100 to 1,000 nm). These codes can be easily read by means of spectrophotometers
and normal scanners. DNA codes, on the other hand, are simply constituted of
deoxyribonucleic acid fragments that may be inserted into labels, traditional packages
and glass materials. This system allows storage of unlimited quantities of information
because of the presence of a key code inserted into the DNA sequence. Clearly, the
alteration of similar codes is not workable with simple tools. So, the only possibility of
sabotage is the physical destruction - by abrasion - of the molecular sequence.
12.3 TTI and Other Solutions - The Viewpoint of Food Industries
The second category of intelligent devices is approximately subdivided in four sub-

classes with concern to the particular information. In detail, the group is often confused
with the so-called time-temperature indicators or TTI. In recent times, researchers
have studied possible applications and real benefits of TTI in terms of food safety
and hygiene [10]. At the same time, the detractors of intelligent devices have always
preferred to attack the whole category targeting TTI.
First of all, the TTI acronym has not to be attributed to simple temperature
indicators. These instruments are exclusively able to record excessive values of storage
temperatures in an irreversible way [3]. The TTI evolution is weightier because of
the possibility of correlating thermal values at the period n which the variations have
been recorded in. The visual result can be recognised as the average sum of all thermal
variations during the whole shelf life, or RSL. In other words, TTI record storage
temperatures and are able to add cumulatively their fluctuations by integration. It has
to be noted that thermal conditions are related to the Food and Packaging integrated
system. As a consequence, all conclusions about RSL are reliable assuming that food
degradation is comparable to TTI reactions [11].
In general, RSL is displayed in a colorimetric way. The chromatic alteration is always

associated to the evolution of the general quality of products, assuming that this is a
123
synergetic sum of n factors [12]. In effect, the main argument against the use of TTI
is the reliable correlation between three factors:
1) The chromatic decay of TTI devices.
2) The most degrading reaction - or chain of reactions - in foods.
3) The storage temperature at the heart of products.
From a technical viewpoint, there are three main types of TTI:
1) ‘Bull’s Eye’ solutions (Figure 12.3). The label shows a circular zone filled with
diacetylenic monomers that are ready to initiate long polymerisation chains. The
process, which is temperature-dependent, allows the chromatic variation of coloured
circles to darker tints [10]. This variation is appreciable with or without optical
scanners and may be correlated to different sensitivities. In addition, the activation
has to be started exactly when foods are packaged. So, Bull’s Eye indicators are simply
frozen until the final use. Normally, the main targets are fresh and frozen products.
2) Chromatographic solutions (Figure 12.4). These instruments tend to reproduce

qualitative columns of chemical analysis. The aim is to induce the progression of
coloured solutions - fat substances - throughout transparent tubes or columns. The
progression can be intended as time and temperature dependent. However, food
operators have some doubt about the correlation between the viscosity of fluid
substances and the behaviour of food fats.
3) Enzymic indicators (Figure 12.5). The synthetic mixture is composed of a lipidic

substrate, a pH indicator and a specific lipase [5] that catalyses the hydrolysis of
fats into glycerol and fatty acids. The colour variation is extremely simple, reliable
and immediately interpretable because of different coloured windows.
Nowadays, the main advantages of TTI are related to:
1) The easy use and reading by normal consumers.
2) The possibility of just-in-time (JIT) and shortest remaining shelf life (SRSL)
strategies instead of FIFO.
3) The objective compliance with Codex Alimentarius, Step 9, Principle 4 (every

