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Interface Engineering in Organic Field-Effect Transistors
Interface Engineering in Organic Field-Effect
Transistors

Xuefeng Guo
Hongliang Chen
Authors All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Xuefeng Guo publisher do not warrant the information
Peking University contained in these books, including this book,
202 Chengfu Rd to be free of errors. Readers are advised to keep
Haidian District in mind that statements, data, illustrations,
100871 Beijing procedural details or other items may
China inadvertently be inaccurate.

Prof. Hongliang Chen Library of Congress Card No.: applied for

Zhejiang University
No. 866 Yu Hang Tang Rd British Library Cataloguing-in-Publication Data
Xihu District A catalogue record for this book is available
310027 Hangzhou from the British Library.
China
Bibliographic information published by
Cover Image: © blackdovfx/Getty Images the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed bibliographic
data are available on the Internet at
<http://dnb.d-nb.de>.

© 2023 WILEY-VCH GmbH, Boschstraße 12,

69469 Weinheim, Germany

All rights reserved (including those of

translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other
means – nor transmitted or translated into a
machine language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even when
not specifically marked as such, are not to be
considered unprotected by law.

Print ISBN: 978-3-527-35145-9

ePDF ISBN: 978-3-527-84046-5
ePub ISBN: 978-3-527-84047-2
oBook ISBN: 978-3-527-84048-9

Typesetting Straive, Chennai, India

 v

Contents

Preface ix
Author Biographies xi
List of Acronyms and Abbreviations xiii

1 Introduction 1
1.1 Different Interfaces in OFETs 1
1.2 Brief Historic Overview of Interface Engineering in OFETs 3
1.3 Scope of the Book 3

2 Interfacial Modification Methods 7

2.1 Noncovalent Modification Methods 7
2.1.1 Charge Insertion Layer at the Electrode Surface 7
2.1.2 Dielectric Surface Passivation Methods 9
2.2 Covalent Modification Methods 12
2.2.1 SAM Modification of Electrodes 12
2.2.2 SAM Modification of Dielectrics 12
2.2.2.1 SAM/SiO2 Dielectrics 14
2.2.2.2 SAM/High-k Dielectrics 14
2.2.2.3 Self-Assembled Monolayer Field-Effect Transistors (SAMFETs) 28
2.3 Efforts in Developing New Methods 31

3 Semiconductor/Semiconductor Interface 33
3.1 Influence of Additives on a Material’s Nucleation and Morphology 37
3.1.1 Solvent Additives 37
3.1.2 Nucleating Agents 41
3.1.3 Template-Mediated Crystallization 43
3.1.4 Blending with Insulating Polymers 45
3.1.5 Blending with Polymer Elastomer: Nanoconfinement Effect 50
3.2 Enhancing the Performance Through Semiconductor
Heterojunctions 55
3.2.1 Planar Bilayer Heterostructures 57
3.2.2 Molecular-Level Heterojunction 61
3.2.3 Supramolecular Arrangement of the Heterojunctions 64
vi Contents

3.3 Integrating Molecular Functionalities into Electrical Circuits 69

3.3.1 Charge-Trapping-Induced Memory Effect 69
3.3.2 Photochromism-Induced Switching Effect 72

4 Semiconductor/Electrode Interface 77
4.1 Work Function Tuning for Better Contact 79
4.1.1 SAM Modification 80
4.1.2 Charge Insertion Layer Modification 84
4.1.3 Polymer-Based Electrodes 89
4.1.4 Carbon Nanomaterial-Based Electrodes 92
4.1.5 Covalent Bond Formation at the Molecular Level 97
4.2 Installing Switching Effects at Semiconductor/Electrode Interface 100

