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Polymer Photovoltaics
Materials, Physics, and Device Engineering
 View Online

RSC Polymer Chemistry Series

Editor-in-Chief:
Professor Ben Zhong Tang, The Hong Kong University of Science and
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Technology, Hong Kong, China

Series Editors:
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Professor Stephen Craig, Duke University, USA
Professor Jianhua Dong, National Natural Science Foundation of China, China
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Titles in the Series:

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2: M olecular Design and Applications of Photofunctional Polymers and
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5: Healable Polymer Systems
6: Thiol-X Chemistries in Polymer and Materials Science
7: Natural Rubber Materials: Volume 1: Blends and IPNs
8: Natural Rubber Materials: Volume 2: Composites and Nanocomposites
12:26:40.

9: Conjugated Polymers: A Practical Guide to Synthesis

10: Polymeric Materials with Antimicrobial Activity: From Synthesis to
Applications
11: Phosphorus-Based Polymers: From Synthesis to Applications
12: Poly(lactic acid) Science and Technology: Processing, Properties,
Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications
16: Hyperbranched Polymers: Macromolecules in-between of Deterministic
Linear Chains and Dendrimer Structures
17: Polymer Photovoltaics: Materials, Physics, and Device Engineering

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Polymer Photovoltaics
Materials, Physics, and Device
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Engineering

Edited by

Fei Huang
South China University of Technology, Guangzhou, PR China
Email: [email protected]

Hin-Lap Yip
South China University of Technology, Guangzhou, PR China
Email: [email protected]

Yong Cao
South China University of Technology, Guangzhou, PR China
Email: [email protected]
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RSC Polymer Chemistry Series No. 17

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Preface

To achieve broader deployment of photovoltaic (PV) technology, new genera-

tion photovoltaic devices need to be produced from low-cost, non-toxic, and
earth-abundant materials using environmentally friendly and scalable pro-
cesses. Organics/polymer-based photovoltaics (OPV) have the potential to
fulfil all these requirements and therefore have attracted significant global
attention. When compared with inorganic-based photovoltaic cells, the
advantages of OPVs include their potential to be manufactured at extremely
high throughput with ultra low production cost using a solution-based, con-
tinuous roll-to-roll coating process. Their features of ultra light weight and
high flexibility also distinguish OPVs from traditional photovoltaic technol-
ogy. With these unique properties, OPVs offer good form factors for vari-
12:26:41.

ous new applications, and therefore have extremely high commercial value.
Over the past few years, the performance of OPVs has improved significantly,
from ∼7% in 2009 to ∼12% in 2015, and now reaches a level that can be con-
sidered for some specific PV applications. As the interest in polymer solar
cell research continues to grow, this book aims to provide a comprehensive,
up-to-date review of the recent advancements in OPV technology.
This book consists of 13 chapters contributed by leading experts in the OPV
field covering the areas of new chemistry, design and synthesis of OPV mate-
rials, interface engineering, photophysics, morphology control and charac-
terizations, new device concepts and advanced manufacturing process. As
the development of new materials is key to the continuous improvement of
the performance of OPVs, a major portion of the book will be dedicated to
discussing the design concept and synthesis of novel organic semiconduc-
tors for OPV applications.
In Chapter 1, Li and Bo provide an overview of the key chemistry, includ-
ing Stille coupling, Suzuki coupling and direct C–H arylation, for the syn-
thesis of conjugated polymers used for OPVs. The reaction mechanism and

RSC Polymer Chemistry Series No. 17

Polymer Photovoltaics: Materials, Physics, and Device Engineering
Edited by Fei Huang, Hin-Lap Yip, and Yong Cao
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

v
 View Online

vi Preface
the pros and cons of each type of coupling reaction are discussed in detail.
In Chapter 2, Hou and co-workers present the design criteria for develop-
ing state-of-the-art polymer donors for highly efficient OPVs. The polymer
structure–device performance relationships for a few important classes of
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polymers are discussed. In Chapter 3, Matsuo provides a comprehensive dis-

cussion on the design concepts and synthesis of new fullerene acceptors for
OPVs. The effects of chemical functionalization, multi-adduct modification
and the crystal structure of fullerenes on the OPV device performance are
also discussed. In Chapter 4, Yan and co-workers review the recent develop-
ment of efficient n-type semiconducting polymers and their applications as
electron acceptor materials for all polymer-based OPVs. The effects of molec-
ular weight, side chains, crystallinity of polymers and processing conditions
on the bulk heterojunction morphology, as well as the device performance,
are thoroughly discussed. In Chapter 5, Welch and co-workers highlight the
synthesis and structure of several important classes of small molecule donors
that enable the fabrication of highly efficient OPVs, and their structure–­
property–function relationships are discussed. In Chapter 6, Huang and
co-workers give an overview of interface engineering for OPVs. The functions
and the design criteria for efficient interfacial materials and their effects on
OPV performance are discussed. In Chapter 7, Choy explains the functions
and effects of solution processed metal oxide-based interfacial materials
for OPVs. Different preparation methods for the metal oxide interlayers and
their performance in both conventional and inverted OPVs are compared. In
12:26:41.

addition, the concepts of using chemical and metal nanoparticle doping of

the oxide interlayer to introduce plasmonic-electrical effects to improve the
performance of OPVs are presented. In Chapter 8, Heeger and co-­workers
describe how they discovered the ultrafast electron transfer process in nano-
structured bulk heterojunctions and also discuss the ultrafast experimental
results for both the polymer:fullerene and small molecule:fullerene films.
They also present a general strategy to produce highly ordered and aligned
semiconducting polymer films with exceptional high charge carrier mobil-
ities. In Chapter 9, Russell and co-workers review some of the significant
advances that have been made in understanding and manipulating the mor-
phology of the OPV bulk heterojunction (BHJ) layers. Several key character-
ization techniques for morphological study are discussed. In addition, the
major factors that affect the BHJ morphologies are discussed from both ther-
modynamic and kinetic aspects. In Chapter 10, Zhong discusses the current
understanding of the photocurrent generation mechanism in OPVs, covering
the electronic processes including charge generation, charge recombination,
and charge transport. In Chapter 11, Furlan and Janssen discuss the design,
working principle, modeling and characterizations of multi-junction OPVs.
An overview of the high performance multi-junction OPVs with respect to
the material choice, interconnection layer and device configuration is also
provided. In Chapter 12, Yip and Jen provide an overview of the state-of-
the-art semitransparent OPVs for power generating window applications.
Several important factors that are required to achieve high performance
 View Online

Preface vii
semitransparent OPVs, including the development of new transparent elec-
trodes, efficient low-bandgap materials, new device structures, and optical
engineering, are discussed. Finally, in Chapter 13, Youn and Guo discuss
the scalability issues of OPVs, covering cost evaluation, material choice, and
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large-scale manufacturing of OPVs based on roll-to-roll coating processes.

With the comprehensive, up-to-date reviews on the recent advancements
in OPV technology from the leading experts around the world, we hope that
this book will provide a useful source of information and a practical guide for
scientists, engineers and graduate students that are interested in this field.
Fei Huang
Hin-Lap Yip
Yong Cao
12:26:41.
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Contents

Chapter 1 New Chemistry for Organic Photovoltaic Materials 1

Cuihong Li and Zhishan Bo

1.1 I ntroduction 1
1.2 Stille Polycondensation 2
1.2.1 History and Mechanism of the Stille Coupling
Reaction 2
1.2.2 The Reaction Catalyst, Ligand and Solvent 3
1.2.3 Monomers 4
1.2.4 Advantages of the Stille Polycondensation 4
1.2.5 Disadvantages of the Stille Polycondensation 4
1.2.6 Examples of Synthesis of D–A Conjugated
12:27:54.

Polymers by Stille Coupling 5

1.3 Suzuki Polycondensation 11
1.3.1 History and Mechanism of the Suzuki
Coupling Reaction 11
1.3.2 Mechanism of the Suzuki Coupling Reaction 12
1.3.3 Catalyst, Ligand and Solvents 13
1.3.4 Monomers 14
1.3.5 Advantages of the Suzuki Coupling Reaction 14
1.3.6 Drawbacks of the Suzuki Coupling Reaction 15
1.3.7 Examples of the Suzuki Coupling Reaction 15
1.4 C–H Activation/Direct Arylation Polycondensation 18
1.4.1 History and Mechanism of the C–H
Activation Polycondensation 18
1.4.2 Mechanistic Insight 19
1.4.3 Catalysts, Additive and Solvents 20
1.4.4 Monomers 21

RSC Polymer Chemistry Series No. 17

Polymer Photovoltaics: Materials, Physics, and Device Engineering
Edited by Fei Huang, Hin-Lap Yip, and Yong Cao
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

ix
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x Contents
1.4.5 A dvantages of the Direct Arylation
Polycondensation 21
1.4.6 Drawbacks of the Direct Arylation
Polycondensation 21
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1.4.7 Examples of the Direct Arylation

Polycondensation 22
References 25

Chapter 2 New Polymer Donors for Polymer Solar Cells 32

Long Ye, Sunsun Li, and Jianhui Hou

2.1 I ntroduction 32
2.2 Design Requirements and Strategies for
Highly Efficient Polymer Donors 34
2.2.1 Design Requirements for Highly Efficient
Polymer Donors 34
2.2.2 Design Strategies for Highly Efficient Polymer
Donors 37
2.3 Novel D–A Copolymers for Polymer Solar Cells 45
2.3.1 Design Considerations for D–A Polymer Donors 45
2.3.2 D –A Copolymers Based on Thiophene Units 47
2.3.3 D –A Copolymers Based on Bridged
Biphenyl Derivatives 49
12:27:54.