CCP has to be continually inspected) and related BRC and IFS Protocols.
4) The observed trend in favour of minimally processed and assembled foods.
124
Figure 3 Bull’s Eye indicators show the presumptive degradation in a

colorimetric way. The darkening of the circular zone is appreciable with and
without optical scanners
Figure 12.4 ‘Chromatographic’ indicators show the progression of coloured

substances throughout transparent tubes. This shift can be correlated with the
decrease of remaining shelf life
125
Figure 12.5 Enzymic solutions contain a synthetic mixture. Lipids are demolished
by a specific lipase. The acidification is displayed by normal pH indicators
The last point is very evident in the EU where active packages, in direct contact with
food atmospheres, are considered extraneous or incompatible with fresh foods [1].
In contrast, Japanese consumers tend to prefer active packaging while RFID tags
sales are not comparable.
On the other hand, there are three objections against the use of TTI. First of all, every
monitoring instrument should be adapted to inform the consumer about the intrinsic
quality of packaged foods. From the hygienic viewpoint, this quality is related to
the reduction or the complete elimination of microbiological, chemical and physical
risks, according to Codex Alimentarius principles. However, it is known that the
so-called risk-analysis may give different conclusions, depending on the particular
product and the process [11]. Consequently, TTI should be realised on the basis of
much information. The associated hazard is the design of standardised indicators
with very different results, product by product. This situation is clearly an important
inconvenience because different risks have different weights.
The second argument is emerging by the behaviour of some food companies. Actually,
there is the jeopardised tendency to reduce shelf life values to the shortest term in
relation to perishable foods and dairy products. Manufacturers prefer this strategy
because of the consumeristic approach. Consequently, TTI sales could diminish in
the future [1]. However, the role of these instruments from the hygienic point of view
should be considered. In detail, the safety of foods is strictly dependent on the correct
storage [13]. In addition, all edible products are subjected to some type of alteration
according to the 1st Law of Food Degradation [11]. So, every official verdict or
126
analysis about unacceptable products (clear degradation, microbial spreading, etc.)

should be considered on the basis of the related thermal history.
Other intelligent indicators are designed to perceive the presence of undesired

oxygen and/or carbon dioxide into modified atmosphere packaging (MAP) packages
[14]. These devices are named leakage indicators [3]. The basic idea is the insertion
of Redox indicators (methylene blue, and so on) or acid/ base systems and the
consequent revelation of active components. It has to be noted that the most
important failure of these devices is strictly related to the microbial spoilage and
consequent variations in the oxygen/carbon dioxide ratio. This interference has to
be expected before considering eventual failures in the MAP process. In addition,
the correct storage of these indicators is generally fixed at 5-8 °C in order to prevent
anticipated reactions [5].
Finally, a particular mention should be done about ‘freshness’ indicators. Actually,

these devices are able to detect the production and consequent accumulation of gaseous
substances by microbial spoilage. These detectable targets are hydrogen sulfide (by
reaction on myoglobin saturated substrates), ammonia, tri-methylamine N-oxide [15],
and acetic acid [3]. In relation to consumeristic approaches, these systems are considered
extraneous or incompatible with fresh foods, like active devices. Consequently, related
sales are not good in the EU in respect of other solutions [1, 3].
12.4 New Proposals - The Consumer’s Viewpoint
The previous paragraphs have displayed the current offerings for intelligent packaging.
Actually, these offers are well known, however food companies would like to make
use of slightly different devices. Basically, the final consumer and the manufacturer
cannot be well qualified about smart or intelligent packaging. On the other hand, the
opinion of consumers (and food companies) is strictly necessary in order to design
and implement new solutions. The explicit confirmation comes from BRC Global
Standard Food, Version 5, point 3.4, about the necessity to determine requests and
expectations of customers.
In a general way, recent market research tends to highlight the opinion that large
groups of normal people (age: 30-65) are not well disposed towards ‘assembled’
foods. The European situation has been discussed with concern over active packages.
A particular case study has been verified in Italy some year ago. After the discovery of
a food scandal, the main networks have proposed radio and TV commercials related
to different brands or food types. These messages were to assure the consumer about
the substantial difference between farm-made and ‘assembled’ foods.
127
Figure 12.6 The visible degradation of ‘Replica’ tags ‘mimes’ exclusively the
behaviour of packaged foods, according to the principle: ‘One food, one replica;
two foods, two replicas’
On this basis, food technologists can surely help with the development of new intelligent
devices that may be largely appreciated. These replica indicators (Figure 12.6) may
be realised with different substances that should mime the composition of packaged
foods (fermentable sugars, and so on). In detail, a hypothetic multifunctional indicator
may contain an edible substrate composed of:
a) Food-grade rennet casein and agar agar (as blocking agent).
b) Simple sugars, lactose or biodegradable polysaccharides (starch and methyl-

