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Conjugated Polymers
Properties, Processing, and Applications
Conjugated Polymers
Properties, Processing, and Applications
Edited by
John R. Reynolds, Barry C. Thompson, and
Terje A. Skotheim
Cover art by Ellen Skotheim. A collage, based on images from important developments in conducting polymers as represented
by the 4th edition of the Handbook.
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2019 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed on acid-free paper
International Standard Book Number-13: 978-1-138-06570-3 (Hardback)
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to pub-
lish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the
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Contents
Editors.. .....................................................................................................................vii
Contributors.............................................................................................................. ix
1 Conjugated Polymer-Based OFET Devices........................................................1

Mark Nikolka and Henning Sirringhaus
2 Electrical Doping of Organic Semiconductors with Molecular Oxidants
and Reductants..................................................................................................21
Stephen Barlow, Seth R. Marder, Xin Lin, Fengyu Zhang, and Antoine Kahn
3 Electric Transport Properties in PEDOT Thin Films. . ................................... 45
Nara Kim, Ioannis Petsagkourakis, Shangzhi Chen, Magnus Berggren, Xavier Crispin,
Magnus P. Jonsson, and Igor Zozoulenko
4 Thermoelectric Properties of Conjugated Polymers. . ....................................129
Kelly A. Peterson, Eunhee Lim, and Michael L. Chabinyc
5 Electrochemistry of Conducting Polymers.................................................... 161
P. Audebert and F. Miomandre
6 Electrochromism in Conjugated Polymers – Strategies for Complete
and Straightforward Color Control................................................................ 201
Anna M. Ö sterholm, D. Eric Shen, and John R. Reynolds
7 Mechanical Properties of Semiconducting Polymers................................... 249
Mohammad A. Alkhadra, Andrew T. Kleinschmidt, Samuel E. Root, Daniel Rodriquez,
Adam D. Printz, Suchol Savagatrup, and Darren J. Lipomi
8 Magnetic Field Effects in Organic Semiconductors; Low and High
Fields, Steady State and Time Resolved. . ....................................................... 277
Eitan Ehrenfreund and Z. Valy Vardeny
9 Organic Electro-Optic Materials................................................................... 299
Larry Dalton
10 Establishing the Thermal Phase Behavior and its Inf luence on
Optoelectronic Properties of Semiconducting Polymers. . ............................ 329
Natalie Stingelin
v
vi Contents
11 Poly(3-alkylthiophenes): Controlled Manipulation of Microstructure

and its Impact on Charge Transport.............................................................. 351
Michael McBride, Guoyan Zhang, Martha Grover, and Elsa Reichmanis
12 Microstructural Characterization of Conjugated Organic
Semiconductors by X-Ray Scattering . . ............................................................ 391
Maged Abdelsamie and Michael F. Toney
13 Soft X-Ray Scattering Characterization of Polymer Semiconductors.......... 427
Long Ye, Samuel J. Stuard, and Harald Ade
14 Morphology Evolution and Interfacial Design of Conjugated Polymer-
Based Photovoltaics. . ...................................................................................... 459
Yao Liu and Thomas P. Russell
15 The Relevance of Solubility and Miscibility for the Performance of
Organic Solar Cells........................................................................................ 485
Stefan Langner, Jose Dario Perea Ospina,
Chaohong Zhang, Ning Li, and Christoph J. Brabec
16 Processing-Structure-Function Relationships of Polymer-Acid-
Templated Conducting Polymers for Solid-State Devices............................. 515
Melda Sezen-Edmonds and Yueh-Lin Loo
17 Conjugated Polymer Thin Films for Stretchable Electronics........................535
Aristide Gumyusenge, William McNutt, and Jianguo Mei
18 Conducting Polymers for Electrochemical Capacitors.................................. 561
Luciano M. Santino, Yang Lu, Yifan Diao, Hongmin Wang, and Julio M. D’Arcy
19 Redox-Active Polymers as an Organic Energy Storage Material. . ................ 587
Kenichi Oyaizu and Hiroyuki Nishide
20 Electrochromics: Processing of Conjugated Polymers and Device
Fabrication on Semi-Rigid, Flexible, and Stretchable Substrates................. 595
Matthew Baczkowski, Sneh Sinha, Mengfang Li, and Gregory Sotzing
21 Separation Techniques Using Conjugated Polymers.. ................................... 629
Cheng-Wei Lin, Wai H. Mak, Brian T. McVerry, and Richard B. Kaner
22 Organic Bioelectronics Based on Mixed Ion–Electron Conductors. . ........... 679
Magnus Berggren, Erik O. Gabrielsson, Daniel T. Simon, and Klas Tybrandt
23 Conducting and Conjugated Polymers for Biosensing Applications.. .......... 697
C. Pitsalidis, A.M. Pappa, C.M. Moysidou, D. Iandolo, and R.M. Owens
24 Conjugated Poly/O ligo-Electrolytes for Cancer Diagnosis and Therapy. . ....743
Lingyun Zhou, Guillermo C. Bazan, and Shu Wang
25 Biomedical Applications of Organic Conducting Polymers......................... 783
Alexander R. Harris, Paul J. Molino, Caiyun Wang,
Gordon G. Wallace, and Zhilian Yue
Index. . ...................................................................................................................... 813
Editors
John R. Reynolds, a native Californian, obtained his B.S. in Chemistry at San Jose State University
(1979) followed by his M.S. (1982) and Ph.D. (1984) in Polymer Science and Engineering at the University
of Massachusetts. He became interested in the field of conducting and electroactive polymers through
a position with the IBM Research Laboratories in the late 1970s. After developing his own research
effort at The University of Texas at Arlington (1984-1991), he moved to the University of Florida where
he was a Professor of Chemistry and Associate Director of the Center for Macromolecular Science
and Engineering until Spring 2012, when his group moved to Georgia Tech where he is a Professor
of Chemistry and Biochemistry, and Materials Science and Engineering. He serves as Director of the
Georgia Tech Polymer Network (GTPN) and is a member of the Center for Organic Photonics and
Electronics (COPE) management team.
Barry C. Thompson was born in Milwaukee, Wisconsin in 1977 and moved to Gallipolis, Ohio at a
young age, where he attended elementary and high school. Barry then attended the University of Rio
Grande in Rio Grande, Ohio, where he majored in Chemistry and Physics and minored in Mathematics.
After completing his undergraduate studies at Rio Grande, Barry moved to the University of Florida to
pursue a Ph.D. in Chemistry with Prof. John R. Reynolds as an NSF Graduate Research Fellow. During
his Ph.D. studies, Barry focused on the design and synthesis of electroactive conjugated polymers for
electrochromic and photovoltaic applications. Upon completion of his Ph.D. in 2005, Barry moved to
Prof. Jean Fréchet’s lab at UC Berkeley to further pursue his interests in polymer-based photovoltaics
as an ACS-PRF Postdoctoral Fellow. After a three-year stay at Berkeley, Barry moved to the University
of Southern California, Department of Chemistry and Loker Hydrocarbon Research Institute as an
Assistant Professor of Chemistry. Barry was promoted to Associate Professor with Tenure in 2015.
Terje A. Skotheim is the founder of Lightsense and has a successful record in developing new technolo-
gies and launching new products in fields as diverse as advanced lithium-sulfur batteries, MEMS devices,
photovoltaic cells, and biosensors, through several startups. His research interests have spanned across
several disciplines in materials science, including conducting polymers, semiconductors, ion conduc-
tors and diamond-like carbon. He has held research positions and co-founded companies in Europe
and the US, and was head of the conducting polymer group at DOE’s Brookhaven National Laboratory
before launching his career as an entrepreneur. He received his B.S. in physics from the Massachusetts
Institute Technology and his Ph.D. in physics from the University of California at Berkeley.
vii
Contributors
Maged Abdelsamie Magnus Berggren

Stanford Synchrotron Radiation Lightsource Laboratory of Organic Electronics, Department
(SSRL), SLAC National Accelerator Laboratory of Science and Technology
Stanford University Linköping University
Menlo Park, California Norrköping, Sweden
Harald Ade
Christoph J. Brabec
Organic and Carbon Electronics Lab (ORaCEL)
Institute of Materials for Electronics and Energy
Department of Physics
Technology (iMEET)
North Carolina State University
Friedrich-Alexander University
Raleigh, North Carolina
Erlangen-Nürnberg
Mohammad A. Alkhadra Erlangen, Germany
Department of NanoEngineering and
University of California, San Diego
San Diego, California Forschungszentrum Jülich GmbH
Helmholtz-Institut Erlangen-Nürnberg
Pierre Audebert (HI ERN)
PPSM – CNRS – Ecole Normale Supérieure Egerlandstrasse
Paris-Saclay Erlangen, Germany
Paris, France
Shangzhi Chen
Matthew Baczkowski Laboratory of Organic Electronics
Polymer Program Department of Science and Technology
University of Connecticut Linköping University
Storrs, Connecticut Norrköping, Sweden
Stephen Barlow
School of Chemistry and Biochemistry Center for Xavier Crispin
Organic Photonics and Electronics Laboratory of Organic Electronics
Georgia Institute of Technology Department of Science and Technology
Atlanta, Georgia Linköping University
Norrköping, Sweden
Guillermo C. Bazan
Departments of Chemistry & Biochemistry Michael L. Chabinyc
and Materials, Center for Polymers and Materials Department
Organic Solids University of California Santa Barbara
University of California Santa Barbara, California
Santa Barbara, California
ix
x Contributors
Julio M. D’Arcy Magnus P. Jonsson

Department of Chemistry Laboratory of Organic Electronics
Institute of Materials Science & Engineering Department of Science and Technology
Washington University Linköping University
St. Louis, Missouri Norrköping, Sweden
Larry Dalton Antoine Kahn

Department of Chemistry Department of Electrical Engineering
University of Washington Princeton University
Seattle, Washington Princeton, New Jersey
Yifan Diao Richard B. Kaner

Institute of Materials Science & Engineering Department of Chemistry and Biochemistry
Washington University University of California, Los Angeles
St. Louis, Missouri Los Angeles, California
Nara Kim
Eitan Ehrenfreund
Laboratory of Organic Electronics
Physics Department and Solid State Institute
Department of Science and Technology
Technion
Linköping University
Israel Institute of Technology
Norrköping, Sweden
Haifa, Israel
Andrew T. Kleinschmidt
Erik O. Gabrielsson
Department of NanoEngineering
Laboratory of Organic Electronics, Department
of Science and Technology
San Diego, California
Norrköping, Sweden
Stefan Langner
Institute of Materials for Electronics and Energy
Martha Grover
Technology (iMEET)
School of Chemical and Biomolecular
Engineering
Erlangen-Nürnberg
Georgia Institute of Technology
Erlangen, Germany
Atlanta, Georgia
Mengfang Li
Aristide Gumyusenge Polymer Program
Department of Chemistry University of Connecticut
Purdue University Storrs, Connecticut
West Lafayette, Indiana
Ning Li
Alexander R. Harris Institute of Materials for Electronics and Energy
Intelligent Polymer Research Institute Technology (iMEET)
University of Wollongong Friedrich-Alexander University
Wollongong, Australia Erlangen-Nürnberg
Erlangen, Germany
Donata Iandolo
Department of Chemical Engineering and Eunhee Lim
Biotechnology, University of Materials Department
Cambridge University of California Santa Barbara
Cambridge, United Kingdom Santa Barbara, California
Contributors xi
Cheng-Wei Lin Seth R. Marder