2.3.4 D –A Copolymers Based on Bridged

Bithiophene Derivatives 52
2.3.5 D –A Copolymers Based on Benzodithiophene
Analogues 55
2.3.6 D –A Copolymers Based on
Indacenodithiophene Analogues 60
2.4 Novel Terpolymer Donors for Polymer Solar Cells 63
2.4.1 Design Considerations for Terpolymer Donors 63
2.4.2 Novel Terpolymers Based on One Donor Unit 64
2.4.3 Novel Terpolymers Based on Two Donor Units 67
2.5 Summary and Outlook 69
References 69

Chapter 3 Fullerene Derivatives as Electron Acceptors in

Polymer Solar Cells 78
Yutaka Matsuo

3.1 D
 esign Concepts of Fullerene Acceptors 78
3.2 PCBM 79
3.2.1 Synthesis of PCBM 79
3.2.2 Fundamental Properties of PCBMs 80
3.2.3 PCBM Derivatives in Photovoltaic Applications 81
3.2.4 [70]PCBM 83
3.2.5 Mix-PCBM 83
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Contents xi
3.3 1
 ,4-Di(organo)fullerene 84
3.3.1 Silylmethylfullerene (SIMEF) 84
3.3.2 1,4-Di(aryl)fullerene 86
3.4 Diphenylmethanofullerene (DPM) 88
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3.4.1 Synthesis of Diphenylmethanofullerene 88

3.4.2 Photovoltaic Application 89
3.5 Fulleropyrrolidine 89
3.5.1 Synthesis of Fulleropyrrolidine 90
3.5.2 Photovoltaic Applications 90
3.6 56π-Electron Conjugated Fullerene Derivatives 91
3.6.1 Diels–Alder Reactions 91
3.6.2 Indene-C60 Bis-Adducts (ICBA) and
Related Compounds 91
3.7 Dihydromethanofullerene 94
3.7.1 Synthesis of Dihydromethanofullerene 94
3.7.2 56π-Dihydromethanofullerene 95
3.8 Summary 97
Acknowledgements 97
References 97

Chapter 4 Polymer Acceptors for All-Polymer Solar Cells 101

He Yan, Christopher R. McNeill, and Cheng Mu
12:27:54.

4.1 I ntroduction 101

4.2 Materials Aspects for All-Polymer Solar Cells 103
4.2.1 All-PSCs Based on Large Bandgap
(2–2.5 eV) Donor Polymers 105
4.2.2 All-PSCs Based on Polythiophene
Donor Polymers 107
4.2.3 All-PSCs Based on Medium or
Low Bandgap Polymers 113
4.3 Morphology of Polymer:Polymer Blends 116
4.3.1 Solution Deposition 117
4.3.2 Molecular Weight 118
4.3.3 Crystallinity 119
4.3.4 Side Chains 120
4.3.5 Mini-Summary 121
4.4 Conclusions 122
References 122

Chapter 5 Design and Synthesis of Small Molecule Donors for

High Efficiency Solution Processed Organic Solar Cells 127
Seth McAfee, Gregory C. Welch, and Corey V. Hoven

5.1 I ntroduction 127

5.2 Device Operation 128
5.3 Small Molecule Donor Design 130
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xii Contents
5.4 H
 istorical Perspective 131
5.5 Dye Based Molecules (BODIPY, Squaraine, and
Merocyanine) 131
5.6 Dye Based Molecules – Diketopyrrolopyrrole 133
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5.7 Dye Based Molecules – Isoindigo 141

5.8 Porphyrins 147
5.9 Oligothiophenes (Donor–Acceptor–Donor–
Acceptor–Donor) 153
5.10 Oligothiophenes (Acceptor–Donor–Acceptor) 161
5.11 Comments on Device Optimization 170
5.12 Conclusions and Future Outlook 172
References 173

Chapter 6 Interface Engineering of Polymer Solar Cells 179

Kai Zhang, Chunhui Duan, Fei Huang, and Yong Cao

6.1 I ntroduction 179

6.2 Functions and Design Criteria of the
Interfacial Layer 180
6.2.1 Functions of Interfacial Materials 181
6.2.2 Design Criteria for Interfacial Materials 183
6.3 Interfacial Materials for Conventional Polymer
Solar Cells 184
12:27:54.

6.3.1 Anode Contact 184

6.3.2 Cathode Contact 191
6.4 Interfacial Materials for Inverted Polymer Solar Cells 201
6.4.1 Anode Contact 201
6.4.2 Cathode Contact 202
6.5 Summary 210
References 211

Chapter 7 Solution Processed Metal Oxides and Hybrid Metal

Oxides as Efficient Carrier Transport Layers
of Organic Optoelectronic Devices 220
Wallace C. H. Choy

7.1 I ntroduction 220

7.2 Solution-Processed Metal Oxides as Electron
Transport Layer (ETL) 221
7.2.1 Zinc Oxide (ZnO) 222
7.2.2 Titanium Oxide (TiOx) 225
7.2.3 Cs2CO3 229
7.2.4 Other Metal Oxide Based ETLs 230
7.3 Doped and Hybrid Metal Oxides for Enhanced
Electron Transport of ETL 232
7.3.1 Doped and Hybrid TiOx 232
7.3.2 Doped and Hybrid ZnO 234
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Contents xiii
7.4 S
 olution-Processed Metal Oxides Functioning as
Hole Transport Layers (HTLs) 235
7.4.1 Solution-Processed Molybdenum Oxide
(MoOx) as HTLs 235
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7.4.2 Solution-Processed Vanadium Oxide (V2Ox)

as HTL 240
7.4.3 Solution-Processed Tungsten Oxide (WOx)
as HTL 242
7.4.4 Doped and Hybrid Metal Oxides as HTL 243
7.5 Summary 246
Acknowledgments 247
References 248

Chapter 8 New Science and New Technology in Semiconducting

Polymers 255
L. Kaake, D. Moses, C. Luo, A. K. K. Kyaw, L. A. Perez,
S. Patel, M. Wang, B. Grimm, Y. Sun, G. C. Bazan,
E. J. Kramer, and Alan J. Heeger

8.1 C oherence and Uncertainty in Nanostructured

Organic Photovoltaic Materials 255
8.1.1 The Mechanism for Ultrafast Electron
Transfer 255
12:27:54.

8.1.2 Ultrafast Experimental Results 258

8.2 High Mobility Thin-Film Transistors (TFTs)
Fabricated from Semiconducting Polymers 261
8.3 Conclusion 269
Acknowledgements 270
References 270

Chapter 9 Morphology of Bulk Heterojunction Polymer

Solar Cells 272
Feng Liu, Yao Liu, and Thomas P. Russell

9.1 I ntroduction 272

9.2 Characterization Methods 274
9.2.1 Lateral Morphology Characterizations 274
9.2.2 Vertical Morphology Characterizations 278
9.2.3 Surface Morphology Characterization 279
9.2.4 Crystalline Structure Characterization 280
9.3 Important Morphology Observations 281
9.3.1 PPV Polymers and Solvent Effect 282
9.3.2 P3HT and Thermal Annealing 282
9.3.3 PCPDTBT and Chemical Additives 284
9.3.4 PTB7 and Hierarchical Structure 285
9.4 Conclusion 286
References 287
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xiv Contents
Chapter 10 Charge Generation, Recombination and Transport
in Organic Solar Cells 292
Chengmei Zhong

10.1 I ntroduction 292

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10.2 The Charge Generation Process in Organic

Solar Cells 293
10.2.1 The Exciton Theory of Charge Generation 294
10.2.2 The CT State, Charge Generation and
Geminate Recombination 296
10.2.3 The Ultrafast Charge Generation Theory 298
10.3 Charge Recombination in Organic Solar Cells 300
10.4 Charge Transport in Organic Solar Cells 302
10.5 Conclusion 304
References 305

Chapter 11 Multi-Junction Polymer Solar Cells 310

Alice Furlan and René A. J. Janssen

11.1 Introduction 310

11.1.1 Principles of Multi-Junction Polymer
Solar Cells 310
11.1.2 Early Developments 312
12:27:54.

11.1.3 Outline 314

11.2 Optimization and Characterization of
Multi-Junction Polymer Solar Cells 314
11.2.1 Electrical and Optical Modeling 314
11.2.2 Characterization of Tandem Cells 317
11.3 Photoactive Layers 319
11.3.1 Fullerenes 324
11.3.2 Wide Bandgap Donors 324
11.3.3 Small Bandgap Donors 327
11.4 Recombination Layers 327
11.4.1 Regular Configuration 328
11.4.2 Inverted Configuration 329
11.4.3 Loss-Less Contacts 330
11.5 Advancing the Efficiency of Solution Processed
Multi-Junction Cells 331
11.5.1 Polymer Tandem Cells 331
11.5.2 Small Molecule Tandem Cells 336
11.5.3 Polymer Multi-Junction Cells 336
11.6 Special Device Configurations 341
11.7 Processing Issues for Multi-Junction Polymer
Solar Cells 343
11.7.1 Laboratory Scale Devices 343
11.7.2 Large Area and Printed Multi-Junction Cells 344
11.8 Conclusions 346
References 346
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Contents xv
Chapter 12 Semi-Transparent Polymer Solar Cells for Power
Generating Window Applications 352
Hin-Lap Yip and Alex K.-Y. Jen
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12.1 I ntroduction 352

12.2 Optical Assessment 355
12.2.1 Color Rendering Properties 355
12.2.2 Optical Simulations 357
12.3 Transparent Electrodes for ST-OPV 359
12.3.1 Transparent Conductive Oxides 359
12.3.2 Conducting Polymers 360
12.3.3 Ultrathin Metal Films 360
12.3.4 Metal Nanowires 361
12.4 Low Bandgap Polymers 363
12.5 Semitransparent Tandem Solar Cells 367
12.6 Photonic Crystal-Enhanced ST-OPV 370
12.7 Conclusions 372
References 373

Chapter 13 Solution Processed Organic Photovoltaics (OPVs) 376

Hongseok Youn and L. Jay Guo

13.1 I ntroduction 376

12:27:54.