cellulose), able to turn brown because of simple enzymic reactions [16-19].
c) Unsaturated triglycerides or fat acids (oleic and ricinoleic acids); food-grade oils
(soya, sunflower).
d) Carotenoids and/or riboflavine, very susceptible to sunlight [3, 20, 21].
e) Gelatine (or similar colloids) as a co-indicator of degradation because of its

hydrophilicity [22].
Similar mixtures have already been devised for different purposes [23]. The following
features have to be highlighted:
128
1) Visible degradation of a biodegradable matrix that is able to ‘mime’ exclusively

the behaviour of packaged foods, according to the principle: ‘One food, one
replica; two foods, two replicas’.
2) Predetermined composition of biodegradable mixtures.
3) Fixed composition of tag atmospheres.
4) Possibility of acid-base or Redox indicators and specific enzymes (lipase, amylase).

In particular, Redox indicators can show immediately dangers in terms of
favourable conditions for the spoilage of pathogen bacteria (Escherichia coli,
Listeria monocytogenes), if they are present in the real food [14].
5) Reliability of results, on the basis of correlations between the decay of packaged

foods and the visible degradation of like-food mixtures.
In relation to the necessity of different indicators for different products, it should be

highlighted that every food has different pH, Redox potential (Eh) and water activity
(Aw). These parameters depend on the different composition [11] and other factors
(provenence, processing, presence of ‘wild’ cultures, etc.). Consequently, pathogenic
contaminations are possible in particular conditions only [14, 24, 25]. So, it is strictly
necessary to develop a good replica for every food type.
New approaches may be realised considering the biodegradable and ‘replicative’

nature of these indicators. An interesting development could be the insertion of
inoffensive bacteria with the final goal to produce evident and reproducible reactions.
These bacteria could be constituted of Lactobacillus casei, Lactobacillus bifidus or
Lactobacillus bulgaricus cultures, because of the large applications in yoghurts. The
previously-mentioned agents are capable of proteolytic and fermentative reactions
producing acid substances (optimal temperature: 40 °C, with detectable activity at 10
°C). So, the related spoilage would be easily displayed by means of normal acid-base
indicators and should demonstrate the real situation of a substrate that is similar to
the packaged food.
For the same reason, the insertion of well known food yeasts and moulds is possible.
Two examples are:
a) Penicillium roquefortii (inserted in blue and green cheeses). This mould is able to
spread at 12-13 °C (optimal temperature: 25-30 °C) in the absence of light and
produces grey mycelia [26].
b) Brevibacterium linens (present in ‘wet crust’ cheeses). This yeast is well known
because of its ability to produce red pigments.
129
However, this solution could not be appreciated by normal consumers because of the
hypothetical microbial dissemination – by breakage - in the environment. Naturally,
the consumer should be informed about the absence of real risks associated to
Lactobacillaceae or moulds, but the acceptance of a similar device is not sure. Existing
regulations are not ready to accept the authorised release of ‘living’ indicators. In
addition, there are two risks to be considered: (1) the eventuality of mutant bacteria and
(2) the release of powerful bacteriophages. For these reasons, ‘living’ indicators may be
proposed as monitoring instruments for manufacturers and official inspectors only.
12.5 Food Companies Under Attack - Sabotage and Class Actions
Another difficulty is represented by possible hostile actions against food companies