Department of Chemistry and Biochemistry School of Chemistry and Biochemistry
University of California, Los Angeles School of Materials Science and Engineering
Los Angeles, California Center for Organic Photonics and Electronics
Georgia Institute of Technology
Xin Lin Atlanta, Georgia
Department of Electrical Engineering
Princeton University Michael McBride
Princeton, New Jersey School of Chemical and Biomolecular
Engineering
Darren J. Lipomi Georgia Institute of Technology
Department of NanoEngineering Atlanta, Georgia
San Diego, California William McNutt
Department of Chemistry
Yao Liu Purdue University
Beijing Advanced Innovation Center West Lafayette, Indiana
for Soft Matter Science and
Engineering Brian T. McVerry
Beijing University of Chemical Technology Department of Chemistry and Biochemistry
Beijing, China University of California, Los Angeles
and Los Angeles, California
Department of Polymer Science and

Jianguo Mei
Engineering
University of Massachusetts
Purdue University
Amherst, Massachusetts
West Lafayette, Indiana
Yueh-Lin Loo
Fabien Miomandre
Department of Chemical and Biological
PPSM – CNRS – Ecole Normale Supérieure
Engineering
Paris-Saclay
Princeton University
Paris, France
and
Paul J. Molino
Andlinger Center for Energy and the
Intelligent Polymer Research Institute
Environment
University of Wollongong
Princeton University
Wollongong, Australia
Princeton, New Jersey
Yang Lu Chrysanthi M. Moysidou

Institute of Materials Science & Engineering Department of Chemical Engineering
Washington University and Biotechnology, University of
St. Louis, Missouri Cambridge
Cambridge, United Kingdom
Wai H. Mak
Department of Chemistry and Hiroyuki Nishide
Biochemistry Department of Applied Chemistry
University of California, Los Angeles Waseda University
Los Angeles, California Tokyo, Japan
xii Contributors
Mark Nikolka Adam D. Printz

Cavendish Laboratory Department of NanoEngineering
University of Cambridge University of California, San Diego
Cambridge, United Kingdom San Diego, California
Anna M. Österholm Elsa Reichmanis

School of Chemistry and Biochemistry School of Chemical and Biomolecular
Georgia Institute of Technology Engineering and School of Chemistry and
Atlanta, Georgia Biochemistry
and
Kenichi Oyaizu
Department of Applied Chemistry School of Materials Science and Engineering
Waseda University Georgia Institute of Technology
Tokyo, Japan Atlanta, Georgia
Roisin M. Owens John R. Reynolds

Department of Chemical Engineering School of Chemistry and Biochemistry, School of
and Biotechnology, University of Materials Science and Engineering
Cambridge Georgia Institute of Technology
Cambridge, United Kingdom Atlanta, Georgia
Anna-Maria Pappa Daniel Rodriquez

Department of Chemical Engineering Department of NanoEngineering
and Biotechnology, University of University of California, San Diego
Cambridge San Diego, California
Samuel E. Root
Jose Dario Perea Ospina Department of NanoEngineering
Institute of Materials for Electronics and Energy University of California, San Diego
Technology (iMEET) San Diego, California
Erlangen-Nürnberg Thomas P. Russell
Erlangen, Germany Department of Polymer Science and
Engineering
Kelly A. Peterson University of Massachusetts
Materials Department Amherst, Massachusetts 01003, United States
University of California Santa Barbara Beijing Advanced Innovation Center for Soft
Santa Barbara, California Matter Science and Engineering
Beijing University of Chemical Technology
Ioannis Petsagkourakis Beijing, China
Laboratory of Organic Electronics
Department of Science and Technology and
Linköping University Materials Sciences Division
Norrköping, Sweden Lawrence Berkeley National Laboratory
Berkeley, California
Charalampos Pitsalidis
Department of Chemical Engineering Luciano M. Santino
and Biotechnology, University of Department of Chemistry
Cambridge Washington University
Cambridge, United Kingdom St. Louis, Missouri
Contributors xiii
Suchol Savagatrup Michael F. Toney

Department of NanoEngineering Stanford Synchrotron Radiation Lightsource (SSRL)
University of California, San Diego SLAC National Accelerator Laboratory
San Diego, California Menlo Park, California
Melda Sezen-Edmonds Klas Tybrandt

Department of Chemical and Biological Engineering Laboratory of Organic Electronics, Department
Princeton University of Science and Technology
Princeton, New Jersey Linköping University
Norrköping, Sweden
D. Eric Shen
School of Chemistry and Biochemistry Georgia Valy Vardeny
Institute of Technology Department of Physics & Astronomy
Atlanta, Georgia University of Utah
Salt Lake City, Utah
Daniel T. Simon
Gordon G. Wallace
Laboratory of Organic Electronics, Department
of Science and Technology
Norrköping, Sweden
Caiyun Wang
Sneh Sinha
Polymer Program
University of Connecticut
Storrs, Connecticut
Hongmin Wang
Henning Sirringhaus Institute of Materials Science & Engineering
Cavendish Laboratory Washington University
University of Cambridge St. Louis, Missouri
Shu Wang
Gregory Sotzing Beijing National Laboratory for Molecular
Polymer Program Sciences, Key Laboratory of Organic Solids
University of Connecticut Institute of Chemistry
and Chinese Academy of Sciences
Beijing, China
University of Connecticut and
Storrs, Connecticut University of Chinese Academy of Sciences
Beijing, China
Natalie Stingelin
School of Materials Science and Engineering and Long Ye
School of Chemistry and Biochemistry Organic and Carbon Electronics Lab (ORaCEL)
Georgia Institute of Technology Department of Physics
Atlanta, Georgia North Carolina State University
Raleigh, North Carolina
Samuel J. Stuard
Organic and Carbon Electronics Lab (ORaCEL) Zhilian Yue
Department of Physics Intelligent Polymer Research Institute
North Carolina State University University of Wollongong
Raleigh, North Carolina Wollongong, Australia
xiv Contributors
Chaohong Zhang Lingyun Zhou

Institute of Materials for Electronics and Energy Beijing National Laboratory for Molecular
Technology (iMEET) Sciences, Key Laboratory of Organic
Friedrich-Alexander University Solids
Erlangen-Nürnberg Institute of Chemistry
Erlangen, Germany Chinese Academy of Sciences
Beijing, China
Fengyu Zhang
and
Department of Electrical Engineering
Princeton University University of Chinese Academy of Sciences
Princeton, New Jersey Beijing, China
Guoyan Zhang Igor Zozoulenko

School of Chemical and Biomolecular Laboratory of Organic Electronics
Engineering Department of Science and Technology
Georgia Institute of Technology Linköping University
Atlanta, Georgia Norrköping, Sweden
1
Conjugated Polymer-
Based OFET Devices
1.1 Introduction........................................................................................... 1
1.2 State of OFET Technology/Applications/
Commercialization Efforts................................................................... 3
1.3 Recent Developments in Polymer OFET Materials – From
Crystalline Polythiophenes to Donor–Acceptor Polymers............. 3
1.4 Charge Transport in Polymer OFETs.................................................5
1.5 Role of Disorder.....................................................................................7
1.6 Charge Carrier Mobility and Artefacts............................................ 10
Mark Nikolka 1.7 Stability of OFETs................................................................................ 12
and Henning 1.8 Outlook.................................................................................................. 15
Sirringhaus References......................................................................................................... 16
1.1 Introduction
Easy processability, mechanical flexibility and the endless possibilities of molecular modifications to
achieve, for example, performance improvements or analyte selectivity in sensing applications have
staged organic field-effect transistors (OFETs) as one of the future trendsetting technologies. To date,
OFET integration in applications ranging from rudimentary sensors and circuits to flexible low-
resolution displays for electronic paper has been demonstrated. Concomitantly, more and more promis-
ing applications for OFETs such as fully flexible organic light-emitting diode (OLED) and organic TFT
addressed liquid crystal displays (OLCDs), image sensing applications (e.g. X-Ray sensors), organic logic
circuits and sensors for wearable applications come within reach.1–4 These novel applications require the
use of high-performance, high-stability organic semiconductors with good uniformities imposing tight
constraints on the choice of organic semiconductors. For a long time, small molecular semiconduc-
tors were deemed the best materials class to meet these rigorous requirements owing to high-mobility
band transport observed in covalently bonded small molecule single crystals5,6; charge transport in
such systems is widely thought to approach fundamental limits imposed by the weak van der Waals
bonding and the polaronic nature of charge carriers in these molecular solids. Conjugated polymers,
on the other hand, were considered too disordered to achieve similarly high charge carrier mobility
and for a long time were considered inferior for industrial applications. Nevertheless, whereas small
molecular organic semiconductors such as rubrene or pentacene potentially are able to deliver high
performances in research laboratories, their high degree of crystallinity, polycrystalline nature and the
inevitably resulting device-to-device variations in performance have caused concerns for large area
applications, especially in the key displays market where device uniformity is as important as device
1
2 Conjugated Polymers
performance. Due to their good film forming properties and more uniform thin film microstructures,
conjugated polymers could offer potential advantages in order to meet these tight uniformity require-
ments. Therefore, conjugated polymers that can form percolating networks of chains allowing for both
intrachain as well as interchain charge transport have attracted renewed interest in the community.
These research efforts have led to a number of breakthroughs that have allowed conjugated polymers to
approach performance values that were formerly thought impossible.
A lot of research has been conducted to improve the performance of polymers, with field-effect
charge carrier mobilities having improved by six orders of magnitude over the past 30 years. In this
respect, much of the latest advancements have been made by the class of amorphous/semi-crystalline
donor–acceptor polymers. Some of these new donor–acceptor polymers already demonstrated extraor-
dinary charge transport properties, such as hole and electron mobilities exceeding 1 cm2/Vs,7,8 allow-
ing them to match and partially even exceed the performance of amorphous silicon (a-Si) thin film
transistor (TFT) technology – a material class that is, for instance, applied in many LCD backplanes
nowadays. Nevertheless, despite extensive research, charge transport in these materials is still insuffi-
ciently understood, which constrains the design of new high-performance materials and makes it diffi-
cult to have clear molecular design criteria for materials that can deliver improved device performance.
Furthermore, low operational and air stability of conjugated polymer devices remains a major concern
to date, leading to product lifetimes that are too short for demanding large-scale applications. In this
chapter, we review the current state of the art as well as address a range of challenges that still have to
be overcome. We will particularly focus on the role and origin of environmental and operational stress
instabilities, the control of the degree of energetic disorder, as well as the issue of device non-uniformity
and non-ideality of device characteristics that can lead to difficulties in estimating accurately reported
charge carrier mobility values. Many of the above issues pose a major challenge for the upscaling of
polymer OFETs and we will review which steps have to be taken to addressing them (Figure 1.1) 9–11.
FIGURE 1.1 Left: Schematic structure of an active matrix LCD and OLED display representing key applications
for polymer OFET devices. Images adapted from Sears, The evolution of display technology; In the case of an
LCD display a matrix of TFTs modulates the light emitted from a strong backlight by polarizing liquid crystals;
for an OLED display, the TFT array directly addresses the light emitting OLED pixels requiring high currents,
performances and stability. Right: Evolution of charge carrier mobilities of semiconducting polymers. The asterisk
denotes materials which were aligned using a special technique10 – The quoted mobility value can nevertheless be
considered inflated and significantly below 10 cm2/Vs. (With permission from Himmelberger, et al., MRS Commun.
5, 1–13 (2015)).
Conjugated Polymer-Based OFET Devices 3
1.2 State of OFET Technology/Applications/