13.2 Material Cost Issues in OPVs 377

13.3 Fabrication Technologies Toward Low-Cost
and Scalable OPVs 379
13.3.1 Slot–Die Coating Process 379
13.3.2 Inkjet Printing Process 381
13.3.3 Traditional Roll-to-Roll Printing Process 381
13.4 Materials for Functional Layers 384
13.4.1 Flexible Substrates 384
13.4.2 Silver Back Electrode 384
13.4.3 Active Layer and Coating Issues 385
13.4.4 Interfacial Layer (PEO, PEIE) 387
13.4.5 Hole Transport Layer (HTL)/Electron
Transport Layer (ETL) 388
13.5 Issues in Scalable OPVs 391
13.5.1 Effect of Device Size 391
13.5.2 Isolation of Defects 393
13.6 Conclusion 394
References 395

Subject Index 397

Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00001

CHAPTER 1

New Chemistry for Organic

Photovoltaic Materials
CUIHONG LIa AND ZHISHAN BO*a
a
College of Chemistry, Beijing Normal University, 100875 Beijing,
People’s Republic of China
*E-mail: [email protected]
12:26:53.

1.1 Introduction
Organic semiconducting materials have become the cornerstone of organic
electronics, including photovoltaic cells, light-emitting diodes, field effect
transistors, and electrochromic devices. The synthesis of new organic semi-
conducting materials and the development of new synthetic methods for pre-
paring semiconducting organic materials are two important issues that have
attracted great attention. In this chapter, we mainly focus on the new chem-
istry for the synthesis of conjugated polymers used for organic photovoltaics.
Palladium-mediated cross-coupling reactions such as Suzuki–Miyaura,
Sonogashira, Heck, and Stille reactions have been widely used in the syn-
thesis of π-conjugated semiconducting materials. Recently, some new π-con-
jugated donor–acceptor type copolymers have shown great prospects for
photovoltaic cell applications. Power conversion efficiencies (PCEs) above
9% have been achieved for bulk heterojunction (BHJ) polymer solar cells
(PSCs).1 Conjugated polymers synthesized by Heck and Sonogashira cou-
pling reactions are seldom used for organic photovoltaic (OPV) applications.
Most high efficiency conjugated polymers for OPV are synthesized by Stille

RSC Polymer Chemistry Series No. 17

Polymer Photovoltaics: Materials, Physics, and Device Engineering
Edited by Fei Huang, Hin-Lap Yip, and Yong Cao
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

1
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2 Chapter 1
and Suzuki cross-couplings. The classical synthetic routes toward donor–
acceptor (D–A) type copolymers are palladium catalyzed AA/BB-type (hetero)
aryl–(hetero)aryl cross-couplings of dihaloarylene monomers and suitably
functionalized bifunctional aromatic counterparts, mostly arylene dibo-
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ronic acids/diboronic esters (Suzuki-type coupling) or distannyl arylenes

(Stille-type coupling). Recently, the C–H arylation cross-coupling reaction,
the so-called direct arylation for the syntheses of π-conjugated polymers,
has been reported.2 Direct C–H arylation has been expected as an alterna-
tive route to replace the widely used Stille and Suzuki reactions. Only limited
examples of D–A type conjugated polymers synthesized by the direct C–H
arylation have been reported as donor materials to achieve high PCE in PSCs.
In this chapter, we summarize the synthetic methods for D–A conjugated
polymers, namely, Stille, Suzuki–Miyaura, and direct C–H arylation polycon-
densation. In addition, D–A conjugated polymers synthesized by these meth-
ods and used for photovoltaic applications will be described.

1.2 Stille Polycondensation

1.2.1 History and Mechanism of the Stille Coupling Reaction
Eaborn and Kosugi developed the first examples of cross-coupling reactions
between organostannanes and electrophilic partners between 1976 and
1977.3 Soon the body of work was well known, when it became established
12:26:53.

as the title of the Stille coupling in 1978.4 Stille and co-workers reported the
preparation of ketones from acyl chlorides and organostannanes by the use
of palladium-catalyzed cross-coupling.5 Following this, the Stille reaction
quickly took its place as one of the most useful protocols for forming sp2 car-
bon–carbon bonds in organometallic chemistry. Yu and co-workers further
developed this methodology in 1993 for use in polycondensation reactions
for heteroaromatic diblock copolymers.6 They optimized reaction conditions
and prepared high molecular weight copolymers.
The reaction mechanism itself is known to be far more complex and has
been the subject of extensive work.7 The generally accepted process involves
an oxidative addition step, a transmetalation step, and a reductive elimina-
tion step, as shown in Scheme 1.1. The Pd(0) species is the active catalyst.
Thus, the whole reaction includes Pd(0)-mediated cross-coupling of organo-
halides, triflates, and acyl chlorides with organostannanes. The Pd(ii) cat-
alysts used in Stille reactions are reduced to Pd(0) by the organostannane
monomers, enabling entry into the catalytic cycle. The detailed catalytic
cycle steps are as follows: (1) oxidative addition: the organohalide or triflate
oxidatively adds to the Pd(0) active catalyst and forms a Pd(ii) intermediate
[PdL2R1X] (L = ligand; R1 = alkenyl, alkynyl, aryl; X = Br, I, Cl, or OTf); (2) trans-
metalation, which is generally regarded as the rate-determining step and is
the most complex and thus has been the subject of much debate. It is gen-
erally accepted as a process of cleavage of the Sn–C bond by an electrophilic
Pd(ii) complex and ligand substitution on a Pd(ii) complex; (3) reductive
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New Chemistry for Organic Photovoltaic Materials 3

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Scheme 1.1 General

 mechanism of the Stille reaction.

elimination, the final step in the process, which generates the desired prod-
uct and allows the palladium catalyst to reenter the catalytic cycle.

1.2.2 The Reaction Catalyst, Ligand and Solvent

12:26:53.

The effects of catalytic systems on cross-coupling reactions have been

extensively studied. Pd(PPh3)4 is the most commonly employed catalyst in
the Stille reaction. For Pd(PPh3)4, ligand PPh3 is easily oxidized by traces
of oxygen in reaction system to its oxide, Ph3PO.8 Excess PPh3 can inhibit
the Stille reaction process. Researchers have developed a more air-stable
source of palladium-(0), [Pd2(dba)3], which has been widely used in Stille
cross-couplings. Additionally, the other catalyst systems have also been
widely used in the Stille reactions, such as benzyl(chloro)bis(triphenylphos-
phine) palladium-(ii), bis(acetonitrile)palladium(ii) dichloride, 1,1′-bis(di-
phenylphosphino)ferrocene palladium(ii) dichloride and allylpalladium(ii)
chloride dimer. Meanwhile, the ligand in catalyst systems has been widely
studied because it plays a critical role in the kinetics of the Stille reaction.
Ligands such as (4-MeO-C6H4)3P, PPh3, tri(2-furyl)phosphine, and AsPh3 were
employed with Pd2(dba)3 as the catalyst precursors to optimize the reaction
conditions.
Benzene, toluene, xylene, mesitylene, tetrahydrofuran (THF), N,N-dimethyl-
formamide (DMF), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO),
dioxane, and chloroform are widely used solvents for Stille cross-coupling
reactions. Toluene is generally a good choice for Stille polymerization car-
ried out at temperatures above 120 °C. The higher boiling chlorobenzene
can be used in some microwave-assisted Stille polycondensations owing to
the need for higher temperatures, in excess of 200 °C. Highly polar solvents
such as DMF and NMP can help solubilize the resulting polymer, which can
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4 Chapter 1
function as a catalyst-stabilizing effect for the palladium center. Therefore,
they can be used in mixed solvent systems with toluene or another cosolvent,
for example toluene/DMF or toluene/NMP. For the mixed solvent systems,
a high yield of high molecular weight polymers can be obtained.6b Solvents
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such as THF and dioxane can work as catalyst stabilizers and solvents for the
resulting polymers.

1.2.3 Monomers
Difunctional monomers, such as diorganohalides/ditriflates and distannanes,
are generally used in Stille couplings. According to the reaction mechanism,
diorganohalides or ditriflates carrying electron-withdrawing groups can facil-
itate the first oxidative addition step. For the second transmetalation step, the
process may also be facilitated by organotin compounds with electron-rich
properties. Thus, high molecular weight polymers can be prepared by elec-
tron-rich organotin compounds and an electron-deficient halide or triflate.
Different halides exhibit discrepant reactivity. Generally, diiodo monomers
show higher reactivity than dibromo monomers and dichloro monomers.

1.2.4 Advantages of the Stille Polycondensation

The major advantages of Stille polycondensation are the tolerance of many
12:26:53.

functional groups and the mild reaction conditions. These features are espe-
cially important for the synthesis of conjugated polymers bearing functional
groups. The organotin monomers can be conveniently prepared, and they
are far less sensitive to oxygen and moisture than many other organome-
tallic compounds, e.g., Grignard reagents, organozinc and organolithium
reagents.7a Stille polycondensation is broadly applicable to the synthesis of a
wide variety of donor–acceptor conjugated polymers for OPVs, and provides
a facile route to prepare high molecular weight, narrowly dispersed polymers
under mild conditions.

1.2.5 Disadvantages of the Stille Polycondensation

First, the purification of many tin compounds is difficult because of their
instability under silica gel column chromatography. Difficulties in the puri-
fication of monomers can pose a substantial problem in the synthesis of
high molecular weight polymers, because the purity of monomers is cru-
cial to achieving a precise stoichiometry between two monomers. Second,
Stille couplings require the use of highly toxic organostannyls, which are not
environmentally friendly. Generally, the organotin compounds are prepared
using chlorotrimethylstannane or chlorotributylstannane; chlorotrimeth-
ylstannane is more reactive than chlorotributylstannane.9 Trimethyltin
compounds are often more easily purified by recrystallization than their
tributyltin counterparts, but the toxicity of chlorotrimethylstannane is 100
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New Chemistry for Organic Photovoltaic Materials 5

times greater than that of chlorotributylstannane. Moreover, the trimethyltin
derivatives tend to be more volatile when they are exposed to air. The diffi-
culty in purification and the high toxicity of organostannyls make the use of
Stille cross-couplings an unwelcome choice.
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1.2.6 
Examples of Synthesis of D–A Conjugated Polymers by
Stille Coupling
The Stille polycondensation mainly involves the coupling reactions of ditin
compounds with dihalide compounds and can be performed using conven-
tional heating. Significantly, microwave irradiation was found to improve the
number average molecular weight (Mn) and yield, and decrease the polydis-
persity index (PDI). This section will describe several examples in which D–A
low bandgap conjugated polymers synthesized by Stille cross-couplings were
used as donor materials in single junction bulk heterojunction polymer solar
cells to achieve high PCE (>7%).
Liang et al. reported the synthesis of polymer P1 by Stille polycondensation
between a dibromo compound and ditin compound.10 Pd(PPh3)4 was used as
the catalyst, toluene and DMF (4 : 1) were used as the solvent, and the polym-
erization was carried out at 120 °C for 12 h under N2 protection. PTB7 was
obtained with average molecular weight (Mw) of 97.5 kDa and a PDI of 2.1. A
PCE over 7% was obtained for BHJ PSCs based on PTB7. Later, the PCE was
increased to 9.2% after device optimization (Scheme 1.2).11
12:26:53.