and retailers. Basically, the related risk is double because all intelligent systems can be
destroyed, ripped out, damaged and/or reprogrammed (RFID tags). As a consequence,
every legal action against justified Class Actions (degradated foods and poor storage)
may be very difficult.
RFID tags are vulnerable to PC attacks and mechanical damage. For these reasons, the
matter has to be resolved on the IT ground. Actually, the thorny subject is the defence
of food companies against the possible accusation of selling food and beverages without
related control tags. Because of the difficulty of producing films (cans, bottles, and so on)
with integrated intelligent devices, the best solution should be the creation of removable
‘multi-coupon’ tags. The basic idea is the possibility to trace out the thermal history of food
commodities, step-by-step, allowing Warehouse managers to pull out (and refrigerate) one
of the n tags of a packaged product or pallet. Thus, three objectives can be reached:
1) Evidence and record of the quality of packaged products (pallets), step-by-step.
2) Storage of traceability data, pallet by pallet, in case of RFID tags.
3) Evidence of the ‘tracking’ coupon, product by product, in case intelligent tags should
be partially or totally destroyed.
In addition, it should be noted that the subdivision of intelligent tags in n independent

coupons allows the option to store the totality of remaining devices near the last
warehouse/market, lot by lot.
12.6 Conclusions
The aim of this Chapter has been to demonstrate that intelligent packaging can be very
useful for all the components of food chains. Producers, intermediate distributors, retailers
130
have sufficient reasons to find a profitable or practical use for the previously mentioned
systems. However, supply chains must work in strict association with the packaging
industry to work out shared solutions. In effect, there are several ‘implicit’ proposals
that must be discussed and satisfied. Some of these suggestions have been described here
without too technical specifications. According to food producers, the realisation of these
or similar ideas may help the growth of the whole manufacturing sector.
References
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2. S. Parisi, Alterazioni in Imballaggi Metallici Termicamente Processati, Gulotta

Press, Palermo, Italy, 2004, p.9.
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Agro-Alimentari’, Edizione 2002, Lezioni di Food Packaging, Agosto, State
University of Milan, Milan, Italy, 2002, p.1-5 and 174-179. http://www.
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Asia’s Emerging Markets, Atradius Credit Insurance NV and The Economist
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and B. De Meuleunaer, Food Additives and Contaminants, 2002, 19,
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Nazionale Microbiologia degli Alimenti Conservati in Stato di Refrigerazione,
Bologna, Italy, 2005, p.93.
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Zandvoort, Food Additives and Contaminants, 2005, 22, 10, 975.
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Summo, Italian Journal of Food Science, 2007, Special Issue, p.400.
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Lanza and C. Nicolosi Asmundo, Italian Journal of Food Science, 2004,
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19. P. Pittia, G. Sacchetti and D. Mastrocola, Italian Journal of Food Science,

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Italian Journal of Food Science, 2007, Special Issue, p.260.
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p.129.
132
A
bbreviations for Electronics
3D Three dimensional
ACN Acrylonitrile
AFM Atomic force microscope
AM Active matrix
APS Ammonium persulfate
a-Si:H Hydrogenated amorphous silicon
B&W Black and white
BAP Battery assisted passive
BRC British Retail Consortium
CCP Critical control point
CMOS Complementary metal-oxide semi-conductor
CNT Carbon nanotube(s)
CO2 Carbon dioxide
CT Computed tomography
DBSA Dodecyl benzenesulfonic acid
DC Direct current
DIN Deutsches Institut für Normung eV - the German Institute for
Standardisation
DMSO Dimethyl sulfoxide
DNA Deoxyribonucleic acid
DSC Differential scanning calorimetry
EPC Electronic Product Code
EU European Union
FIFO ‘First In, First Out’ strategy
FT-IR Fourier transform infrared spectra/spectroscopy
GMO Genetically-modified organism
GO Gate overlap
133
HACPP Hazard Analysis and Critical Control Points language