Commercialization Efforts
Over the last decade, organic semiconductors have steadily left the realms of an emerging technology
and in many areas have successfully been commercialized. One of the most prominent examples in
this respect is the use of OLED displays for smart phones and high-resolution television screens. Here,
Samsung has pioneered the development of active-matrix organic light-emitting diode (AMOLED) dis-
plays which incorporate OLEDs driven by a backplane of inorganic thin-film transistors. Also, for light-
ing applications OLEDs have enjoyed popular demand and companies such as Philips, Osram, Novaled,
LG Chem and Konica Minolta have successfully brought large area OLED lighting panels to the market.
In contrast, OFET technology to date has only been commercialised in certain niche applications.
Although applications such as simple logic circuits or chemical and biological sensors have repeatedly
been demonstrated in research laboratories, no significant commercialization attempt has, thus far,
fully succeeded. The most advanced commercialization efforts to date have been in flexible electronic
paper (E-paper) displays by companies including Polymer Vision and Plastic Logic. E-paper does not
have demanding drive requirements and at the time these requirements were well matched to the per-
formance that could be delivered by OFETs. However, E-paper is also not capable of delivering vibrant
colour and video displays which has limited its market success. Nevertheless, Plastic Logic in Germany
has developed a stable, high yielding manufacturing process for OFET-based flexible E-paper displays
and is selling these displays for niche applications that benefit from the bistability, low power consump-
tion and excellent readability in bright sunlight conditions, such as electronic readers or signage displays.
The recent advancements in the performance of conjugated polymer OFET technology are now allow-
ing it to target more mainstream markets such as high-resolution video rate LCD and OLED displays.
For instance, by now the ability to reliably achieve performances above those of amorphous silicon (a-Si)
renders polymer OFETs as an attractive alternative to a-Si in state-of-the-art LCD backplane displays.
The opportunity to process light weight displays on flexible foil gives OFET driven LCDs an edge over
its traditional competitor. The UK based company FlexEnable, which was spun-out of Plastic Logic, has
developed and demonstrated a flexible OFET-LCD platform that in price, reliability and yield is compa-
rable to standard amorphous-LCD technology. This offers OFET technology an attractive entry into the
large-scale display market12 and enables flexible, light-weight, unbreakable colour and video displays for
applications in automotives or consumer electronics.
Looking ahead, the industrial “gold-standard” in the display industry is gradually shifting further
towards even more demanding applications such as current-driven OLED displays. In this display class,
the transistor directly addresses the light emitting pixel and hence imposes an unprecedented require-
ment on both mobility and stability on the OFETs. Despite these harsh performance requirements,
some display manufacturers have already shown prototypes of fully flexible OLED backplane displays
based on organic TFT technology. Companies such as Sony, Samsung and LG have all demonstrated
fully flexible, full-color OLED displays and independently announced significant investment into this
technology. Although not yet driven by polymer OFETs, there is scope and interest for their integra-
tion in the near-term future, taking polymer OFETs a step closer to industrialization and full-scale
commercialization. However, this will require further improvement in both materials’ performance –
field-effect mobilities of 10–15 cm2/Vs are required for OLED driving and operational stability.
1.3 Recent Developments in Polymer OFET Materials – From

Crystalline Polythiophenes to Donor–Acceptor Polymers
The first ever polymer field-effect transistor reported by Koezuka et al. in 1987 was based on electrochem-
ically deposited polythiophene and exhibited a rather moderate field-effect mobility of 2 10−5 cm2/Vs.13
Only one year later, the addition of solubilizing side chains resulted in the first solution processed
polythiophene transistors exhibiting similarly low performances.14 The reason for choosing polythio-
phene in both cases was based on a design strategy that had evolved and prevailed in the field for a long
time: The design of rigid-rod-like polymers that, very similarly to small molecular semiconductors, are
able to form crystalline structures with enhanced π–π stacking and long-range order. Polythiophene
with its rigid backbone of conducting conjugated rings was hence deemed the best candidate to achieve
similar performances as had been observed for small molecules such as pentacene, rubrene or sexithio-
phene before.15–20 For almost two decades polythiophenes remained the material of choice with charge
carrier mobility values steadily improving to reach values above 0.1 cm2/Vs by the late 1990s. To a sig-
nificant degree, this achievement was enabled through a better control of thin-film morphology and the
control the growth of ordered microcrystalline domains.21,22 This approach of tailoring the material’s
crystallinity has led to a range of excellent rigid-rod polymer candidates and brought forth materials
such as poly(2,5-bis(3-tetradecylt hiophene-2-yl)t hieno[3,2-b]thiophene) (pBTTT), which for the first
time could exhibit field effect mobilities above 1 cm2/Vs23,24 and hence compete with current amorphous
silicon (a-Si) TFT technology that is crucial for commercialization in products such as LCD-backplane
displays. The sketch presented in Figure 1.2 shows the prevailing morphology observed for rigid-rod
polymer exhibiting clearly defined π–π-stacking of the polymer backbones oriented mostly edge-on
with respect to the substrate plane.
In the mid-2000s, the new class of donor–acceptor (D–A) polymers emerged which fundamentally
deviated from the hitherto prevailing rigid-rod design motive. In contrast to the relatively short electron
donating units of polythiophenes, donor–acceptor polymers comprise alternating electron rich donor
units and electron poor acceptor units along their backbone. Owing to the presence of both electron rich
and electron poor moieties, as well as a relatively small bandgap usually ranging between 1.0 and 1.9 eV,
donor–acceptor polymers generally exhibit pronounced ambipolar charge transport which means
that they are capable of exhibiting good electron and hole conductance when applying positive and
negative gate voltages to the OFET. Although initially substantially poorer performing than polythio-
phenes, donor–acceptor polymers recently have led to a significant increase in reported charge carrier
mobilities, with many reports claiming field-effect mobilities approaching and even exceeding values
of 10 cm2/Vs.25–28 Although in many of these reports mobilities are extracted from non-ideal device
characteristics which could potentially lead to an overestimation of mobility values (an issue we will
address later in this chapter), these performances nevertheless display the potential of D–A type poly-
mers approaching the performance of small molecular semiconductors. This is particularly surpris-
ing when considering, that D–A-type polymers are significantly less crystalline than polythiophenes
or the formerly mentioned small molecules. In Figure 1.3 some examples of recent high-performance
donor–acceptor polymers are shown, along with some more traditional rigid-rod polymers, sometimes
termed homopolymers (i.e. having a purely electron donating character). Understanding the origin of
FIGURE 1.2 Film morphology of a crystalline polythiophene polymer (Left) compared to an amorphous/semi-
crystalline donor–acceptor polymer (Right). Each square represents one monomer unit having chemical structures
as represented in Figure 1.3. Side chains are omitted in this sketch.
FIGURE 1.3 Chemical structure of the common rigid-rod polymers PBTTT, P3HT as well as popular donor–
acceptor polymers such as N2200, CDT–BTz, DPP–TT–T and IDT–BT. Acceptor units (e.g. DPP, BT) are circled in
light gray and donor units (e.g. IDT, CDT, (oligo)thiophene) are circled in dark gray.
the superior performance of these structurally more disordered polymers over polythiophenes has been
a major challenge in the field and more recently the key to opening the door for polymer transistors to
be used in highly demanding applications.
1.4 Charge Transport in Polymer OFETs

To understand the origin of high-performance in conjugated polymer OFETs, we have to take a look at
the mechanism for charge transport in these materials. We should, however, firstly address the elephant
in the room and point out that studies of charge transport are naturally entangled with the choice of
device architecture and factors such as the device geometry, contact resistance and charge transport
interfaces. Some of these factors have successfully been addressed through extensive research effort
over the past decades and optimized device architectures have been conceived (Figure 1.4). For instance,
the use of fluorinated polymer dielectrics with low dielectric constants such as CYTOP29 or TEFLON30
or conventional inorganic dielectrics such as aluminium oxide (Al2O3), hafnium oxide (HfO),31 benzo-
cyclobutene (BCB) or silicon dioxide (SiO2)1 treated with dipole-shielding self-assembled monolayers
(SAMs) based on octadecyltrichlorosilane (OTS),32 hexamethyldisilazane (HMDS) or phosphonic acid
(PA)33 have given charge transport interfaces with low interfacial trap densities. Figure 1.5a illustrates
the importance of shielding the charge carriers in the accumulation layer of the OFET from the ran-
domly oriented dipole moments in the gate dielectric to avoid a widening of the density of states (DOS)
at the crucial charge transport interface; this in turn has been shown to result in a detrimental localiza-
tion of charge carriers and as a result, a reduction in charge carrier mobility. Evidence that careful opti-
mization of both charge transport interface and the control of processing conditions have now become
possible is served by the routine realization of notoriously sensitive n-type charge transport and light-
emitting polymer OFETs that are very sensitive to electron trap states at the interface.34–37 A bottleneck
in any OFET architecture still remains the injection/extraction of charge carriers into the semiconduct-
ing polymer. In contrast to silicon–MOSFETs where carriers are injected from highly doped regions
of either n++ or p++ doped silicon, OFETs require a matching of the electrode’s work function to the
polymer’s HOMO or LUMO level (Figure 1.5b). For many materials, this remains a challenge as the
choice of (stable) electrode metals is limited; the resulting mismatch of energy levels can hence lead to
considerable contact resistances. For many current generation donor–acceptor polymers thus far, the
HOMO level is positioned between 5.0 and 5.3 eV which allows for relatively efficient injection from gold
electrodes facilitating p-type OFETs with sufficiently low contact resistances.
FIGURE 1.4 Device architecture related factors that can lead to poor OFET performance: a) Presence of dipoles
in the dielectric broadens the DOS at the interface resulting in a localization of charges and a reduction in charge
carrier mobility. (With permission from Sirringhaus, B. H. Device physics of solution-processed organic field-
effect transistors. Adv. Mater. 17, 2411–2425 (2005).); b) Work function misalignment between the position of the
semiconductor’s LUMO level (or electron affinity, EA)/HOMO level (or ionization potential, IP) and injecting metal
electrode’s work function leads contact resistance and non-ideal device performance.
FIGURE 1.5 Schematic representation of an amorphous polymer with the backbone broken up in conjugated seg-
ments and charges hopping along these segments (b) Broadening of the HOMO and LUMO levels of a polymer due
to energetic and structural disorder. A range of a Gaussian density of states (DOS) (black line) is approximated by
an exponential DOS (red line). (With permission from Brondijk, Device Physics of Organic Field-Effect Transistors,
PhD thesis (University of Groningen, 2012)).
Nevertheless, despite the above mentioned device specific factors, the biggest challenge still remains
the design of polymer semiconductors that are able to transport charges efficiently. In conjugated poly-
mers, variations in the backbone structure (e.g. kinks, defects, variations of torsion angles, etc.) as well
as small variations in the intermolecular environment give rise to a range of delocalization lengths
experienced by charge carriers along different polymer chains or parts of polymer chains. This results in
energy level fluctuations and consequently the polaronic energy levels within a polymer film are inho-
mogeneously distributed and widened. Additionally, despite there being a few counterexamples, the
presence of solubility enhancing side chains generally make it more difficult for the conjugated units to
aggregate and to exhibit close π–π stacking. This allows only for weak interactions to take place between
isolated chains contrasting the much stronger intermolecular coupling seen in most small molecular
systems. Many of these effects are commonly summarized under the term disorder. One of the earliest
and simplest models describing charge transport in such disordered materials is the mobility edge (or
multiple trapping and release) model developed by Nevill Mott in 1967.38 The model makes the assump-
tion that electronic states are localised below a certain energy level (called mobility edge) and charge
transport occurs by thermal excitation of carriers from these trap states to spatially extended, mobile
states above the mobility edge. Although being developed originally for the description of amorphous
silicon,39 the mobility edge (ME) model had some success in describing charge transport in organic
semiconductors such as sexithiophene.40 Also for solution processed conjugated polymers the ME model
has had some phenomenological success, as for instance demonstrated by charge transport modeling
work on the fluorine copolymer PQT-12.41,42
Nevertheless, in the case of polymers, the structural aspects outlined above (mostly) prevent energy
band formation, such that charge transport is widely agreed to happen by hopping of charge carriers
instead.1 To describe this type of transport, Allen Miller and Elihu Abrahams developed a relatively sim-
ple model which predicts the frequency νij of charge carrier hopping between the shallow impurity sites
i and j in a lattice with weak coupling and at cryogenic temperature.43 The resulting Miller Abrahams
hopping rate is given by
 ε j − εi
νij = ν0e
(− α Rij ) e − KT for ε j > εi , i.e. upward hop