P2 was prepared by Wei et al. with Stille polymerization of a dibromo

compound and ditin compound using [Pd2dba3/P(o-tolyl)3] as the catalyst
precursor.12 The Mn of 9.7 kg mol−1 with a PDI of 1.4 was determined by gel
permeation chromatography (GPC) using chloroform as the eluent. P2 is
readily soluble in hot chlorinated solvents such as chloroform, chloroben-
zene, and dichlorobenzene. With the blends of P2:PC71 BM (1:1.5, w/w) as the
active layer, a PCE of 7.3% was achieved using 1,6-diiodohexane (DIH) as the
processing additive (Scheme 1.3).12
Chu et al. reported a new alternating copolymer of dithienosilole and thieno-
pyrrole-4,6-dione (P3), which was synthesized by Stille coupling of a ditin com-
pound and dibromo compound in refluxing toluene/dimethylformamide (10 : 1)
with Pd(PPh3)4 as the catalyst.13 The purified polymer has a Mn of 28 kDa and
a PDI of 1.6, as determined by GPC using chlorobenzene (CB) as the eluent. P3

Scheme 1.2 Synthesis

 of polymer P1 by Stille polycondensation.
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6 Chapter 1
could be readily dissolved in chlorinated solvents even at room temperature.
When blended with PC71BM, P3 exhibited a PCE of 7.3% (Scheme 1.4).
You et al. reported the first fluorinated D–A conjugated polymers applied in
PSCs with an exceptional performance. P4 was synthesized by Stille coupling
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of a ditin compound and dibromo compound.14 The polymerization was

carried out at 120 °C for 20 min under microwave irradiation with Pd2dba3
and P(o-tolyl)3 as the catalyst precursors and o-xylene as the solvent. P4 was
obtained in a yield of 89% with Mn of 33.8 kDa. A PCE of 7.2% was obtained
for P4 T:PC61BM BHJ based PSCs (Scheme 1.5).
Fluorinated polymer P5 was synthesized in a similar method by You et al.15
PSCs based on P5 showed a PCE above 7% when blended with PC61BM as the

Scheme 1.3 Synthesis

 of polymer P2.
12:26:53.

Scheme 1.4 Synthesis

 of polymer P3.

Scheme 1.5 Synthesis

 of polymer P4.
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New Chemistry for Organic Photovoltaic Materials 7

active layer, and a PCE above 6% is still maintained at an active layer thick-
ness of 1 μm (Scheme 1.6).
The copolymer P6 was obtained through Stille coupling polymerization of two
monomers with a yield of 86%.16 P6 has a Mn of 40.5 kDa with a PDI of 3.20. PSCs
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based on P6 showed a PCE of 6.00% when blended with PC71BM as the active
layer. A PCE of 8.4% was achieved from the inverted PSC by using a PFN–Br inter-
facial layer to modify the ZnO electron extraction layer (Scheme 1.7).17
Amb et al. reported the synthesis of the first dithienogermole (DTG)-con-
taining conjugated polymers by Stille polycondensation and their photovol-
taic performance.18 When P7:PC70BM blends are utilized in inverted bulk
heterojunction solar cells, the cells display a PCE of 7.3%. In inverted PSCs,
when surface-modified ZnO–polymer nanocomposites were used as the elec-
tron-transporting layer, a PCE of 7.4% was achieved (Scheme 1.8).19
Huo et al. developed new poly[benzo(1,2-b:4,5-b′)dithiophene-co-thieno­
(3,4-b)thiophene] (PBDTTT) derivatives having the thienyl substituted
[benzo(1,2-b:4,5-b′)dithiophene] (BDT) and the alkylcarbonyl-substituted
12:26:53.

Scheme 1.6 Synthesis

 of polymer P5.

Scheme 1.7 Synthesis

 of polymer P6.

Scheme 1.8 Synthesis

 of polymer P7.
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8 Chapter 1
20
thieno-[3,4-b]thiophene (TT-C). The polymer P8 was prepared by Stille cou-
pling of the bis(trimethyltin) BDT monomers and the bromides (TTC) in
a solvent mixture of toluene and DMF (5 : 1) with Pd(PPh3)4 as the catalyst.
PSCs based on P8 and PC70BM reached a PCE of 7.59%. A PCE of 8.79% for
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a single-junction BHJ PSC was obtained with metallic nanoparticles (NPs)

embedded in the active layer.21 The PCE was further increased to 9.13% in
inverted PSCs by using 1,8-diiodooctane (DIO) as the processing additive
(Scheme 1.9).
Xu et al. reported the synthesis of P9 by Stille coupling of IDTT-di-Tin and
diiodo-DFBT with Pd2dba3 and P(o-tol)3 as catalyst precursors.22 PSC devices
based on P9 showed an improved PCE of 7.03% without the use of any addi-
tives or post-solvent/thermal annealing processes (Scheme 1.10).
Wu et al. reported the synthesis of polymer P10 through Stille coupling of
the bis(trimethyltin) monomers and the dibromo monomers.23 P10:PC71BM
based PSCs exhibit a PCE above 7.79% without any further treatment such
as the use of additives or annealing in device fabrication (Scheme 1.11).
Dong et al. prepared a copolymer P11 by Stille coupling. The P11-based
device showed an impressive PCE of 7.11% in inverted PSCs (Scheme 1.12).24
P12 was synthesized by microwave-assisted Stille coupling using Pd2dba3
and P(o-tolyl)3 as the catalyst precursor, and chlorobenzene (CB) as the sol-
vent. PSCs based on P12:PC71BM blends afforded PCE up to 7.2% without
thermal annealing or the use of processing additives (Scheme 1.13).25
12:26:53.

Scheme 1.9 Synthesis

 of polymer P8.

Scheme 1.10 Synthesis

 of polymer P9.
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New Chemistry for Organic Photovoltaic Materials 9

Son et al. reported the synthesis of polymer P13 by Stille coupling using
Pd(PPh3)4 as the catalyst and DMF and anhydrous toluene (1 : 4) as the
reaction cosolvent. After optimization of the polymer’s solubility and
morphological compatibility with PC71BM, PSCs achieved a PCE of 7.6%
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(Scheme 1.14).26

Scheme 1.11 Synthesis

 of polymer P10.
12:26:53.

Scheme 1.12 Synthesis

 of polymer P11.

Scheme 1.13 Synthesis

 of polymer P12.

Scheme 1.14 Synthesis

 of polymer P13.
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10 Chapter 1
Liao et al. reported the synthesis of P14 by Stille coupling with Pd(PPh3)4 as
the catalyst in a solvent mixture of toluene and DMF (5 : 1). Fullerene deriv-
ative (PCBE–OH)-doped ZnO nanometer-thick film (40 nm) was used as the
cathode interfacial layer for the effective collection of electrons. PSCs with
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the P14:PC71 BM active layer and the ZnO–C60 modified cathode give a PCE of
9.35% (Scheme 1.15).1
Wang et al. reported the synthesis of P15 by Stille coupling with Pd(PPh3)4
as the catalyst. P15 can dissolve in chloroform, toluene and 1,2,4-trichloroben-
zene (TCB) at room temperature. The best device performance, with a rela-
tively high PCE of 8.30%, was obtained for P15:PC71BM (1 : 1.5) (Scheme 1.16).27
Li et al. prepared polymer P16 using Stille coupling. A toluene/DMF (10 : 1,
v/v) solvent mixture was used to obtain high molecular weight materials.
PSCs based on P16:PC71BM furnished a PCE of 7.1% (Scheme 1.17).28
Hou et al. prepared a new copolymer, P17, with Stille coupling. PSCs based
on P17:PC71BM (1 : 1.5, w/w) gave the best PCE of 8.07% (Scheme 1.18).29
Chen et al. reported the synthesis of P18 by Stille coupling.30 With P18 as
the donor and PC71BM as the acceptor in inverted PSCs, the highest PCE
of 7.64% was achieved with an active layer 230 nm thick (Scheme 1.19).
12:26:53.

Scheme 1.15 Synthesis

 of polymer P14.

Scheme 1.16 Synthesis

 of polymer P15.
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New Chemistry for Organic Photovoltaic Materials 11

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Scheme 1.17 Synthesis

 of polymer P16.

Scheme 1.18 Synthesis

 of polymer P17.
12:26:53.

Scheme 1.19 Synthesis

 of polymer P18.