5 Semiconductor/Dielectric Interface 103

5.1 Dielectric Modification to Tune Semiconductor Morphology 105
5.1.1 Dielectric Surface Energy Control 106
5.1.1.1 Modify with SAM 106
5.1.1.2 Surface Modification with Polymers 112
5.1.2 Dielectric Microstructure Design 113
5.1.2.1 Roughness Effect 114
5.1.2.2 Nano-fabrication Created Microstructure 116
5.1.2.3 Self-assembled Morphology of Dielectric 118
5.2 Eliminating Interfacial Traps 120
5.2.1 Dielectric Surface Passivation (Treatment) Methods 121
5.2.1.1 Polymer Encapsulation of Dielectrics 122
5.2.1.2 Gap Dielectrics 124
5.2.2 SAM/SiO2 Dielectrics 126
5.2.2.1 Provide Efficient Insulating Barrier Height 127
5.2.2.2 Control Surface Polarity and Carrier Density 128
5.2.3 SAM/High-k Dielectrics 131
5.2.3.1 Fundamentals of SAM-Modified High-k Dielectrics 132
5.2.3.2 SAM/High-k Hybrid Dielectrics for Flexible Substrate 134
5.2.4 Self-assembled Monolayer Field-Effect Transistors (SAMFETs) 137
5.2.4.1 Molecule Design for SAMFETs 137
5.2.4.2 Morphology Control of SAMFET 139
5.3 Integrating New Functionalities 141
5.3.1 Photoresponsive Dielectrics 142
5.3.2 Other External Stimuli-Responsive Dielectrics 144
5.3.2.1 Pressure Sensor 145
5.3.2.2 Thermal Sensor 147
5.3.2.3 Magnetic Sensor 147
5.3.2.4 Multifunctional Sensor 148
5.3.3 Integrating Memory Effect at the Dielectrics 148
 Contents vii

6 Semiconductor/Environment Interface 155

6.1 Device Optimization to Improve Sensing Performance 156
6.1.1 Monolayer Functionalization 156
6.1.2 Bilayer Heterojunction Approach 158
6.1.3 Remote Floating Gate 159
6.2 OECT-Based and EGOFET-Based Sensors 160

7 Interfacing Organic Electronics with Biology 165

7.1 Integration of OFETs/OECTs with Nonelectrogenic Cells 166
7.2 Integration of Flexible Bioelectronics with Electrogenic Cells 170
7.3 Light/Cell/Device Interfaces 174

8 Concluding Remarks and Outlook 179

8.1 New Challenges in Molecular Design 179
8.2 High-Quality OSC Films: Self-Assembly Control 180
8.3 High-Performance Scalable Flexible Optoelectronics 180
8.4 Exploration of Novel Structures: Organic/2D Heterostructures and
Vertical Structures 181
8.5 Instability: Stability in Aqueous Media and Thermal Stability in Hygienic
Applications 181
8.6 Multifunctional Sensor Systems 183

References 185
Index 251
 ix

Preface

The development of microelectronics into modern integrated circuits over the

past 75 years was the result of continuous efforts of huge teams of scientists and
engineers. The device performance of microelectronic devices is mainly determined
by the properties of the materials used and their corresponding interfaces, just as
Nobel laureate Herbert Kroemer coined, “the interface is the device.” Understand-
ing and governing the charge transfer phenomena occurring at the interfaces could
revolutionize a number of related fields, including batteries, catalysis, data storage,
energy harvesting, imaging displays, sensing devices, and even solar cells. For these
reasons, interface engineering of these heterojunctions has captured the attention
of a broad cross section of scientific and industrial communities.
In comparison with traditional complementary metal oxide semiconductor
transistors, the advantages of organic field-effect transistors (OFETs) originate from
how OFETs can be manufactured, including the considerable variety in molecular
design, low cost, lightweight, mechanical flexibility, solution processability, and
large-area fabrication. The key concept of this book is to use interface engineering
strategies to improve the inherent properties of OFETs as well as to build novel
functional devices based on OFETs. Both are of great importance for laying the
foundation for the OFET research. For the first point, rapid progress has been made
on each isolated component of OFETs to improve the performance, with major
emphasis on organic semiconducting material design and relevant film processing
methods. Although the improved electronic properties of these materials could
offer device performance advantages, interfacial barriers between the semicon-
ductors, dielectric layers, and electrodes are often treated as secondary concerns
in comparison with the generation and preservation of carrier population in the
semiconductor itself. In pursuit of high performance, OFETs will inevitably require
an optimized carrier transport pathway that leverages all the device layers and their
corresponding interfaces. This should be as important as the material design and
relevant film processing methods.
The second point is that how to “use” OFETs is another important issue in
OFET research. Of course, huge progress has been made to develop a variety of
functional devices based on OFETs, such as chemo/biosensors, photodetectors,
integrated circuits, and flexible electronics. They can be realized by using various
strategies, for example, designing functional semiconducting materials, developing
x Preface