 1 for ε j < εi , i.e. downward hope
where νij is the maximum hopping rate (sometimes this is referred to as hopping attempt frequency)
and α is the inverse localization length indicating how well a charge carrier is able to tunnel across the
distance R ij. It should be noted here, that the model is elementarily made up of only two independent
components: A first quantum mechanical tunneling contribution as well as a second temperature acti-
vated component. Consequently, it can be energetically more favourable to hop over a large distance
with a small activation energy instead of hopping to a near site with a large activation energy. Since
only energetic site differences derived from a density of states (often Gaussian or exponential) are con-
sidered, the approach of Miller–Abrahams hopping allows to describe charge transport in disordered
systems without the knowledge of complex transfer integrals or reorganization energies; this would
be strictly required for more complex models such as the popular Marcus model that also accounts
for the polaronic nature of charges inside of organic semiconductors. In fact, in a simplified picture
knowing the number of molecular sites as an estimate for the number of hops N needed to travel across
a device with distance L, it is possible to calculate the drift velocity v of charge carriers. From this and
the applied electric field E, the charge carrier mobility μ = v/E can easily be extracted as a parameter
characterizing the efficiency of charge transport in a semiconductor. Due to the relative simplicity of
the Miller–Abrahams hopping rate, it has been adapted in various charge transport models termed
variable range hopping (VRH) models. Here, for instance, Bässler has pioneered one of the first charge
transport models based on hopping in a system with spatial and energetic disorder.44 The Bässler model
itself assumes a hopping rate following Miller–Abrahams expression along with a broadening of the
HOMO and LUMO levels described by a Gaussian DOS – a shape which is supported by the observation
of Gaussian shaped optical spectra.44 Recent adaptations of the Bässler model are the charge transport
models developed by Vissenberg–Matters45 as well as Brondijk et al.46, which are similar to the Bässler
model47 but make varying assumptions about the shape of the DOS and allow modeling of the current
that would be expected in an OFET architecture. In this case, however, there are a number of free fit
parameters in the model which make the model parameters difficult to deduce unambiguously and with
a high level of confidence.
1.5 Role of Disorder
The lack of long-range delocalized transport, as seen for inorganic semiconductors such as silicon, and
the presence of hopping transport make conjugated polymers extremely sensitive to the distribution
of available states. For a long time, it has hence been the prevailing polymer design motif to mimic
the crystalline structure of inorganic materials in an attempt to narrow the distribution of states and
even achieve some degree of long-range charge carrier delocalization. The control of morphology and
crystallinity has therefore been a fundamentally integral part of any OFET research activity. It is for
this reason that the emergence of high-performing D–A copolymers with their structurally disordered
amorphous to semi-crystalline morphology has been puzzling the community. To understand the supe-
rior performance of some of these D–A copolymers, it is essential to consider the two key factors that
enable good charge transport properties.
A first key factor that has been shown to be important in achieving high carrier mobilities is a sufficiently
high long-range order of the polymer chains. One way of achieving such long-range order is a sufficiently
high molecular weight that ensures that there are efficient chain interconnections between aggregates/crys-
tallites. Recently several studies were able to shed some light on this aspect by combining a molecular- and
microstructural picture of charge transport in polymers. For instance, Salleo and coworkers were able to
demonstrate that polymers are fundamentally limited by lattice disorder which can be overcome by charge
transport along the extended polymer chains. Therefore, for efficient charge transport it is not necessary
that the film is highly crystalline, short-range intermolecular aggregation or nanometre sized crystalline
domains are sufficient to allow efficient long-range charge transport as long as these domains are connected
by tie-chains.48 The transport through these so-called tie-chains thus enables seemingly structurally disor-
dered conjugated polymers to exhibit high charge carrier mobilities. Figure 1.6 illustrates this concept for
the case of a semi-crystalline, weakly ordered and fully amorphous polymer. The tie-chains in the weakly
ordered polymer are enabling efficient charge transport through the structurally disordered microstruc-
ture; this allows for similar percolation of charges as in the case of a more crystalline polymer.
However, although a high molecular weight might constitute a means to achieving long-range order
in various polymer semiconductors, it does not necessarily result in a good transistor material. In some
cases, long-range ordering can only be achieved through additional means that can induce backbone
elongation and inter-grain connectivity. For instance the combination of pre-aggregation in solution,
as well as shear-alignment, has been shown to result in significantly improved charge carrier mobili-
ties of 2 cm2/Vs for the polymer N2200.49 Also, in the case of the more crystalline polymers P3HT and
PBTTT, the use of pre-aggregation and/or external alignment has shown to be highly successful route
towards enhanced charge carrier mobilities.50,51 However, because of this long-range alignment of poly-
mer backbones or, equivalently, aggregation, pronounced device-scale mobility anisotropy will often be
inevitable. As a result, generally the charge carrier mobility along the alignment direction of the poly-
mer backbone will be enhanced over the performance observed in the isotropic case. The charge carrier
mobility perpendicular to the alignment direction, on the other hand, can be substantially reduced.52
A second key factor has been identified to be a low degree of energetic disorder in the polymer film.
Although achieving long-range order constitutes an important ingredient for high performances, it does
not fully explain why recent generation D–A copolymers generally tend to outperform crystalline poly-
thiophenes or polymers with high long-range order by up to an order of magnitude. For this, it is impor-
tant to understand that individual polymer chains themselves possess a strong local mobility anisotropy
with varying barriers encountered for intra- and interchain charge transport. The energetic disorder
exhibited by a polymer is a representation of this disorder and the resulting distribution of accessible
states. In simple terms, it therefore reflects the energetic landscape encountered by a charge when moving
FIGURE 1.6 Microstructure of conjugated polymer films. Representative of microstructure of (a) semi-
crystalline, (b) weakly ordered, and (c) amorphous polymer films. (With permission from Noriega et al., Nat.
Mater. 12, 1038–1044 (2013)).
through the polymer. Assessing this disorder, unfortunately, is not straightforward, making it difficult to
correlate polymer structure to charge transport properties. However, recent studies using a combination of
techniques such as photothermal deflection spectroscopy (PDS), thermoelectric Seebeck measurements53
as well as charge transport measurements, in combination with charge transport models54–56, have demon-
strated that the degree of energetic disorder is exceptionally low in these high-mobility D–A copolymers.
In this way, it has been possible to explore the origin of high performance in some donor–acceptor
polymers to an extraordinarily planar, torsion-free polymer backbone. The resulting low energetic dis-
order essentially ensures that the charge carriers can move efficiently along the tie chains in between
aggregates and are not impeded in their motion by chain conformations that constitute transport
bottlenecks along the polymer chain. Figure 1.7 shows the planar backbone of the polymer IDT–BT
compared to the somewhat twisted backbone of the rigid-rod polymer pBTTT and how it materializes
itself in an unusually low disorder that is approaching a disorder-free domain; this is retained even
once the polymer is in a completely amorphous phase (Figure 1.7c). Such a high degree of backbone
planarity can be detected by pressure dependent Raman measurement (Figure 1.7b)57 or by calculat-
ing the gas-phase torsion potentials of IDT–BT (Figure 1.7d). As a consequence of this low disorder
FIGURE 1.7 Resilience of torsion-free polymer backbone conformation to side-chain disorder. a) Simulations of
the backbone conformation of IDT–BT and PBTTT in side-chain-disordered and non-interdigitated structures.
The side chains and hydrogen atoms are omitted for clarity. Yellow, sulphur atoms; blue, nitrogen atoms; b) Pressure
dependence of the intensity ratio of the Raman transitions at 1,542 cm−1 and 1,613 cm−1 (top) and the Raman spec-
trum of IDT–BT measured using a diamond-anvil cell (bottom). a.u., arbitrary units; c) Simulation of the backbone
conformation of IDT–BT in the amorphous phase. A single chain from the simulated unit cell has been highlighted
in bright yellow (other colours as in a). d) Calculated gas-phase torsion potentials of IDT–BT and PBTTT. For
PBTTT, the potential for torsion between the thiophene and thienothiophene units is shown. (With permission
from Venkateshvaran et al., Nature 515, 384–388 (2014)).
backbone configuration, charge carriers, though still based on hopping, can access almost all available
states yielding the observed high charge carrier mobilities reliably above 1 cm2/Vs. Indeed, the feature
of low energetic disorder can be found in all families of high-performing donor–acceptor polymers
explaining why these systems can excel other materials with superior crystallinity. Therefore, polymer
structures with only occasional close contact between individual chains but low energetic disorder and
planar backbone have evolved as a novel design motif for the next generation of high-performance poly-
mer semiconductors.
1.6 Charge Carrier Mobility and Artefacts