1.3 Suzuki Polycondensation

1.3.1 
History and Mechanism of the Suzuki Coupling
Reaction
Over the past two decades, Suzuki polycondensation has become one of
the most efficient methods for the synthesis of conjugated polymers. As
another important cross-coupling protocol, the Suzuki–Miyaura cross-cou-
pling reaction was invented by Suzuki and co-workers in 1979.31 The scope
of the Suzuki reaction for synthetic applications has been surveyed in
several excellent reviews by Kotha, Lahiri, Kashinath, Miyaura and Fu.32
The Suzuki–Miyaura cross-coupling reaction provided deeper insights
into how to connect two specific sp2-hybridized C-atoms more efficiently
and under milder conditions. The Suzuki–Miyaura cross-coupling reac-
tion was first used by Schlueter et al. to prepare poly(para-phenylene)s.33
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12 Chapter 1
Since then, Suzuki polycondensation (SPC) has become one of the most
powerful and widely used methodologies for the synthesis of conjugated
polymers.
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1.3.2 Mechanism of the Suzuki Coupling Reaction

The catalytic cycle of Suzuki coupling is thought to follow a sequence
involving the oxidative addition of an aryl halide to a Pd(0) complex to
form an arylpalladium(ii) halide intermediate, the transmetalation with
a boronic acid, and reductive elimination of the resulting diarylpalla-
dium complex to afford the corresponding biaryl and to regenerate the
Pd(0) complex. Oxidative addition is often the rate-limiting step, and it is
not surprising that the relative reactivity of aryl halides decreases in the
order I > Br > Cl. The role of the base in these reactions is to facilitate the
transmetalation of the boronic acid by forming a more reactive boronate
species that can interact with the Pd center and transmetalate in an intra-
molecular fashion (Scheme 1.20, path A).34 Alternatively, it has also been
proposed that the base replaces the halide in the coordination sphere
of the palladium complex and facilitates an intramolecular transmeta-
lation (path B).35 In fact, the exact nature of the actual catalyst remains
ambiguous.36
Suzuki polycondensation is generally believed to be of the step-growth
type involving so-called AA/BB and AB approaches. In the AA/BB case,
12:26:53.

two different monomers are required, each of which carries either two
boronic acids (or esters) or two leaving groups such as halogen or triflate.
When two aromatic monomers are combined, polyarylene backbones
which contain the two aromatic residues in an alternating fashion are
obtained. In the AB case, the monomer carries both functional groups at
the same time.

Scheme 1.20 General

 mechanism of the Suzuki reaction.
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New Chemistry for Organic Photovoltaic Materials 13

1.3.3 Catalyst, Ligand and Solvents

Almost all Suzuki polycondensations published to date in the literature use
1–3 mol% of catalyst, mostly Pd[P(p-tolyl)3]3, Pd(PPh3)4 or in situ prepared
Pd[P(o-tolyl)3]2. Most catalysts for the Suzuki polycondensation employ tri-
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arylphosphine ligands. New ligands, which include Buchwald’s biaryl-based

phosphines,37 Beller’s diadamantyl phosphines,38 Fu’s tri(tert-butyl)phos-
phine,39 and Hartwig’s pentaphenylated ferrocenyl phosphines,40 have been
developed for Suzuki–Miyaura cross-coupling reactions. Buchwald-type
ligand has been applied to polymerize dichloro monomers using Suzuki
polycondensation.
Because of the hydrolytic deboronation of 2,5-thiophenebis(boronic acid
pinacol ester) under standard Suzuki–Miyaura cross-coupling conditions,
most attempts to synthesize thiophene-containing conjugated polymers from
electron-rich 2,5-thiophene bis(boronic acid pinacol ester) and aryl dibro-
mides by Suzuki polycondensation have failed to afford high molecular weight
polymers. Bo designed and synthesized a new thiophene-containing phospho-
rous compound, L1, which was used as the ligand for a zerovalent palladium
catalyst for Suzuki polycondensation of 2,5-thiophenebis(boronic acid pinacol
ester) and aryl dihalides.41 High molecular weight thiophene-containing conju-
gated polymers were successfully synthesized for the first time from thiophene
based diboronic acid ester monomers. The new catalytic system can enhance
the SPC reaction rate and cope with steric hindrance imparted by the mono-
12:26:53.

mers. With the new ligand SPC proceeded very rapidly, and high molecular
weight fourth generation dendronized polymers could be obtained in a short
time. This method should be also of great interest for the synthesis of pharma-
ceutical and agrochemical compounds and natural products (Scheme 1.21).
The solvent systems will affect the progress of the polycondensation. Most
Suzuki polycondensation are carried out in biphasic mixtures of organic
solvents such as toluene, xylene, THF, or dioxane and an aqueous medium

Scheme 1.21 Synthesis

 of polymers by the Suzuki coupling reaction.
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14 Chapter 1
containing the base. The commonly used bases include K3PO4, K2CO3,
NaHCO3, KOH, KF, and sodium tert-butoxide. However, the choice of base is
still empirical, and no general rule for their selection has been established
at present. The other solvent systems, in particular homogeneous ones, have
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been less explored. Phase transfer catalysts (PTCs) such as tetraalkylammo-

nium salts (tetraethylammonium hydroxide) have also been tried.

1.3.4 Monomers
Aryl halides (bromides or iodides) and triflates substituted with elec-
tron-withdrawing groups are suitable substrates for the cross-coupling
reaction. Aryl triflates and sulphonates are regarded as the synthetic
equivalents of aryl halides. Triflates are, however, thermally labile, prone
to hydrolysis and expensive to prepare. Aryl sulphonates are an attractive
option because they are easily prepared from phenols, are more stable than
triflates and are cheap and easily available starting materials. Suzuki poly-
condensations are carried out mainly between aryl (heteroaryl) halides
and aryl (heteroaryl) boronic acids (esters). Similar to other step-growth
polymerization, monomer purity is a key issue for Suzuki polyconden-
sation, especially when the AA/BB approach is used. Boronic acids eas-
ily form partially and fully dehydrated products, which makes it difficult
to reach the correct 1 : 1 stoichiometry. Alternatively, the corresponding
12:26:53.

cyclic boronic esters are widely used, because the commonly used boronic
pinacol esters can be easily purified by silica gel column chromatography.
Free boronic acids tend to be more reactive than their ester analogs. The
solubility of boronic acids vs. esters in solvents also influences relative
reactivity. The higher reactivity of the acids can be counteracted by their
lower solubility.

1.3.5 Advantages of the Suzuki Coupling Reaction

The palladium catalyzed Suzuki–Miyaura coupling reaction is one of
the most efficient methods for the construction of C–C bonds. The cou-
pling can be carried out under mild reaction conditions, which will not
be affected by the presence of water and heat. The reaction can toler-
ate a broad range of functionality and yield non-toxic byproducts. The
boron-containing byproducts are easily separated from the reaction mix-
ture and handled when compared with other organometallic reagents,
especially in large-scale production. Additionally, the diverse boronic
acids are commercially available and environmentally friendly. Conse-
quently, the cross-coupling reaction has been realized in diverse appli-
cations, not only in academic laboratories but also in industry. These
desirable features make the Suzuki–Miyaura reaction an important tool
in medicinal chemistry as well as in the large-scale synthesis of pharma-
ceuticals and fine chemicals.
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New Chemistry for Organic Photovoltaic Materials 15

1.3.6 Drawbacks of the Suzuki Coupling Reaction

The Suzuki–Miyaura reaction suffers from a few key drawbacks, the first of
which is the requirement for basic conditions. A number of monomers may
be unstable in basic conditions, thus rendering this methodology impracti-
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cal for these applications, or require more complex protection–deprotection

strategies. Also, the Suzuki–Miyaura reaction requires a two-phase sys-
tem; thus, polymers that rapidly decrease in solubility as molecular weight
increases may form precipitate in poor yields or display very low molecular
weights and high polydispersities under Suzuki–Miyaura conditions, which
is disadvantageous for photovoltaic application.

1.3.7 Examples of the Suzuki Coupling Reaction

We will provide a class of low bandgap polymers applied in BHJ PSCs that
are synthesized by Suzuki polycondensation. This section cannot possibly
cover all these different polymers. Emphasis will be placed upon important
classes of conjugated polymers based on bridged phenylenes, for example
poly(2,7-fluorene), poly(2,7-carbazole), and poly(2,7-dibenzosilole) based
D–A conjugated polymers.
In 2003, Svensson et al. reported a low bandgap polymer, P19, and its
application in PSCs. P19 was synthesized by Suzuki polycondensation of
2,7-fluorenediboronic acid pinacol ester and benzothiadiazole based dibro-
12:26:53.

mide using Pd(PPh3)4 as the catalyst and toluene and 20% aqueous tetraeth-
ylammonium hydroxide as the reaction media (Scheme 1.22).42
Similarly, Blouin et al. reported the synthesis of P20 by Suzuki coupling of
2,7-carbazolediboronic acid pinacol ester and benzothiadiazole based dibro-
mide using Pd2dba3 and P(o-tol)3 as the catalyst precursors. PSCs based on
P20 showed a PCE of 3.6%.43 After device optimization by Heeger et al., the
PCE was enhanced to 6.1% (Scheme 1.23).44

Scheme 1.22 Synthesis

 of polymer P19.

Scheme 1.23 Synthesis

 of polymer P20.
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16 Chapter 1
Bo et al. reported the synthesis of P21 by Suzuki polycondensation of
2,7-carbazolediboronic acid pinacol ester and 5,6-bis(octyloxy)benzothiadi-
azole based dibromide using Pd(PPh3)4 as the catalyst precursor and a bipha-
sic mixture of THF–toluene (5 : 1)/aqueous NaHCO3 as the reaction medium.
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P21 based PSCs exhibit a PCE of 5.4% (Scheme 1.24).45

He et al. reported a copolymer, P22, which was synthesized by Suzuki poly-
condensation. With P22:PC71BM (1:4) as the active layer, solar cells with a
PFN/Al bilayer cathode displayed PCEs up to 6.07% (Scheme 1.25).46
P23 was first reported as donor material for PSCs by Leclerc et al. in 2007.47
P23 was prepared with a Mn of 15 kDa by Suzuki polycondensation of 2,7-sila-
fluorenediboronic acid pinacol ester and benzothiadiazole based dibromide.
Preliminary device experiments with this copolymer gave a PCE of 1.6%. In
parallel, Cao et al. reported the synthesis of the same polymer with a high
molecular weight (Mn = 79 kDa). The PCE of P23 based PSCs was increased to
5.4% with a polymer : fullerene ratio of 1 : 2 (Scheme 1.26).48
Bo et al. reported the synthesis of a series of D–A alternating conjugated
polymers P24–31 with 5,6-bis(octyloxy)benzothiadiazole as the acceptor unit by
Suzuki polycondensation of dibromo monomers and 5,6-bis(octyloxy)benzo-
thiadiazole based diboronic acid pinacol ester. P24, with a Mn of 102 kg mol−1
and a PDI of 1.66, gave a PCE of 5.08% in devices with P24:PC71BM as the active
12:26:53.