HALS Hindered amine light stabilisers
HV High viscosity
ID Identification
IFS International Food Standard
IKV German Plastics Processing Institute
IT Information technology
ITO Indium tin oxide
IV I stands for current, V stands for voltage
JIT Just-in-time
KBr Potassium bromide
L/D Length to diameter ratio
LCD Liquid crystal display(s)
LED Light emitting diode
LV Low viscosity
MAP Modified atmosphere packaging
MEMS Micro Electro Mechanical Systems
MOSFET Metal oxide semiconductor field effect transistor
MWNT Multiwall carbon nanotubes
N2 Nitrogen
NaDBS Sodium dodecylbenzenesulfonate
NBR Poly(butadiene-co-acrylonitrile)
NV-RAM Non volatile random access memory
O2 Oxygen
OE Organic electronics
OE-A Organic Electronics Association
OFET Organic field-effect transistor
OLED Organic light-emitting diode(s)
OPV Organic photovoltaic cells
OTFT Organic thin film transistor(s)
PA6 Polyamide 6
PANI Polyaniline
PAni.DBSA Polyaniline dodecylbenzenesulfonate
PC Personal computer
134
Abbreviations for Electronics
PE Polyethylene
PEDOT Poly(3,4-ethylenediocythiophene)
PET Polyethylene terephalate
PET Polyethylene terephthalate
PFBT Pentafluorobenzenethiol
PMOS Positive channel metal oxide semiconductor
PPS Polyphenylene sulfide
PROPOSAL Properties Obviously Selected for Additional Life
PSPICE Circuit simulation tool
PSS Poly(styrenesulfonate)
PVA Polyvinyl alcohol
PVP Poly(4-vinylphenol)
R&D Research and Development
RC Resistance and capacitance
RF Radio-frequency
RFID Radio frequency identification
RH Relative humidity
RMS Root-mean-square
ROLLED Roll-to-roll manufacturing technology
rpm Revolutions per minute
RSL Remaining shelf life
S/D Source/drain
SDS Sodium dodecyl sulfate
Sn/Pb Tin/lead
SnAgCu Tin silver copper
SRSL Shortest remaining shelf life
SWNT Single wall carbon nanotube(s)
TEM Transmission electron microscopy
TFT Thin film transistors
Tg Glass transition temperature
TGA Thermogravimetric analysis
TIPS 6,13-Bis (triisopropylsilylethynyl)
TTI Time-temperature indicator(s)
UV Ultraviolet
135
UV-Vis Ultraviolet-visible spectroscopy

VDMA German Engineering Foundation
WLI White light interferometer
WORM Write once, read many
136
I
ndex
A
Active matrix addressing technique 98
Active matrix organic light emitting diode 106
Flat panel display 105
Active packages 117, 126
Assembled foods 127
Astable multivibrator 99
Atomic force microscope images 14
Automotive engineering 43
B
Bacteria 129
Lactobacillus bifidus 129
Lactobacillus bulgaricus 129
Lactobacillus casei 129
Ball milling process 25
Beer-Lambert law 58, 63
Blends preparation 77
BRC global standard food 127
Bull’s eye indicators 125
C
Cable jacketing 63
Carbon nanotube
Characterisation 37
Nanotube inks 40, 67, 92
Characterisation of nitrile-butadiene rubber - polyaniline - dodecylbenzenesulfonate
blends 78
Chromatographic indicators 125
Codex alimentarius 124, 126
Communications engineering 43
Complementary metal-oxide-semiconductor
Circuits 4
Transistors 9
Conductivity, four-probe 73
137
Conductor paths, injection moulding of 52

Copper indium gallium selenide ink 88
Critical control point 119, 124
D
Differential scanning calorimeter 78
Thermal analysis 81
Direct printing 13
Gravure printing 13, 22-24
Imprinting 13
Ink jet printing 13, 31-34
Laser assisted patterning 13
Microcontact printing 13
Screen printing 13, 23, 25
Dye sensitisation 93
E
Edge waviness 15
Electrical conductivity
Determination of 81
Four-probe technique 81
Electrical engineering 43
Electrodes, printed 1, 18, 31
Electromagnetic shielding 45, 51-52, 54
Electronic applications, injection mouldable 43
Electrospinning 31-32, 40-41
Enzymic indicators 124
Exfoliation of single wall carbon nanotubes 69
F
Fabric construction 92
Fibre processing 92
Sensors, finger-tip 96
First in, first out strategy 122
First Law of Food Degradation 126
Food and package system 118
Food industry 117, 123
Packaging 117
Food moulds 129
Penicillium roquefortii 129
Food yeasts 129
Brevibacterium linens 129
Fourier Transform-infrared
Spectra 70, 74
Spectra of polyaniline 71
138
Index
Spectra of polyaniline - surfactant 71