Although it might appear trivial, it remains a fundamental challenge to accurately determine and com-
pare the performance of conjugated polymer OFETs. In this respect, the charge carrier mobility (μ) is
naturally the main benchmark to compare the performance of OFETs made from various materials and
in different architectures, though it is worth noting that for industrial applications device-dependent
metrics, such as absolute ON current or transconductance at a given applied voltage may be more rel-
evant metrics. To extract an OFET’s charge carrier mobility, a classical model developed for ideal silicon
MOSFETs is widely applied. This model assumes that the potential drops linearly across the transistor’s
channel (also referred to as the gradual channel approximation) and that additionally, no states are pres-
ent in the semiconductors band gap and hence, mobility is independent of charge carrier concentration.
The MOSFET model then gives a simple relation between drain current and gate and drain voltage that
allows extraction of charge carrier mobility µ in both the linear and saturation regime according to,
W
I Dlin = µ Ci (VG − VTh )VSD VSD VG − VTh
L
W
Ci (VG − VTh )
2
I DSat = µ VSD > VG − VTh
L
where
L is the transistor’s channel length (i.e. the distance between the source and the drain electrode)
W is the channel width (i.e. the overall width of the source or drain contact)
VG is the applied gate voltage
VDS the applied drain-source voltage
VTh is the transistor’s threshold voltage
The saturation charge carrier mobility (often quoted as a single reference value due to its importance
for high-current applications such as OLED backplanes) then can be extracted by taking the square
root’s slope of measured transfer characteristics. Figure 1.8 displays how the saturation mobility can
be extracted in an ideal or close to ideal device as for instance observed for many of the low-disorder
polymers we discussed previously.53 In such cases, we would expect a low threshold voltage, a sharp sub-
threshold swing as well as output characteristics that is linear for low voltages and shows flat saturation
behaviour as displayed in Figure 1.8.
However, strictly speaking, many of the assumptions made in the MOSFET model are invalid for
most OFETs as organic semiconductors often do not exhibit the same “ideal” behaviour as for instance
seen for silicon transistors. For instance, in contrast to MOSFETs that operate in inversion mode, OFETs
are operated in accumulation mode, and hence artefacts such as the formation of backchannels are often
observed, leading to output characteristics that do not fully saturate. The broad distribution of states
encountered in conjugated polymers, trapping at impurities or the semiconductor–dielectric interface,
misalignment between the injecting electrode and the semiconductor’s energy levels are some of the
additional factors that can lead to non-ideal FET characteristics and an inflation of extracted charge
Sub-Treshold Slope
(V/dec)
Drain current (ID /A)

Draincurrent(ID/A)
Sqrt (ID)
VTh
Gate Voltage (VG /V) Drain Voltage (VD /V)
FIGURE 1.8 Drain current as a function of gate voltage (transfer characteristics, left) and drain current as a func-
tion of Source-drain Voltage (Output characteristics right) for an ideal polymer OFET with negligible hysteresis
and a small threshold voltage.
carrier mobilities. In the following, we list four more common phenomena that have been observed in
polymer devices and are known to lead to an inflation of reported charge carrier mobility values:
i) A semiconductor with a broad distribution of states (i.e. large disorder) will tend to exhibit a
genuinely field-dependent charge carrier mobility. This originates in the growing number of
states that become accessible at higher gate-voltages. In these systems, the square root of the drain
current will usually be super-linear at higher fields and consequently, higher fields will result in
higher charge carrier mobilities. In such cases, a large discrepancy between the charge carrier
mobility extracted in the linear and the saturation regime can be expected. Consequently, the
linear mobility should be quoted as a lower bound to the device’s performance.
ii) The presence of polarizable dielectrics and the presence of ions in the gate dielectric can cause
the value of the gate dielectric capacitance, Ci, to be underestimated, leading to an overestimation
of carrier mobility. This may manifest itself as well in a large hysteresis in the measured transfer
characteristics. In such circumstances, it is absolutely crucial to determine the steady state capaci-
tance of the gate dielectric.
iii) The presence of contact resistance will lead to a shift in threshold voltage. At higher gate volt-
ages this initial resistance is gradually overcome leading to a steeper than usual rise in current
and hence inflated charge carrier mobility. This effect usually gives rise to an S-shaped or (if
the threshold voltage is large enough) exponential shape of the square root resulting in a severe
overestimation of reported charge carrier mobility values (illustrated schematically in the long-
dashed line curve in Figure 1.9)58;
iv) The square root of the drain current exhibits a kink with higher slopes being observed at lower
gate voltages (illustrated schematically in the short-dashed line curve in Figure 1.9). Interestingly,
this phenomenon occurs mostly for low-bandgap donor–acceptor polymer devices with a bottom
gate architecture comprising SAMs such as OTS.26 Various explanations have been given for the
origin of this phenomenon, relating it to contact resistance or to an unconfined accumulation
layer at lower gate voltages.59,60
Although the exact origin for inflated charge carrier mobility will have to be established in each indi-
vidual case (and in some cases a combination of mechanisms will simply make it impossible to pinpoint
individual causes), it is important to use a robust mobility extraction method that allows a conservative
comparison of the true current-carrying capability of different transistor materials and structures. One
example of addressing the inflation of charge carrier mobilities has recently been proposed by Choi
et al. who define a reliability factor for mobility extraction in non-ideal devices.61 The method is based
on comparing the measured on-current at the highest gate voltage to that of an ideal transistor and the
determination of the effective mobility that such an ideal transistor would need to have to match the
FIGURE 1.9 Illustration of mobility inflation on the basis of the square root of ID.
measured on-current. The reliability factor, which relates the effective mobility to the claimed maxi-
mum mobility extracted from the measured transfer characteristics, can be used to avoid the report-
ing of inflated charge carrier mobilities and lead to a more robust reporting of device performances.
Likewise, it is generally the case that the above artefacts affect the extracted saturation mobility more
than the linear charge carrier mobility. This is also the reason why many conjugated polymer OFETs
will exhibit a saturation mobility that can be up to an order of magnitude higher than the reported
linear mobility. Hence, the ratio between these two mobilities should also give a good estimate of how
accurate and representative the extracted charge carrier mobilities are. This is why in an industrial set-
ting, the on-current of OFETs with a given architecture is a much more applicable figure of merit and is
used to assess performance. Nevertheless, although mobility overestimation is a current problem espe-
cially for values exceeding 10 cm2/Vs there are many examples of reported devices that exhibit close-to-
ideal linear and saturation mobilities well above 1 cm2/Vs; this approaches industrial requirements for
OLCD and OLED backplane displays as long as a sufficiently high stability can be warranted.
1.7 Stability of OFETs
As discussed above, the rapid improvement seen in OFET performance, in particular enabled by novel
D–A copolymers, in many areas has brought OFETs significantly closer towards real-world applications.
It is for this reason that recently their reliability under representative operational and environmental
conditions has been called into closer focus. We would, therefore, like to continue this discussion from
an application point of view and take a look not only at the performance of polymer OFETs but also
their stability. In fact, for industrial applications, the long-term stability under shelf-storage as well as
bias–stress will crucially determine the suitability of OFETs for commercialization. In this respect, the
disordered structure of most conjugated polymers is not only reflected in complex charge transport
mechanisms but often in unsatisfactory levels of stability. Since organic semiconductors are only weakly
held together by van der Waals interactions, they are prone to degradation and potential structural
changes during operation and ingress by environmental species. In this context, it has been understood
for some time that electrons in high-lying energy levels, i.e. materials with low electron affinity, exhibit
a high susceptibility to electron trapping in the presence of water and/or oxygen species in ambient
conditions62, which for a long time has been a major hurdle for the realization of n-type OFETs. In
the current generation of high-performance p-type and ambipolar OFETs this issue is addressed by
designing molecules with deep-lying HOMO and LUMO levels. Generally, ionization potentials deeper
than approx. 5.1 eV are considered to improve stability against oxidative p-type doping by atmospheric
species, such as oxygen, significantly. While this improves the stability of conjugated polymers in oxy-
gen rich environments, these materials have been found to show a tendency to degrade in oxygen poor
environments such as nitrogen or vacuum.63 Here, it is important to point out that degradation due to
environmental species is generally creating both shallow and deep traps for charge carriers. Shallow
trapping happens on a fast time scale and thus it can be easily observed during single transfer or output
measurements. Deep traps manifest themselves in long-term threshold voltage shifts during environ-
mental exposure or operational stress tests. Recently, studies have shown that in current generation
D–A copolymers, many of these traps are related to water molecules and can be passivated with molecu-
lar additives that are incorporated into the film to occupy voids within the films and passivate/dis-
place water molecules away from the charge transporting polymer backbone.63 In this way significant
improvements in the environmental and operational stability can be achieved, but also improvements
of other device parameters such as contact resistance, that is affected by charge trapping when charges
travel from the contacts through the bulk of the polymer to the active interface. One mechanism by
which water is able to create shallow trap states could be related to induced torsion along the polymer
backbone and thus, an increased disorder; this mechanism renders high-performing donor–acceptor
polymers with a narrow distribution of states particularly susceptible.
For applications that require prolonged operation, such as in active-matrix addressed light emit-
ting diode displays, a high level of threshold voltage stability is furthermore of paramount importance.
Naturally, the effects of environmental degradation described above apply to prolonged FET operation
as well and have to be addressed. However, during bias or current stress, additional trapping mecha-
nisms take place which might not occur during a single transfer or output measurement. When an
FET is operated for a prolonged time, charge carriers can continuously get trapped in the dielectric,
in localized states at the dielectric/semiconductor interface or in deep-localized states in the organic
semiconductor. These trapped charges form an immobile charge density distribution that shields the
gate induced field and thus, gives rise to an ongoing threshold voltage shift scaling with the stress dura-
tion.64 Since most of the mobile charges are not affected by this degradation mechanism, the trapped
carriers often do not lead to a change in the shape of the transfer characteristics or the extracted field-
effect mobility, as would be the case during shallow trapping. The major culprit of stress instability has
nevertheless also been related to water molecules65,66 involving the electrochemical oxidation of residual
water at the semiconductor-dielectric interface according to the basic electrochemical reaction
4 H + + O 2 + 4 e − → 2H 2 O
which converts mobile holes on the organic semiconductor to more immobile protons. The protons
generated in this reaction are assumed to diffuse into the dielectric until an equilibrium between the
surface concentration [os+] of holes in the accumulation layer and the volume concentration [H+] of pro-
tons in the dielectric (in the vicinity of the surface) is obtained. Due to its diffusive nature, the resulting
stress function has been shown to exhibit the shape of a stretched exponential, and thus scientifically
justifies a fit of the time-dependent threshold voltage shift according to
  t 
β
∆V = V0  1 − exp  −  
  τ 
where
β represents an empirical exponent
τ is the trap relaxation time
The above interpretation can describe accurately the stressing behaviour observed for many polymer
OFETs as well as explain the slow recovery exhibited by OFETs after stressing.65,66 There have been
several approaches to address this issue to achieve satisfactory levels of device performance. The use of
molecular additives to displace water molecules in the porous polymer films has recently been shown
to result in high-performance polymer OFETs that exhibit levels of environmental and threshold stabil-
ity comparable to the widely used amorphous silicon transistor technology.63 Figure 1.10 summarizes
how the incorporation of a small amount of a molecular additive such as the small molecules TCNQ,
F4-TCNQ or Aminobenzonitrile (ABN) results in improved environmental OFET stability (Figure 1.10a)
as well as improved charge carrier injection. The transistor data serves as an example of how ideal,
textbook-like devices with low contact resistance can be obtained that manifest themselves in linear
output characteristics at low source-drain voltages (Figure 1.10b); this becomes even more explicit by
extrapolation of the contact resistance using transfer line measurements (Figure 1.10d). The beneficial
effect of using molecular additives likewise manifests itself in a significantly improved stability under
bias-stress conditions reflective of the high-demanding operational conditions in an active-matrix
OLED backplane display.
FIGURE 1.10 Improving polymer FET performance and the environmental and operational stability through
the use of molecular additives (a) Linear (V DS = –5 V, dashed lines) and saturation (V DS = –50 V, solid lines) transfer
characteristics of IDTBT OFETs with (right panel) and without (left panel) 2 wt.% of TCNQ additive. Measurements
were taken successively for the as-prepared device, after 24 hours exposure to first air and then nitrogen environ-
ments and after a 12 h anneal in nitrogen. The device structure is shown as an inset (channel length L = 20 µm, chan-
nel width W = 1 mm); (b) Output characteristics of an OFET with 2 wt.% of TCNQ additive; (c) Electron affinity of
the F4TCNQ (top), TCNQ (middle) and ABN (bottom) additives used; (d) Transmission line measurements of the
normalized channel resistance as a function of channel length for FETs comprising IDTBT (blue squares), IDTBT
after air exposure (black diamonds) and IDTBT with 2 wt.% of TCNQ (green triangles), ABN (magenta triangles)
or F4TCNQ (red circles). The contact resistance can be extracted from an extrapolation to zero channel length; (e)
Constant current-stress measurements at 2 µA and room temperature comparing the threshold voltage shift of neat
IDTBT OFETs with and without additives, in nitrogen. The recovery kinetics after removing the current stress are
also shown. (With permission from Nikolka et al., Nat. Mater. 16, 356–362 (2017)).
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See (in this volume)
SOUTH AFRICA (THE TRANSVAAL): A. D. 1896 (JANUARY).
JAMESON, Dr. Leander S.:

Investigation of the Raid by the Cape Colony Assembly.