Scheme 1.24 Synthesis

 of polymer P21.

Scheme 1.25 Synthesis

 of polymer P22.

Scheme 1.26 Synthesis

 of polymer P23.
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New Chemistry for Organic Photovoltaic Materials 17

layer. When TiOx was used as an electron-blocking layer, the PCE was further
increased to 6.05%.49 The 9-arylidene-9H-fluorene based D–A conjugated poly-
mers P25 and P26 were synthesized to investigate the influence of alkyloxy posi-
tion on the performance of PSCs. High molecular weight P25 (HMW-P25) and
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low molecular weight P25 (LMW-P25) were used to investigate the influence of
molecular weight on the performance of PSCs. HMW-P25:PC71BM-based PSCs
showed a PCE of 6.52%; LMW-P25:PC71BM based PSCs showed poor photovol-
taic performance, with a PCE of only 2.75%; and P26:PC71BM based PSCs gave
a PCE of only 2.51%.50 Polymer solar cells with P27:PC71BM as the active layer
demonstrate a PCE of 2.23% with a high open circuit voltage (VOC) of 0.96 V
(Schemes 1.27–1.30).51
P28, with a Mn of 27.7 kg mol−1 and a PDI of 3.1, gave a PCE of 4.48% when
a P28:PC71BM blend (1 : 3, by weight) was used as the active layer.52 P29, with
3,6-difluorocarbazole as the donor unit, has a Mn of 9.1 kg mol−1 and a PDI of
2.63. Polymer solar cells based on P29 and PC71BM demonstrate a PCE of 4.8%.53
P30, with 9-alkylidene-9H-fluorene as the donor unit and 5,6-bis(octyloxy)
benzothiadiazole as the acceptor unit, is of planar structure. PSCs with a
blend of P30 and PC71BM as the active layer demonstrate a PCE of 6.2%.54 P31,
12:26:53.

Scheme 1.27 Molecular

 structure of polymer P24 and P25.

Scheme 1.28 Molecular

 structure of polymer P26 and P27.

Scheme 1.29 Molecular

 structure of polymer P28 and P29.
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18 Chapter 1
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Scheme 1.30 Molecular

 structure of polymer P30 and P31.

with spirobifluorene as the donor unit and 5,6-bis(octyloxy)benzothiadiazole

as the acceptor unit, was synthesized and applied in PSCs. PSCs based on the
blend films of P31 and PC71BM show a high open-circuit voltage of 0.94 V and
a PCE of 4.6% without any post-treatment.55

1.4 
C–H Activation/Direct Arylation
Polycondensation
Conventional synthesis of the π-conjugated polymers mainly relies on tran-
sition metal-catalyzed cross-couplings, such as Stille and Suzuki couplings
(vide supra). The preparation of organotin or organoboron monomers used
for Stille or Suzuki coupling requires multistep reactions and tedious purifi-
cation. Additionally, Stille coupling requires the use of very toxic reagents as
12:26:53.

well as generating toxic byproducts, which is not environmentally friendly. In

particular, some important classes of heteroaryl organotin or organoboron
reagents are not readily accessible and may even be too unstable to undergo
the coupling processes, which may confine the variety of polymer libraries
to some extent. In recent years, transition metal-catalyzed direct C–H ary-
lation of non-preactivated arenes with aryl halides or pseudohalides, called
“direct arylation”, has attracted much attention and worldwide interest. The
direct arylations, with the advantages of synthetic simplicity and atom econ-
omy, without the use of troublesome and toxic (hetero)aryl organometallic
intermediates, would be one of the most ideal routes toward π-conjugated
polymers. These reactions are mostly developed for the synthesis of small
molecules. Indeed, up until now, only a few publications have reported the
use of conjugated polymers synthesized by direct arylation in PSCs.

1.4.1 
History and Mechanism of the C–H Activation
Polycondensation
In the last decade, Fagnou et al. detailed efficient coupling reactions between
electron-deficient aromatic rings and arylhalides catalyzed by palladium
complex in the presence of phosphine ligand and base, a synthetic reaction
now termed “direct arylation”.56 Recently, this reaction has been applied to
the synthesis of conjugated polymers, for example regioregular poly(3-hex-
ylthiophene) (P3HT), although it required rigorous heating in a THF solution
at 120 °C and under high pressure.
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New Chemistry for Organic Photovoltaic Materials 19

1.4.2 Mechanistic Insight

The mechanism of C–H activation has been studied experimentally and com-
putationally, and possible pathways include electrophilic aromatic substitu-
tion, Heck-type coupling and concerted metalation–deprotonation (CMD).57
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Most heterocycles, such as thiophenes and indoles, are believed to follow

a base-assisted CMD pathway. Two catalytic cycles for a CMD coupling of
bromobenzene and thiophene using a palladium/phosphine catalytic sys-
tem and cesium carbonate are shown in Schemes 1.31 and 1.32. Scheme 1.31
depicts a carboxylate-mediated process, while Scheme 1.32 represents the
reaction process without a carboxylate additive. In the presence of carbox-
ylate as the additive (Scheme 1.31), first the carbon–halogen bond is formed
by oxidative addition, and then complex 1 is formed by exchange of the hal-
ogen ligand for the carboxylate anion. Complex 1 then deprotonates the
thiophene substrate while simultaneously forming a metal–carbon bond by
going through transition state 1-TS. The phosphine ligands, or the solvent,
can recoordinate to the metal center, following Pathway 1, or the carboxylate
group can remain coordinated throughout the entire process (Pathway 2).
Finally, reductive elimination renders the aryl coupled product. In the case
of no carboxylate additive, after oxidative addition, the reaction follows
one of the two pathways shown in Scheme 1.32. If a bidentate phosphine is
12:26:53.

Scheme 1.31 General

 mechanism of the C–H activation reaction with a carboxyl-
ate-mediated process.
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20 Chapter 1
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12:26:53.

Scheme 1.32 General

 mechanism of the C–H activation reaction without a carbox-
ylate additive.

employed, C–H activation of thiophene can follow Pathway 1, where depro-

tonation is assisted intermolecularly (2-TS). When a monodentate phosphine
is used, the reaction may follow Pathway 1 or Pathway 2. The latter mecha-
nism most closely resembles Pathway 2 in Scheme 1.31 where the carbonate
coordinates to the metal center to give the zwitterionic species. Here, depro-
tonation occurs intramolecularly through transition state 1′-TS. Reductive
elimination then renders 2-phenylthiophene.

1.4.3 Catalysts, Additive and Solvents

In most polymerization examples, Pd(OAc)2 was used as the palladium cata-
lyst. Some research groups have exploited the highly stable Herrmann–Beller
catalyst. Catalytic addition of pivalic acid can aid the C–H activation. Some
groups have found that polymerization in the absence of phosphine ligand
can give high molecular weight materials.
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New Chemistry for Organic Photovoltaic Materials 21

Polar (dimethylacetamide (DMAC), DMF, NMP, THF) and nonpolar (toluene)
solvents are suitable for these reactions and should be selected according
to the polymer solubility. DMAc is not a suitable solvent for polymerization
and always gives brown soluble material. Addition of carboxylic acid may be
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beneficial in nonpolar solvents owing to the high polarity of the C–H bond
transition states. However, C–H bond activations have been accomplished in
toluene and xylenes without carboxylic acids.58

1.4.4 Monomers
Several electron-rich monomers and electron-deficient monomers can be
used for direct arylation polymerization. Direct arylation of 2-halo-3-alkylth-
iophenes for the preparation of polymers (P3RT) was first published in the late
1990s.59 Monomers and dimers can be used to synthesize poly(3,4-ethylene-
dioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT)
by direct arylation polymerization with aryl bromides.58a Interestingly, func-
tional groups were tolerant to direct arylation polymerization conditions and
polymers were obtained in relatively low molecular weights (Mn = 3–4 kDa)
when EDOT monomers were substituted with different functional groups.60
In addition, 2,2′-bithiophene or fused bithiophene based monomers can
undergo facile C–H bond activation.
Electron-deficient thiophene-based monomers including thieno[3,4-c]
pyrrole-4,6-dione (TPD), furo[3,4-c]pyrrole-4,6-dione (FPD) monomers,
12:26:53.

diketopyrrolopyrrole and isoindigo can be copolymerized with bromi-

nated thiophene-based electron-rich monomers such as benzodithiophene,
dithienosilole, and dithienogermole by direct arylation polymerization.
Additionally, electron deficient 4,4′-dinonyl-2,2′-bithiazole and 1,2,4,5-tetra-
fluorobenzene are highly reactive toward direct arylation polymerization.61

1.4.5 Advantages of the Direct Arylation Polycondensation

Direct arylation should bring significant benefits in the synthesis of donor–
acceptor polymers by decreasing the number of monomer preparation steps,
producing only acid as a byproduct, and freeing of undesired waste from the
metal-containing reagents. This is particularly significant because the tradi-
tional Suzuki and Stille couplings inherently possess a number of problems:
synthesis of monomers is time-consuming, purifying the organotin mono-
mers is difficult, and organotin compounds are highly toxic. Therefore, it is
highly desirable to develop new direct arylation methodology that is environ-
mentally friendly, scalable, and high yielding for mass production, to meet
the requirement for synthesis of donor–acceptor polymers used for PSCs.