Spectra of polyaniline - surfactant-single walled nanotubes 71
Spectrometer 78, 80
H
Hazard analysis and critical control points language 119
Hindered amine light stabilisers 58-59
I
Infrared Excalibur instrument 70
Ink jet printing techniques 31
Piezoelectric ink jet printing 31, 41
Thermal ink jet printing 31
Injection moulding 45, 49, 54
Intelligent devices 117-118
Freshness indicators 118, 127
Leakage indicators 118
Temperature indicators 118
Time-temperature indicators 118, 123-124
Bull’s eye solutions 124
Chromatographic solutions 124
Enzymic solutions 126
Intelligent monitoring 119
Intelligent packaging 117, 127, 130
K
Knitted fabrics laddering of 91
Kruss Easy Drop 36
L
Lactobacillaceae 130
M
Material warming 50
Melapur 200 65-66
Metal oxide semiconductor field effect transistor 110
Microelectromechanical systems 95
Modified atmosphere packaging packages 127
Multivibrator 101
O
Optical micrograph 40-41, 79
Optical microscope 78
Organic electronics-A roadmap 3, 5, 10
Organic electronics 1-4, 10, 21
139
Applications 2
Materials 4
Technology 4, 95
Organic field effect transistor 8, 105
Organic light-emitting diodes 21, 22, 105, 106, 108, 110-113
Characteristics of all-printed 26
Printing 22
Organic thin film transistor 2, 7, 17-18, 95-96, 98-99, 100, 102, 105-108, 110-111,
113
P
Polyaniline 67-70, 72-74
Absorbance spectra of 72
Organic dispersions of 68
Polyaniline - dodecylbenzenesulfonate, synthesis of 77
Polyaniline - single walled nanotubes, organic nanocomposite dispersions of 69
Polyaniline - single walled nanotubes - surfactant, absorbance spectra of 72
Polyaniline - surfactant, absorbance spectra of 72
Patterning techniques 6
Poly(3,4-ethylenediocythiophene) - poly(styrenesulfonate) inks, characterisation of 36
Pendant drop method 36
Phase inversion phenomenon 70
Photovoltaic technology 88
Piezoresistive materials 96
Piezoresistive sensor 98
Piezoresistivity 96
Pixel circuits designs 106
Polyaniline synthesis 68
Polyethylene matrix 48
Polyethylene terephthalate 90
Fabrics 91
Polymer degradation 57, 58
Polymer electronics 57, 63
Polymer matrix 64, 67
Polymer stabilisation 57, 58
Polymers, degradation and stabilisation of 58
Polymerisation 68, 92
Positive channel metal oxide semiconductor devices 97
Printing techniques 6, 7, 21
Products Released on Properties Obviously Selected For Additional Life (PROPOSAL)
122
PSPICE 105, 113
R
Radio frequency identification tags 13, 95, 118-122, 126, 130
Redox indicators 127, 129
140
Index
Robotic finger tip specifications 97

Roll-to-roll printed organic light-emitting diodes demonstrators 27
Roll-to-roll printing 21-22
Rotary screen printing 23
Rubber blends 77
S
Scanning electron microscope micrograph 41
Screen printing of aluminium cathode 25
Sencel 98
Sensor array 98
Shelf life, remaining 118
Shelf life, shortest remaining 124
Single wall carbon nanotubes 67-68
Single wall nanotubes 69-70, 72-74
Smart packaging 117
Solar cell 88-90, 92-93
Solar textile 87, 90, 93
Solution mixing 77
Stabilisers for polymer electronics 60
Surface roughness of printed electrodes 14
T
Textile construction 90
Fibres 90
Fabrics 91
Thermal gravity analysis 61
Thin film transistor applications, all-printed 13
Thin film transistor displays 95
Touch sensing 95
Transmission electron microscopy 78, 79
U
UV absorbers 61-63
UV-vis spectroscopy 70, 72-74
V
Van der Pauw equation 81
Van der Pauw technique, four-probe 78
Voltage programming circuit 109-110, 112
Voltage programming pixel circuit 107
141
142
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Polymer Electronics –