SOUTH AFRICA (CAPE COLONY): A. D. 1896 (JULY).

Indemnity for the Raid claimed by South African Republic.

SOUTH AFRICA (THE TRANSVAAL): A. D.1897 (FEBRUARY).

British Parliamentary investigation of the Raid.

SOUTH AFRICA (THE TRANSVAAL): A. D. 1897 (FEBRUARY-
JULY).
----------JAMESON, Dr. Leander S.: End--------
----------JAPAN: Start--------
JAPAN: A. D. 1890-1898.
Rise of Parliamentary parties.
Working of Constitutional Government.
"When the Emperor's nominal authority was converted into a

reality by the overthrow of the Shogun in 1868, the work was
largely due to the four clans of Satsuma, Choshu, Hizen, and
Tosa. Their aim was to destroy the Shogunate and to create an
Imperial Government, and though many other motives actuated
them, these were the two main ideas of the revolution which
grew in importance and left political results. No sooner,
however, was the Imperial Government established than it was
found that the Satsuma clan was strongly divided. There were
within it a party in favour of reform, and another party, led
by Shimazu Saburo and Saigo Takamori, who clung to old
traditions. The sword had not yet given place to the
ballot-box, and the result of a bloody contest was the
annihilation of the reactionaries. There remained, therefore,
the Satsuma men loyal to the Emperor and to the absolute
government of 1868, and with them the Choshu, Hizen, Tosa, and
other clans. Some of these clans had not always been friendly
in the past. They found it difficult to work together now.
Marquis Ito has observed that Japanese politicians are more
prone to destroy than to construct, and an opportunity to
indulge this proclivity soon presented itself.
{278}
Although the four clans were equally pledged to secure
representative government eventually, jealousy of one another
drove two of them to take up this cry as a pretext for
dissolving the alliance. The Tosa clan, now represented by
Count Itagaki, seceded accordingly in 1873, and the Hizen
clan, represented by Count Okuma, followed its example eight
years afterwards. The former organised a party called the
Fuyu-to, or Liberals, and the latter the Kaishin-to, or
Progressives. The two remaining clans of Satsuma and Choshu
were called for shortness the Sat-Cho. Such was the origin of
parliamentary parties in Japan. There was no political issue
at stake; the moving cause was simply clan jealousy, and hence
it was that Hizen and Tosa did not join hands, though both
strenuously opposed the Sat-Cho Government and each posed as
the friend of the people. Consequently, when the first Diet
met, in November, 1890, the Sat-Cho Ministry, with Marquis
Yamagata as Premier, found itself face to face with a bitter
and, it must be added, an unscrupulous opposition."
H. N. G. Bushby,
Parliamentary Government in Japan
(Nineteenth Century, July, 1899).
"The history of the Japanese Parliament [see CONSTITUTION OF
JAPAN, in volume 1], briefly told, is as follows: The first
Diet was opened in November, 1890, and the twelfth session in
May, 1898. In this brief space of time there have been four
dissolutions and five Parliaments. From the very first the
collision between the Government and the Diet has been short
and violent. In the case of the first dissolution, in
December, 1891, the question turned on the Budget estimate,
the Diet insisting on the bold curtailment of items of
expenditure. In the second dissolution, in December, 1893, the
question turned on the memorial to be presented to the Throne,
the Opposition insisting in very strong terms on the necessity
of strictly enforcing the terms of treaties with Western
Powers, the Diet regarding the Cabinet as too weak-handed in
foreign politics. The third dissolution, in June, 1894, was
also on the same question. The Cabinet, in these two latter
cases, was under the presidency of Marquis Ito (then Count),
and was vigorously pushing forward negotiations for treaty
revision, through the brilliant diplomacy of Count Mutsu, the
Foreign Minister. This strict-enforcement agitation was looked
upon by the Government as a piece of anti-foreign agitation—a
Jingo movement—and as endangering the success of the
treaty-revision negotiations. In fact, the revised treaty with
Great Britain was on the latter date well-nigh completed, it
being signed in July following by Lord Kimberley and Viscount
Aoki. It was at this stage that the scepticism of foreign
observers as to the final success of representative
institutions in Japan seemed to reach its height. … Marquis
Ito and some of the most tried statesmen of the time were out
of office, forming a sort of reserve force, to be called out
at any grave emergency. But great was the disappointment when
it was seen that after Marquis Ito, with some of the most
trusted statesmen as his colleagues, had been in office but
little over a year, dissolution followed dissolution, and it
seemed that even the Father of the Constitution was unable to
manage its successful working. … There is no question that the
Constitutional situation was at that time exceedingly critical.
"But when the war broke out the situation was "But when the
war broke out the situation was completely changed. In the
August following the whole nation spoke and acted as if they
were one man and had but one mind. In the two sessions of the
Diet held during the war the Government was most ably
supported by the Diet, and everybody hoped that after the war
was over the same good-feeling would continue to rule the
Diet. On the other hand, it was well known that the Opposition
members in the Diet had clearly intimated that their support
of the Government was merely temporary, and that after the
emergency was over they might be expected to continue their
opposition policy. Sure enough, many months before the opening
of the ninth session, mutterings of deep discontent,
especially with reference to the retrocession of the Liaotung
peninsula, began to be widely heard, and it was much feared
that the former scenes of fierce opposition and blind
obstruction would be renewed. However, as the session
approached (December, 1896), rumours were heard of a certain
'entente' between the Government and the Liberal party, at
that time the largest and the best organised in the country.
And in the coming session the Government secured a majority,
through the support of the Liberals, for most of its important
Bills.
"Now this 'entente' between Marquis Ito and the Liberals was a
great step in advance in the constitutional history of the
country, and a very bold departure in a new direction on the
part of the Marquis. He was known to be an admirer of the
German system, and a chief upholder of the policy of Chozen
Naikaku, or the Transcendental Cabinet policy, which meant a
Ministry responsible to the Emperor alone. Marquis Ito saw
evidently at this stage the impossibility of carrying on the
Government without a secure parliamentary support, and Count
Itagaki, the Liberal leader, saw in the Marquis a faithful
ally, whose character as a great constructive statesman, and
whose history as the author of the Constitution, both forbade
his ever proving disloyal to the Constitution. The 'entente'
was cemented in May following by the entrance of Count Itagaki
into the Cabinet as the Home Minister. On the other hand, this
entente' led to the formation of the Progressist party by the
union of the six Opposition parties, as well as to the union
of Count Okuma, the Progressist leader, and Count Matsugata,
leader of the Kagoshima statesmen. Their united opposition was
now quite effective in harassing the administration. At this
stage certain neutral men, particularly Count Inouye,
suggested compromise, offering a scheme of a Coalition
Cabinet. … But Count Itagaki was firm in opposing such a
compromise, saying it was tantamount to the ignoring of party
distinction, and as such was a retrogression instead of being
a forward step in the constitutional history of the country.
He finally tendered his resignation. When Marquis Ito saw that
the Count was firm in his determination, he, too, resigned,
saying that he felt so deeply obliged to the Liberals for
their late parliamentary support that he would not let the
Count go out of office alone. Thus fell the Ito Ministry after
five years' brilliant service.
{279}
"The new Cabinet, formed in September, 1896, had Count

Matsukata for Premier and Treasury Minister; Count Okuma for
Foreign Minister; and Admiral Kabayama, the hero of the Yaloo
battle, for Home Minister. There were at this time three
things that the nation desired. It wanted to be saved from the
impending business depression. It wished to see Japanese
Chauvinism installed at the Foreign Office, and the shame of
the retrocession of the Liaotung peninsula wiped off. It
hoped, lastly, to see a Parliamentary Government inaugurated
and all the evils of irresponsible bureaucracy removed. The
statesmen now installed in office aspired to satisfy all these
desires, and they were expected to work wonders. But,
unfortunately, the Cabinet lacked unity. … Early in the fall
[of 1897] Count Okuma resigned office, saying that he felt
like a European physician in consultation over a case with
Chinese doctors. … Count Okuma led away the majority of the
Progressist party, and the Government was left with but an
insignificant number of supporters. As soon as the Diet met,
the spirit of opposition manifested was so strong that the
Ministers asked the Emperor to issue an edict for dissolution.
It was expected that the government would at once appeal to
the country with some strong programme. But to the
astonishment of everybody the Ministry resigned the very next
day. In the midst of the general confusion which followed,
Marquis Ito's name was in the mouth of everybody. He was
unanimously hailed as the only man to bring order into the
political situation. In January following [1898] the new
Cabinet was announced with Ito for Premier, Count Inouye for
the Treasury, and Marquis Saionji, one of the best cultured,
most progressive, and, perhaps, also most daring of the
younger statesmen, for Education Minister."
Tokiwo Yokoi,
New Japan and her Constitutional Outlook
(Contemporary Review, September, 1898).
JAPAN: A. D. 1895.
The war with China.
Treaty of Shimonoseki.
Korean independence secured.
Part of Feng-tien, Formosa and the Pescadores ceded by China.
Relinquishment of Feng-tien by Japan.