1.4.6 Drawbacks of the Direct Arylation Polycondensation

For it to be a reliable synthetic methodology with a wide application range,
there are still several problems related to direct arylation polycondensa-
tion reactions that need to be solved. First, the low molecular weight of the
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22 Chapter 1
polymer obtained is disadvantageous for the photovoltaic application. Sec-
ond, the poor selectivity of the C–H bond in direct arylation will resulted in
branched and cross-linked polymer structures that affect the solubility and
optoelectronic properties of polymers.
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1.4.7 Examples of the Direct Arylation Polycondensation

The first example of synthesis of poly(3-alkylthiophene)s by direct arylation
was reported in 1999.59 Recently, the syntheses of high molecular weight
poly(fluorene-alt-tetrafluorobenzene), poly(fluorene-alt-dithiophene), and
poly(thienopyrroledione-alt-dithiophene) by direct arylation were pub-
lished.61b,62 Here, we provide a few examples to show the use of direct ary-
lation to synthesize low bandgap conjugated polymers that are promising
donor materials for PSCs.
A series of DTDPP-based copolymers with an alternating D–A sequence and
homopolymer P32 were synthesized by the direct arylation polycondensation.
The polymer was endowed with the common features of excellent π-conjuga-
tion and ideal planarity, which lead to remarkably low band gaps (1.22 eV).
Photovoltaic properties of these polymers were not reported (Scheme 1.33).63
P33, with a higher molecular weight, up to 70 kDa, was synthesized via palla-
dium catalyzed direct arylation between dithiophene derivative and dibromo
compound with K2CO3, Pd(OAc)2 (10 mol%) and pivalic acid (30 mol%) in a
small volume of N-methylpyrrolidone (NMP) in a 10 mL Schlenk tube. For
12:26:53.

the first time, OPV characteristics of polymers synthesized via direct aryla-
tion were compared to those synthesized via Suzuki coupling. A blend ratio
P33 : PC61BM of 1 : 3 was used to fabricate OPV devices and give the highest
PCE of 2.24%, which represents a moderate enhancement in performance
obtained via Suzuki-coupled polymer (2.01%) (Scheme 1.34).64
Direct arylation polycondensation using the phosphine-free catalytic sys-
tem can be adapted to the synthesis of bithiazole-based alternating copo-
lymers (P34). In comparison with conventional polycondensation via other
cross-coupling reactions, the polycondensation proceeded with a reduced
amount of Pd catalyst (2 mol%) in a short reaction time (10 min to 3 h).
Owing to the difference in reactivity of the C–H bond, controlling the reac-
tion time was effective for suppressing the side reaction at the unexpected
C–H bond (Scheme 1.35).65

Scheme 1.33 Synthesis

 of polymer P32.
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New Chemistry for Organic Photovoltaic Materials 23

High molecular weight P35, using nonactivated dithiophene derivative and
dibromo derivative as coupling monomers, was obtained in good yields (up
to 80%) with a Mn of up to 40 kDa (Scheme 1.36).66
Wang et al. reported that direct arylation polycondensation of 2-bro-
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mo-3-hexylthiophene using Herrmann’s catalyst and a triarylphoshine ligand

yielded regioregular poly(3-hexylthiophene) with a high molecular weight.67
This catalytic system also can be used to direct arylation polycondensation of
a thieno[3,4-c]pyrrole-4,6-dione derivative with a dibromobithiophene deriv-
ative, to give D–A polymer P36. Photovoltaic characterization was not tried
(Scheme 1.37).62b
A 2,2′-bithiophene-based monomer has more than one type of reactive
C–H bond, although reactions typically occur in the 5- and 5′-positions
first. Attempts to copolymerize 2,2-bithiophene with dibromo compound
rendered materials with low solubility due to cross-linking in the 3,3′- and
4,4′-positions of the bithiophene monomer. To evade these side reactions,
the other reactive C–H bonds on the thiophene monomers were blocked with
methyl groups. P37 and P38 were synthesized by direct heteroarylation polym-
erization. However, the film absorption onsets were hypsochromically shifted
compared to the “unprotected” bithiophene analogs. The methyl groups
indeed cause twisting in the polymer backbone and disrupt conjugation.
12:26:53.

Scheme 1.34 Synthesis

 of polymer P33.

Scheme 1.35 Synthesis

 of polymer P34.

Scheme 1.36 Synthesis

 of polymer P35.
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24 Chapter 1
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Scheme 1.37 Synthesis

 of polymer P36.
12:26:53.

Scheme 1.38 Synthesis

 of polymer P37 and P38.

Scheme 1.39 Synthesis

 of polymer P39.

Scheme 1.40 Synthesis

 of polymer P40.

Although protection of the 3,3′,4,4′-positions of bithiophene circumvented

cross-linking on this monomer, the planarity of the copolymers was dis-
rupted and optimal packing properties diminished (Scheme 1.38).68
A D–A conjugated polymer, P39, with a Mn of 41 kDa was synthesized by
Heeger et al. using a direct heteroarylation procedure. A relatively high PCE
of over 6% was obtained from BHJ solar cells based on a photoactive film
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New Chemistry for Organic Photovoltaic Materials 25

comprising a composite of P39 and PC71BM. This is the best result for poly-
mers prepared via the direct heteroarylation method and used for BHJ solar
cells (Scheme 1.39).69
A selenophene–TPD copolymer, P40, with a Mn of 36 kDa and a PDI of 1.97
Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00001

was synthesized using the direct heteroarylation polymerization in a 94%

yield. PSCs with the blend P40 and PC71BM as the active layer gave a PCE of
about 5.8% (Scheme 1.40).70

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12:26:53.

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28 Chapter 1
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cene-Containing Wide-Band-Gap Conjugated Polymers for High-Open-

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Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00032

CHAPTER 2

New Polymer Donors for

Polymer Solar Cells
LONG YEa,b, SUNSUN LIa,b, AND JIANHUI HOU*a
a
State Key Laboratory of Polymer Physics and Chemistry, Beijing National
Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy
of Sciences, Beijing 100190, P. R. China; bUniversity of Chinese Academy of
Sciences, Beijing 100049, P. R. China
*E-mail: [email protected]
12:26:57.

2.1 Introduction
Polymer solar cells (PSCs) have been the subject of extensive study owing
to their promising potentials of easy fabrication, high flexibility and light
weight when compared with other photovoltaic technologies.1–4 In the
past decade, great achievements have been obtained in developing new
active layer materials with broad absorption bands, appropriate molecular
energy levels and high mobilities. In order to realize more efficient PSCs,
many strategies including interface engineering, morphology control and
innovative device architectures have been devoted to optimizing conju-
gated photovoltaic polymers, thus promoting power conversion efficien-
cies (PCEs) to new heights.5–12 Clearly, the application of novel photovoltaic
polymers with superior photovoltaic properties is one of the main driving
forces in improving the photovoltaic performance of PSCs.5
In this chapter, we describe and discuss the recent advances in the poly-
meric photovoltaic donor materials in PSC devices. First, we summarize

RSC Polymer Chemistry Series No. 17

Polymer Photovoltaics: Materials, Physics, and Device Engineering
Edited by Fei Huang, Hin-Lap Yip, and Yong Cao
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

32
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New Polymer Donors for Polymer Solar Cells 33

and discuss the requirements and design strategies of donor polymers
in highly efficient PSCs. Design strategies such as backbone tuning, side
chain optimization and post-production are introduced along with several
excellent examples. Second, the design concepts and representative donor–
Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00032

acceptor (D–A) copolymers will be discussed. We will provide insights into

the correlation between device performance and detailed material prop-
erties, and rational guidance for molecular designing and fine-tuning of
novel photovoltaic polymers. Notably, the blooming developments of novel
two-dimensional conjugated polymers are emphasized. Third, novel terpoly-
mers have been introduced, which indicates that conjugated terpolymers
exhibit great potential for OPV application. Finally, we summarize the
future directions and approaches to developing higher performance donor
polymers for photovoltaic applications.
In 1995, Heeger and co-workers introduced the bulk-heterojunction
(BHJ) structure by simply blending polymer and fullerene as active materi-
als, which is considered the best PSC device architecture.13,14 The extensive
studies of donor polymer photovoltaic materials have been well discussed
and reviewed.15–25 Although thousands of donor polymers with different
backbones and side groups have been developed, synthesized and applied in
PSCs, donor polymers can be roughly classified into two types according to
their structures, namely the classical and novel donor polymers.
Three types of the first used homopolymer donor materials, i.e. the deriva-
tives of poly(1,4-phenylene vinylene) (PPVs), polythiophene (PTs), poly(thienyl-
ene vinylene) (PTVs) etc.,26–31 and are regarded as the classical polymer
donors (see Scheme 2.1). Among the classical donor polymers, regioregular
12:26:57.

poly(3-hexyl) thiophene (P3HT) is the most widely studied polymer in the

Scheme 2.1 The

 molecular structures of classical polymer donors.
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34 Chapter 2
30,31
field of PSC. The photovoltaic performance of P3HT/PCBM has been
widely studied by numerous groups. It should be noted that the photovol-
taic properties of P3HT/PCBM based PSC devices are strongly dependent on
the molecular weight and regioregularity of P3HT as well as the device fab-
Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00032

rication method.31 In this regard, various strategies have been developed to

optimize the performance of P3HT based PSCs. The breakthrough in the pho-
tovoltaic performance of P3HT/PCBM was reported by Yang et al.32 and Heeger
et al.33 in 2005, respectively. Yang and co-workers32 introduced the slow-growth
method to optimize the morphology of P3HT/PCBM, and a high PCE of 4.4%
was realized, which was the highest value reported in the past decade. As an
alternative, Heeger et al.33 utilized a process of post-annealing, and P3HT/
PCBM based PSC devices with PCE surpassing 5% were achieved. In 2009,
Li et al. introduced a novel fullerene acceptor, namely Indene-C60 bisadduct
(ICBA), with high-lying LUMO level in the P3HT-based PSCs, which pro-
moted the performance of P3HT to a new height.34 After that, solvent addi-
tives and device engineering methods were utilized and promoted the PCE
of P3HT/ICBA to over 6%.35–37 Other P3HT-analogue polymers, for example
PbTV,38 poly(3-pentylthiophene) (P3PT),39 P3HDTTT,40 PT-C3,41 etc. were also
explored in the device fabrications owing to their optimized molecular energy
or absorption characteristics. However, PCEs of ∼7% represent the bottleneck
of PSCs based on the classical donor polymers owing to the limited absorp-
tion ranges and molecular energy levels. In recent years, the novel donor poly-
mers have played important roles in promoting the PCEs of the PSC field.
In the following section, we will provide representative examples for donor–
acceptor copolymers based on two or more conjugated building blocks. For
12:26:57.

instance, silole-containing polymers, indacenodithiophene-based polymers,

benzodithiophene-based polymers, etc. will be introduced and discussed.