Editors: Frances Gardiner

iSmithers – A Smithers Group Company

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

©2009, Smithers Rapra

All rights reserved. Except as permitted under current legislation no part

ISBN (Hard-backed): 978-1-84735-421-1

Typeset by Argil Services

1 Roadmap for Organic and Printed Electronics ................................................1

1.1 Introduction ..........................................................................................1

1.2 Applications ..........................................................................................2

1.3 Organic Electronics Association (OE-A) Roadmap for Organic

1.5 Summary and Outlook ........................................................................10

1.6 Global Network for an Emerging Industry ..........................................10

2 Technical Issues in Printed Electrodes for All-Printed Thin-Film Transistor

2.1 Introduction ........................................................................................13

2.2 Surface Roughness of Printed Electrodes .............................................14

2.3 Edge Waviness in Printed Electrodes ....................................................15

2.4 Solution-Process Organic TFT .............................................................17

2.5 Conclusion ..........................................................................................18

2.6 Acknowledgement ...............................................................................18

3 All-Printed Flexible Organic Light-emitting Diodes .......................................21

Gravure Printing of Poly(3,4-ethylenediocythiophene):poly(styrene sulfonate)

Screen Printing of Aluminium Cathode .........................................................25

Characteristics of All-Printed OLEDS............................................................26

Roll-to-Roll Printed OLED Demonstrators ...................................................27

4 Roadmap for Organic and Printed Electronics ..............................................31

4.1 Process Modelling and Simulation of Ink Jet Printing ..........................32

4.2 Characterisation of PEDOT-PSS Inks and Products .............................36

4.3 Characterisation of Carbon Nanotube - PEDOT:PSS

4.4 Electrospinning of Carbon Nanotube Inks ...........................................40

4.5 Conclusions .........................................................................................41

5 Highly Conductive Plastics – Custom-formulated Functional Materials

5.1 Introduction ........................................................................................43

5.2 Characteristics of the Hybrid Compound Within the Injection

5.2.4 Temperature Dependency on the Conductivity ........................50

6 Additives in Polymer Electronics ...................................................................57

6.1 Introduction ........................................................................................57

6.2 Degradation and Stabilisation of Polymer ............................................57

6.3 Stabilisers for Polymer Electronics .......................................................60

6.4 Functional Additives for Polymer Electronics ......................................63

7 A Facile Route to Organic Nanocomposite Dispersions of Polyaniline – single

7.1 Introduction ........................................................................................67

7.2 Materials .............................................................................................68

7.3 Experimental Section ...........................................................................68

7.5 Results and Discussions .......................................................................70

7.7 Acknowledgements ..............................................................................74

8 Preparation and Characterisation of Novel Electrical Conductive Rubber

8.1 Introduction ........................................................................................77

8.2 Experimental .......................................................................................77

9.1 Introduction ........................................................................................87

9.2 Why Textiles? ......................................................................................88

9.3 Solar Cells ...........................................................................................88

9.4 Technological Speciﬁcations.................................................................89

9.5 Suitable Textile Constructions .............................................................90

9.7 The Future ...........................................................................................93

10.1 Introduction ........................................................................................95

10.2 General Description of the System .......................................................96

10.3 Operation Mechanism .........................................................................96

10.4 Robotic Finger Tip Speciﬁcations.........................................................97

10.5 System Design ......................................................................................97

11 An Organic Thin Film Transistor Pixel Circuit for Active-Matrix Organic

11.1 Introduction ......................................................................................105

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