CHINA: A. D. 1894-1895.
JAPAN: A. D. 1896.
Affairs in Formosa.
Retirement of Marquis Ito.
Progressists in power.
Destructive sea-wave.
Serious risings of the Chinese in Formosa against the newly

established Japanese rule in that island were said to have
been caused by insolent and atrocious conduct on the part of
the Japanese soldiery. Possibly a decree which prohibited the
importation of opium into Formosa, and which placed the
medicinal sale of the drug under close restrictions, had
something to do with the discontent. In Japan, the able
statesman, Marquis Ito, was made unpopular by his yielding of
the Liao Tung peninsula (in the Fêng-tien province of
China,—see, in this volume, CHINA: A. D. 1894-1895), under
pressure from Russia, Germany and France. He retired from the
government, and Count Matsukata became Premier in September,
with a cabinet of the Progressist (Kaishinto) party, which
advocated resistance to Russia, and opposition generally to
the encouragement of foreign enterprises in Japan. A frightful
calamity was suffered in June, when a prodigious wave, probably
raised by some submarine volcano, overwhelmed a long stretch
of northeastern coast, destroying some 30,000 people, and
sweeping out of existence a number of considerable towns.
Annual Register, 1896.
JAPAN: A. D. 1897.
New tariff.
A new tariff, regulating the customs duties levied in all

cases wherein Japan is not bound by treaty stipulations, was
adopted in March, 1897. The duties imposed range from 5 to 40
per cent., ad valorem, the higher being laid upon liquors and
tobacco. The "Japan Gazette" is quoted as saying in
explanation: "The statutory tariff fixes the duties to be
collected on every article imported into Japan from countries
that have not concluded tariff conventions with her, or that
are not entitled to the most-favored-nation treatment in
regard to the tariff. Spain, Portugal, Greece, and many other
countries have no tariff conventions with Japan and no
favored-nation clause, in regard to tariff, in their new
treaties with this country. The United States, Belgium,
Holland, Russia, and others have the favored-nation clause and
will get the benefit of the lesser duties on items named in
the different mentioned tariffs. There will, therefore, be two
columns of figures in the printed general tariff list, showing in
the first column the duties on the articles named in the
conventional tariffs, and in the second column the duties on
the same articles imported from countries that have no tariff
convention with Japan, and that are not entitled to
favored-nation treatment. For instance, most textile articles
are subject to a duty of 10 per cent in the conventional
tariff column and to a duty of 15 per cent in the statutory
column."
United States Consular Reports,

July and September, 1897,
pages 475 and 91.
JAPAN: A. D. 1897 (October).

Introduction of the gold standard.

MONETARY QUESTIONS: A. D. 1897 (MARCH).
JAPAN: A. D. 1897 (November).

Treaty with the United States and Russia to suspend pelagic
sealing.

BERING SEA QUESTIONS.
JAPAN: A. D. 1897-1898.
Contentions with Russia in Korea.

KOREA: A. D. 1895-1898.
JAPAN: A. D. 1898-1899.
The struggle between clan government and party government.
"When, in January 1898, Marquis Ito made an attempt to win the

country back to non-party government and efficiency by forming
an independent Ministry in defiance of the Liberal demands, he
was acting no doubt from no mere clan instinct, but, as he
conceived, in the highest interests of the realm. His
experiment was not destined to succeed. In the general
election of March 1898, 109 Progressives and 94 Liberals were
returned as Representatives in a House of 300. A common hunger
for office and a common sense of humiliation at their
treatment by the greater statesmen of the clans united the two
parties under one banner as they had not been united since 1873.
At last they took up in earnest the crusade against clan
government, which, logically, they should have commenced
together exactly a quarter of a century before. They called
their coalition the 'Kensei-to,' or Constitutional Party.
Japan is a country of rapid progress, but she is lucky that
for twenty-five years the formation of the Kensei-to was
deferred while she was content to be guided through difficult
times by clansmen more skilled in statecraft than the usurient
nobodies who were kicking at the heels of Counts Okuma and
Itagaki.
{280}
"Meanwhile Marquis Ito had to decide how he would act. He had

tried to govern with the help of a party and had partially
succeeded. He had tried to govern without one, and had
discovered that it was impossible. The two parties could no
longer be played off one against the other. They were united,
and with fifty new recruits formed the Kensei-to, 253 strong.
There remained only nineteen clan government sympathisers,
calling themselves National Unionists, and twenty-eight
Independents. In these difficult circumstances Marquis Ito's
decision was a bold one, and in its consequences far-reaching.
He advised that Count Okuma, the Progressive leader of the
Kensei-to should be summoned to form a Cabinet in conjunction
with his Liberal colleague, Count Itagaki. His advice was
followed by the Emperor, but with the significant condition
that the Ministries of War and the Navy were to be retained by
clansmen. The Emperor was not disposed to allow constitutional
experiments in these departments. On the 28th of June 1898,
Marquis Ito resigned, and on the 30th the Okuma-Itagaki
Cabinet was formed.
"It now seemed to many that the death-blow had been given to
clan government, and that at last the era of government by
party had commenced. … The elements of which the Kensei-to was
composed were the two great ones of the Progressives, led by
Count Okuma, and the Liberals, led by Count Itagaki. These two
parties acted together in a condition of veiled hostility.
There was coalition without any approach to amalgamation. A
common hunger for office, a common dislike for clan
government, obscured for a little while a mutual jealousy and
distrust. Meanwhile the Kensei-to as a whole, and both wings
of it, were divided into endless clubs, cliques, and
associations. Our own Temperance, Colonial, Church, and China
parties are affable and self-effacing in comparison. Thus, to
name only a few of the political divisions of the Kensei-to,
there were the territorial associations of the Kwanto-kai (led
by Mr. Hoshi), the Hokuriku-kai (led by Mr. Sugita), the
Kyushu Kurabu (led by Mr. Matsuda), the Tohoku-dantai, the
Chugoku-kai, and the Shigoku-kai; there were the Satsuma
section, the Tosa section, the Kakushinto, the Young
Constitutionalists, the Senior Politicians (such as Baron
Kusumoto, Mr. Hiraoka, the chief organiser of the coalition,
and others), the Central Constitutionalist Club, and so forth.
Each clique had its private organisation and animosities; each
aspired to dictate to the Cabinet and secure portfolios for
its members in the House. They combined and recombined among
themselves. … Clearly, however loyally the two leaders wished
to work together, each must find it impossible in such
circumstances to preserve discipline among his own followers.
Indeed, the leaders scarcely tried to lead. … It was
impossible to carry on the Government under such conditions.
The Okuma-Itagaki Cabinet fell, and Field Marshal the Marquis
Yamagata, Premier of the first Japanese Ministry, was summoned
by the Emperor. Once more a clan Ministry, independent of
party, was formed; once more it seemed as though party
government was to be indefinitely postponed. … Marquis
Yamagata formed his Ministry in November 1898, on strictly
clan lines. … Being an old soldier, he wisely determined to
profit by experience and seek an ally. No one knew better than
himself the need of passing the Land Tax Bill, on which the
efficiency of the national defence and the future of Japan
depended. … It was natural, therefore, for him to approach the
Liberals, who had shown themselves favourable to an increase
of the Land Tax. … On the 27th of November the support of the
Liberals was assured, an event which prompted the 'Jiji' to
express its joy that Marquis Yamagata had become a party man,
leaving 'the mouldy, effete cause of the non-partisan
Ministry.' The Government party consisted now of the National
Unionists (in favour of clan government' and loyal followers
of Marquis Yamagata), the Liberals, and a few so-called
Independents (who, of course, speedily formed themselves into
a club), giving the Government a majority of about fifteen or
twenty votes in the House. …
"The first session of Marquis Yamagata's second Ministry will

always be remembered in Japan because the Land Tax Bill was
successfully passed through both Houses. … But the most
important episode of the session, from a parliamentary point
of view, was a remarkable act of self-denial on the part of
the Liberals. In March of this year [1899] they agreed not to
demand office from Marquis Yamagata for any of their number,
though they were to be free to accept such offices as he might
of his own bounty from time to time be able to offer them. If
this unprecedented pledge be loyally adhered to, it marks a
very great stride towards effective party government in the
future. … The hope of the Liberals now lies, not in the
immediate enjoyment of the sweets of office, but in winning
over Marquis Ito to their party. If he were to show the way,
it is probable that many more of the leading clan statesmen
would take sides, in which case, to adopt Mr. Bodley's phrase,
political society would be divided vertically as in England, not
horizontally as in France, and either party on obtaining a
majority in the House would be able to find material in its
own ranks for an efficient Cabinet. At present neither is in
that happy position."
H. N. G. Bushby,
Parliamentary Government in Japan
(Nineteenth Century, July, 1899).
JAPAN: A. D. 1899 (May-July).

Representation in the Peace Conference at The Hague.

PEACE CONFERENCE.
JAPAN: A. D. 1899 (July).

Release from the treaties with Western Powers
which gave them exterritorial rights.
Consular jurisdictions abolished.
"Japan has been promoted. The great sign that Europe regards a
Power as only semi-civilised is the demand that all who visit
it, or trade in it, should be exempted from the jurisdiction
of the local Courts, the Consuls acting when necessary as
Judges. This rule is maintained even when the Powers thus
stigmatised send Ambassadors, and is, no doubt, very keenly
resented. It seems specially offensive to the Japanese, who
have a high opinion of their own merits, and they have for
seventeen years demanded the treatment accorded to fully
civilised States. As the alliance of Japan is now earnestly
sought by all Europe this has been conceded, and on Monday,
July 17th, the Consular jurisdiction ceased. (Owing to some
blunder, the powers of the French and Austrian Consuls last a
fortnight longer, but the difference is only formal.) The
Japanese are highly delighted, and the European traders are
not displeased, as with the Consular jurisdictions all
restrictions on trading with the interior disappear."
The Spectator
(London), July 22, 1899.
{281}
The early treaties of Japan with Western Powers, which gave

the latter what are called rights of extra-territoriality, or
exterritoriality, for all their subjects (the right, that is,
to administer their own laws, by their own consular or other
courts, upon their own subjects, within a foreign country),
were modified in 1894. Japan then became free to extinguish
the foreign courts on her soil at the end of five years, upon
giving a year's notice, which she did as stated above. Her
government has thus attained a recognized peerage in
sovereignty with the governments of the Western world. At the
same time, the whole country has been thrown open to foreign
trade—restricted previously to certain ports.
In careful preparation of the Japanese people for this

important change in their relations with the foreign world,
the following imperial rescript was issued at the end of June,
1899: "The revision of the treaties, our long cherished aim,
is to-day on the eve of becoming an accomplished fact; a
result which, while it adds materially to the responsibilities
of our Empire, will greatly strengthen the basis of our
friendship with foreign countries. It is our earnest wish that
our subjects, whose devoted loyalty in the discharge of their
duties is conspicuous, should enter earnestly into our
sentiments in this matter, and, in compliance with the great
policy of opening the country, should all unite with one heart
to associate cordially with the peoples from afar, thus
maintaining the character of the nation and enhancing the
prestige of the Empire. In view of the responsibilities that
devolve upon us in giving effect to the new treaties, it is
our will that our ministers of state, acting on our behalf,
should instruct our officials of all classes to observe the
utmost circumspection in the management of affairs, to the end
that subjects and strangers alike may enjoy equal privileges
and advantages, and that, every source of dissatisfaction
being avoided, relations of peace and amity with all nations
may be strengthened and consolidated in perpetuity."
Obedient to this command, the Minister President of State,