semiconductor processing methods, and tailoring functional interlayers. In this

book, however, we will specifically survey the most recent and important works
employing interface engineering strategies to develop functional OFET devices.
We believe that interfacial modification is a much simpler, more efficient way to
integrate functionalities.
This book will focus on interface engineering of OFETs and aim to provide funda-
mental understandings of the interplay between the molecular structure, assembly,
and emergent functions at the molecular level and consequently offer novel insights
into designing a new generation of multifunctional integrated circuits and sensors
toward practical applications. Actually, the interface engineering strategy can be
leveraged to improve the efficiency and stability of perovskite solar cells. We believe
that this book will draw widespread interest from researchers working on organic
electronics, chemo- and biosensors, solar cells, flexible electronics, and other
device-related fields.
We would like to thank Wiley for offering the opportunity to prepare this
book, especially Ms. Alice Qian. We would also like to express our deep gratitude
to Ms. Katrina Maceda and Ms. Monica Chandra Sekar who have contributed
their time and outstanding expertise to make this book possible. Also, thanks to
Dr. Weining Zhang for the helpful discussions during the preparation of the book.
Finally, we hope that the readers of this book will find it both useful and delightful.

Beijing, China Xuefeng Guo and Hongliang Chen

December 2022
 xi

Author Biographies

Xuefeng Guo received his PhD in 2004 from the Institute of Chemistry, Chinese
Academy of Sciences, Beijing. From 2004 to 2007, he was a postdoctoral research
scientist at the Columbia University Nanocenter. He joined the faculty as a professor
under the “Peking 100-Talent” Program at Peking University in 2008. In 2012, he
won the National Science Funds for Distinguished Young Scholars of China. His
current research is focused on functional nanometer/molecular devices. Professor
Xuefeng Guo has authored over 210 scientific publications and has received
numerous scientific awards, including the First prize of Ministry of Education
Natural Science Award.
Hongliang Chen received his PhD in 2016 from the College of Chemistry
and Molecular Engineering, Peking University, under the guidance of Professor
Xuefeng Guo. From 2016 to 2018, he worked as a research scientist at the Core
R&D department in Dow Chemical Company. Then he moved to Northwestern
University in United States and worked as a postdoctoral research fellow in Professor
Sir Fraser Stoddart’s group from 2018 to 2021. He joined Zhejiang University as
an assistant professor under “ZJU 100-Talent” Program in June 2021. His research
interests are focused on organic functional devices and molecular electronics.
 xiii

List of Acronyms and Abbreviations

1D one-dimensional
2D two-dimensional
3D three-dimensional
AFM atomic force microscopy
AZOs azobenzenes
BCB divinyltetramethyldisiloxane-bis(benzocyclobutene)
BTBT [1]benzothieno[3,2-b][1]-benzothiophene
C8 -BTBT 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene
CIL charge insertion layer
CNTs carbon nanotubes
CT charge-transfer
D–A donor–acceptor
DAE diarylethene
DNTT dinaphtho[2,3-b:2′ ,3′ -f ] thieno[3,2-b]thiophene
DOS densities of state
EA energy gap of OSC
EF Fermi level of electrodes
EVAC vacuum energy level
FLG few-layer graphene
GOs graphene oxides
Gr graphene
HMDS hexamethyldisilazane
HOMO highest occupied molecular orbital
k relative permittivity or dielectric constant
LB Langmuir–Blodgett
LUMO lowest unoccupied molecular orbitals
MWCNTs multiwalled carbon nanotubes
NDI naphthalenediimide
NHCs N-heterocyclic carbenes
OFET organic field-effect transistor
OLET organic light-emitting transistor
OSCs organic semiconductors
P3HT poly(3-hexylthiophene)
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[Inhoud]

De volgende aflevering (No. 311) bevat:

DE WRAAK DER MALABAREN.

 Inhoudsopgave

I. Raffles gaat op jacht. 1

II. Het gevecht met de beren. 5
III. Het verhaal van Dobrinsky. 11
IV. Aan den vooravond van den slag. 15
V. De veldslag. 19
VI. Een gevaarlijke onderneming. 26
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2 Romanofs Romanoffs 1
2 aanstaanden aanstaande 1
3 erkenden herkenden 1
3 hecht heft 2
3 Ik ik 1
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antwoorde antwoordde 1
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4, 6 [Niet in bron] . 1
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