Marquis Yamagata, published the following instruction on the
1st of July: "The work of revising the treaties has caused
deep solicitude to His August Majesty since the centralization
of the Government, and has long been an object of earnest desire
to the people. More than twenty years have elapsed since the
question was opened by the dispatch of a special embassy to
the West in 1871. Throughout the whole of that interval,
numerous negotiations were conducted with foreign countries
and numerous plans discussed, until finally, in 1884, Great
Britain took the lead in concluding a revised treaty, and the
other powers all followed in succession, so that now the
operation of the new treaties is about to take place on the
17th of July and the 4th of August.
"The revision of the treaties in the sense of placing on a

footing of equality the intercourse of this country with
foreign states was the basis of the great liberal policy
adopted at the time of the restoration, and that such a course
conduces to enhance the prestige of the Empire and to promote
the prosperity of the people is a proposition not requiring
demonstration. But if there should be anything defective in
the methods adopted for giving effect to the treaties, not
merely will the object of revision be sacrificed, but also the
country's relations with friendly powers will be impaired and its
prestige may be lowered. It is, of course, beyond question
that any rights and privileges accruing to us as a result of
treaty revision should be duly asserted. But there devolves
upon the Government of this Empire the responsibility, and
upon the people of this Realm the duty, of protecting the
rights and privileges of foreigners, and of sparing no effort
that they may one and all be enabled to reside in the country
confidently and contentedly. It behooves all officials to
clearly apprehend the august intentions and to pay profound
attention to these points."
With still finer care for the honor and good name of Japan,
the following instruction to schools was published on the same
day by Count Kabayma, the Minister of State for Education:
"The schools under the direct control of the Government serve
as models to all the public and private educational
institutions throughout the country. It is therefore my
earnest desire that the behavior of the students at such
schools should be regulated with notably strict regard to the
canons of propriety, so that they may show themselves worthy
of the station they occupy. The date of the operation of the
revised treaties is now imminent, and His Imperial Majesty has
issued a gracious rescript. It may be expected that the coming
and going of foreigners in the interior of the country will
henceforth grow more frequent, and if at such a time students
be left without proper control, and suffered to neglect the
dictates of propriety by cherishing sentiments of petty
arrogance and behaving in a violent, outrageous, or vulgar
manner, not only will the educational systems be brought into
discredit, but also the prestige of the country will be
impaired and its reputation may even be destroyed. For that
reason I have addressed an instruction to the local governors
urging them to guard against any defects in educational
methods, and I am now constrained to appeal to the Government
schools which serve for models. I trust that those upon whom
the functions of direction and teaching devolve, paying
respectful attention to the august intention, will discharge
their duties carefully towards the students, and, by securing
the latter's strict adherence to rules, will contrive that
they shall serve as a worthy example to the schools throughout
the country."
United States Consular Reports,

October, 1899, page 285.
JAPAN: A. D. 1899 (August).

Prohibition of religious instruction in the government schools.
Some important regulations for the national schools were

promulgated in August by the Minister of Education, having the
effect, probably intended, of discouraging attendance at the
Christian mission schools, and stimulating a preference for
the schools of the national system. They forbade religious
exercises or instruction in any schools that adopt the
curriculum of the national schools, while, at the same time,
they allow admission from no others to the higher schools of
the national system without examination. Students in the
middle schools of the national system are exempted from
conscription, while others are not. That the aim in this
policy is to strengthen the national schools, rather than to
interfere with religious freedom, seems probable.
{282}
JAPAN: A. D. 1899 (December).

Adhesion to the arrangement of an "open door" commercial
policy in China.

CHINA: A. D. 1899-1000 (SEPTEMBER-FEBRUARY).
JAPAN: A. D. 1900.
Naval strength.

NAVIES OF THE SEA POWERS.
JAPAN: A. D. 1900 (June-December).

Co-operation with the Powers in China.

CHINA.
JAPAN: A. D. 1900 (July)

Failure of attempts to entrust the Japanese government
with the rescue of the foreign Legations at Peking.

CHINA: A. D. 1900 (JUNE-JULY).
JAPAN: A. D. 1900 (August-October).

The new party of Marquis Ito.
The letters of the Tokio correspondent of the London "Times"

describe interestingly the genesis of a new party of which
Marquis Ito has taken the lead, and which took control of the
government in October, 1900. Various parties, the career of
which the writer reviews, had been formed in opposition to the
veteran statesmen who continued to hold the reins of government
after constitutional forms were introduced in 1880. But very
few of the party politicians who constructed these parties,
says the writer, had held high office. "They were without the
prestige of experience. To put such men on the administrative
stage while the gallery was occupied by the greybeards—the
'Meiji statesmen,' as they are called—who had managed the
country's affairs since the Restoration, would have seemed a
strange spectacle in the eyes of the nation. The Meiji
statesmen, however, persistently declined to be drawn into the
ranks of the political parties. They gave the latter plenty of
rope; they even allowed them to administer the State, which
essay ended in a fiasco; and they took them into alliances
which served chiefly to demonstrate the eagerness of these
politicians for office and emoluments. But there was no
amalgamation. The line of demarcation remained indelible. …
"The political parties, discovering the impossibility of

becoming a real power in the State without the coöperation of
the Meiji statesmen, asked Marquis Ito to assume their
leadership. Marquis Ito may be said to possess everything that
his country can give him. He has the unbounded confidence of
his Sovereign and his countrymen; he is loaded with titles and
honours, and a word from him can make or mar a Ministry. It
seems strange that such a man should step down from his
pedestal to become a party leader; to occupy a position which
can bring no honour and must at once create enemies. Yet
Marquis Ito has consented. He issued his manifesto. It is in
two respects a very remarkable document. First, it tells the
politicians that their great fault has been self-seeking; that
they have set party higher than country; office and emolument
above public duty and political responsibility. Secondly, it
informs them in emphatic terms that Parliamentary Cabinets are
unconstitutional in Japan; that "Ministers and officials must
be appointed by the Sovereign without any reference to their
party connexions. The politicians who place themselves under
Marquis Ito's leadership must eschew the former failing and
abandon the latter heresy. It would be impossible to imagine a
more complete reversal of the tables. The men who, ten years
ago, asked the nation to condemn the Meiji statesmen on a
charge of political self-seeking are now publicly censured by
the chief of these statesmen for committing the very same sin
in their own persons; and the men who for ten years have made
Parliamentary Cabinets the text of their agitation now enrol
themselves in a party which openly declares such Cabinets to
be unconstitutional."
The new party calls itself the "Association of Friends of the

Constitution" (Rikken Seiyukai). "In its ranks are found the
whole of the Liberals, and many members of the Diet who had
hitherto maintained an independent attitude, so that it can
count on 152 supporters among the 300 members of the Lower
House. … The Opposition, the Progressists, command only 90
votes, and the remainder of the House is composed mainly of
men upon whose support the Cabinet can always reckon. In fact,
now for the first time since the Diet opened, does the
direction of State affairs come into the hands of Ministers
who may rest assured of Parliamentary cooperation."
Marquis Yamagata, who had conducted the administration for

nearly two years, resigned in October, and Marquis Ito brought
his new party into power. His Cabinet "does not include one of
the elder statesmen—the 'clan statesmen'—except the marquis
himself. Among the seven portfolios that have changed
hands—those of War and of the Navy are still held as before—
three have been given to unequivocal party politicians,
leaders of the Liberals, and four to men who may be regarded
as Marquis Ito's disciples. … The Yamagata Cabinet consisted
entirely of clan statesmen and their followers. The Ito
Cabinet has a clan statesman for leader and his nominees for
members. It may be called essentially a one man Ministry, so
far does the Premier tower above the heads of his colleagues."
JAPAN: A. D. 1900-1901.
Strategic importance of Korea.
Interest in the designs of Russia.

KOREA: A. D. 1900.
JAPAN: A. D. 1901.
Movement to erect a monument to commemorate the
visit of Commodore Perry.
A movement in Japan to erect a monument at Kurihama, the

landing place of the American expedition, commanded by
Commodore Matthew C. Perry, which visited Japan in 1853 and
brought about the opening of that country to intercourse with
the western world (see, in volume 3, JAPAN: A. D. 1852-1888),
was announced to the State Department at Washington by the U.
S. Consul-General at Yokohama, in March, 1901. The undertaking
is directed by the "American Association of Japan," of which
the Japanese Minister of Justice is President, and its purpose
is to commemorate an event which the Association, in a
published circular, declares to be "the most memorable" in the
annals of Japan. The language of the circular, in part, is as
follows: "This visit of Commodore Perry was in a word the
turning of the key which opened the doors of the Japanese
Empire to friendly intercourse with the United States, and
subsequently to the rest of the nations of Europe on similar
terms, and may in truth be regarded as the most memorable
event in our annals—an event which paved the way for and
accelerated the introduction of a new order of things, an
event that enabled the country to enter upon the unprecedented
era of National ascendancy in which we are now living.
{283}
Japan has not forgotten—nor will she ever forget—that next to
her reigning and most beloved sovereign, whose high virtues
and great wisdom are above all praise, she owes, in no small
degree, her present prosperity to the United States of
America, in that the latter rendered her a great and lasting
service already referred to. After the lapse of these
forty-eight years, her people, however, have come to entertain
but an uncertain memory of Kurihama, and yet it was there that
Commodore Perry first trod on the soil of Japan and for the
first time awoke the country from a slumberous seclusion of
three centuries—there it was where first gleamed the light
that has ever since illumined Japan's way in her new career of
progress."
----------JAPAN: End--------

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Conjugated polymers.

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Conjugated Polymers: Perspective, Theory, and New

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1 Conjugated Polymer-Based OFET Devices........................................................1

11 Poly(3-alkylthiophenes): Controlled Manipulation of Microstructure

Maged Abdelsamie Magnus Berggren

Julio M. D’Arcy Magnus P. Jonsson

Larry Dalton Antoine Kahn

Yifan Diao Richard B. Kaner

Cheng-Wei Lin Seth R. Marder

Department of Polymer Science and

Yang Lu Chrysanthi M. Moysidou

Mark Nikolka Adam D. Printz

Anna M. Österholm Elsa Reichmanis

Roisin M. Owens John R. Reynolds

Anna-Maria Pappa Daniel Rodriquez

Suchol Savagatrup Michael F. Toney

Melda Sezen-Edmonds Klas Tybrandt

Chaohong Zhang Lingyun Zhou

Guoyan Zhang Igor Zozoulenko

1.2 State of OFET Techn​ology​/Appl​icati​ons/

1.3 Recent Developments in Polymer OFET Materials – From

1.4 Charge Transport in Polymer OFETs

1.6 Charge Carrier Mobility and Artefacts

Drain current (ID /A)

Gate Voltage (VG /V) Drain Voltage (VD /V)

JAMESON, Dr. Leander S.:

See (in this volume)

JAMESON, Dr. Leander S.:

See (in this volume)

JAMESON, Dr. Leander S.:

See (in this volume)

----------JAMESON, Dr. Leander S.: End--------

"When the Emperor's nominal authority was converted into a

"The new Cabinet, formed in September, 1896, had Count

See (in this volume)

Serious risings of the Chinese in Formosa against the newly

Annual Register, 1896.

A new tariff, regulating the customs duties levied in all

United States Consular Reports,

JAPAN: A. D. 1897 (October).

See (in this volume)

JAPAN: A. D. 1897 (November).

See (in this volume)

See (in this volume)

"When, in January 1898, Marquis Ito made an attempt to win the

"Meanwhile Marquis Ito had to decide how he would act. He had

"The first session of Marquis Yamagata's second Ministry will

JAPAN: A. D. 1899 (May-July).

See (in this volume)

JAPAN: A. D. 1899 (July).

1.2 State of OFET Technology/Applications/

1.3 Recent Developments in Polymer OFET Materials – From

1.4 Charge Transport in Polymer OFETs

1.6 Charge Carrier Mobility and Artefacts