2.2 
Design Requirements and Strategies for Highly
Efficient Polymer Donors
2.2.1 
Design Requirements for Highly Efficient Polymer
Donors
The basic requirements in the molecular design of high efficiency photo-
voltaic polymers have been discussed and summarized in several reviews.
It is known that the PCE of a PSC is defined as PCE = ( JSC × VOC × FF)/Pin, in
which JSC is the short-circuit current density, VOC is the open-circuit voltage,
FF is the fill factor, and Pin is the input power in the form of solar radi-
ation. Consequently, simultaneous optimization of the above-mentioned
parameters is necessary to maximize the PCE. The VOC of the PSC can be
roughly approximated by the difference between the HOMO level of the
donor and the LUMO of the acceptor, even though other factors are also
found to influence the VOC. The value of FF can be mainly attributed to the
active layer morphology and charge transport through the bulk. The JSC of
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New Polymer Donors for Polymer Solar Cells 35

the solar cell is related to the product of the spectral absorption breadth
and the absorption intensity of the active layer. Basically, the photoelec-
trical conversion of PSCs can be classified into five physical processes:
(i) light absorption and exciton generation; (ii) exciton diffusion to the D–A
Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00032

interface; (iii) charge separation; (iv) charge transport; (v) charge collection.
From the view of the device physical process, important factors including
solubility, absorption, energy level, and mobility as well as morphology
should be considered when developing high performance donor polymers
for photovoltaic applications.

2.2.1.1 Solubility
The main factor relating to the ease of material processibility and photo-
voltaic performance is the polymer solubility in common organic solvents
such as chloroform (CF), chlorobenzene (CB), and dichlorobenzene (DCB).
Good solution processibility can result in good film-forming properties and
a desirable penetrating network, which is helpful for achieving high JSC and
excellent FF. The degree of solubility of a given polymer is governed by several
structural factors, including the degree of polymerization, the chain length
of the aromatic groups, the polarity of the attached substituents, backbone
rigidity, polymer regioregularity, and intermolecular interactions. Therefore,
from the viewpoint of molecular design, appropriate solubility is the first
requirement for novel conjugated polymers.
12:26:57.

2.2.1.2 Absorption Spectrum
The factors limiting the PCE of the PSCs include the low exploitation of
sunlight due to the narrower absorption band of the absorption spectra of
conjugated polymers in comparison with the solar irradiation spectrum.
To attain high JSC, the absorption spectrum of a novel polymer is needed
to match well with the solar radiation spectrum. From a photo-harvesting
point of view, the donor polymer should have a broad and intense absorption
with a high extinction coefficient (ε), on the order of 10−5 cm−1, in order to
maximize the incident photon harvest. Often the film or solution extinction
coefficient is the preliminary parameter used to evaluate the performance of
novel photovoltaic polymers. Narrowing the bandgaps of donor polymers is
helpful for absorbing more solar light, which provides the possibility of high
JSC. Up to now, great efforts have been devoted to developing low bandgap
(LBG) polymers.

2.2.1.3 Energy Level
The value of VOC for a PSC can be expressed by the empirical equation VOC =
[EHOMO(D) − ELUMO(A) − 0.3 eV]/e, where e is the elementary charge, EHOMO(D)
is the highest occupied molecular orbital (HOMO) of the polymer and 0.3 eV
 View Online

36 Chapter 2
is an empirical value for efficient charge separation. The lowest unoccu-
pied molecular orbital (LUMO) of [6,6]-phenyl-C61(or C71)-butyric acid methyl
ester (PCBM) is generally considered to be −3.9 eV. To overcome the exciton
binding energy (∼0.3 eV), the LUMO level of polymers should be −3.6 eV. In
Published on 08 September 2015 on http://pubs.rsc.org | doi:10.1039/9781782622307-00032

2006, Scharber et al.42 proposed a simple relation in correlating the HOMO

level and band gap of the polymer with the device performance (VOC, PCE)
of photovoltaic polymers, which can be used as a guideline for the selection
and design of new polymer donors for highly efficient PSCs, towards 10%
PCE. Appropriately lowering the HOMO level and reducing the voltage loss,
such as ΔLUMO, might be the key to simultaneous achievement of high VOC
and JSC.

2.2.1.4 Mobility
In fact, narrowing the band gap alone is not necessarily enough to achieve
the expected JSC. Other parameters, such as charge carrier mobility, intermo-
lecular interaction and molecular packing, have influence on JSC as well. Hole
mobility ( μh) is a significant parameter in evaluating the photovoltaic perfor-
mance of novel donor polymers. In addition, balanced mobility should also
be considered because FF is related to the ratio of hole-to-electron mobil-
ity of the D–A blends to some extent. Since the typical electron mobility of
PCBM is ∼10−4 cm2 V −1 s−1, the μh should be at least 10−4 cm2 V −1 s−1 for the
high performance donor polymers.
12:26:57.

2.2.1.5 Morphology
Besides the intrinsic properties of photovoltaic polymers, such as bandgaps
and molecular energy levels, morphological properties of the polymer/PCBM
blends, including crystallinity, domain size and domain purity, are also of
great importance for the photovoltaic performance of the PSC devices.9–12
The charge transfer, transport and collect are strongly dependent on the bulk
and vertical nano-scale morphology of the active layer.10,11 An optimal mor-
phology is crucial for photovoltaic polymers in achieving high efficiency in
BHJ PSC devices.
In order to achieve ideal morphology in photoactive layers, the blend films
can be treated with thermal annealing and solvent-annealing processes.
Alternatively, for high-performance polymer:fullerene blends, the film
morphology is effectively controlled by using mixed solvent systems. A typical
example is the low bandgap polymer poly(diketopyrrolopyrrole-terthio-
phene) (PDPP3T; Figure 2.1a); Ye et al. incorporated three functional solvents
in a novel ternary solvent system (Figure 2.1b), which dramatically promoted
the PCE up to 6.71%.12
Clearly, to obtain an ideal donor polymer, broader and stronger absorp-
tion, high hole mobility, and favorable morphology as well as suitable energy
levels should be realized.
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thinks that, if confronted, they will fight, Darnley will fall, and this
will serve ‘pour excuser votre affaire,’ as the Letter says. Buchanan
adds in his ‘History,’ that Bothwell was present to kill anybody
convenient (fol. 350). It was a wildly improbable scheme, especially
if Mary, as Buchanan says, called in Moray to stop the quarrel, or
share the blame, or be killed by Bothwell.
That the Letter, with some others of the set, is written in an odd,
affected style, does not yield an argument either to the attack or the
defence. If it is unlikely that Mary practised two opposite kinds of
style, it is also unlikely that a forger, or forgers, would venture on
attributing to her the practice. To this topic there will be
opportunities of returning.

Letter IV
This Letter merely concerns somebody’s distrust of a maid of Mary’s.
The maid is about to be married, perhaps to Bastian, but there is
nothing said that identifies either the girl, or the recipient of the
letter. Its tone, however, is that of almost abjectly affectionate
submission, and there is a note of a common end, to which the
writer and the recipient are working, ce à quoy nous tandons tous
deux. If Mary dismisses the maid, she, in revenge, may reveal her
scheme. The writer deprecates the suspicions of her correspondent,
and all these things mark the epistle as one in this series. As it
proves nothing against Mary, beyond affection for somebody, a
common aim with him, and fear that the maid may spoil the project,
there could be no reason for forging the Letter. A transcript of the
original French is in the Record Office.[363] The translators have
blundered over an important phrase from ignorance of French.[364]

Letter V
On the night of April 19, 1567, Bothwell obtained the signatures of
many nobles to ‘Ainslie’s Band,’ as it is called, a document urging
Mary to marry Bothwell.[365] On Monday, April 21, Mary went to
Stirling, to see her child. She was suspected of intending to hand
him over to Bothwell. If she meant to do this, her purpose was
frustrated. On Wednesday, April 23, she went to Linlithgow, and on
Thursday, April 24, was seized by Bothwell, near Edinburgh, and
carried to Dunbar. This Letter, if genuine, proves her complicity; and
is intended to prove it, if forged. On the face of it, the Letter was
written at Stirling. Mary regrets Bothwell’s confidence in an unworthy
person, Huntly, the brother of his wife. Huntly has visited her, and,
instead of bringing news as to how and when the abduction is to
managed, has thrown cold water on the plot. He has said that Mary
can never marry a married man who abducts her, and that the Lords
se dédiroient, which the Scots translator renders ‘the Lordis wald
unsay themselves, and wald deny that they had said.’ The reference
is to their acquiescence in the Ainslie band of April 19. Mary, as
usual, displays jealousy of Bothwell, who has ‘two strings to his bow,’
herself and his wedded wife. The Letter implies that, for some
reason, Mary and Bothwell had not arranged the details of the
abduction before they separated. A transcript of the original French
is at Hatfield; the English translation, also at Hatfield, is not from the
French, but is a mere Anglicising of the Scots version. Oddly enough
the French copy at Hatfield, unlike the rest, is in a Roman hand,
such as Mary wrote. The hand resembles that of the copyist of the
Casket Sonnets in the Cambridge (Lennox) MSS., and that of Mary
Beaton, but it is not Mary Beaton’s hand.

Letter VI
This Letter still deals with the manner of the enlèvement. Mary is
now reconciled to the idea of trusting Huntly.
She advises Bothwell as to his relations with the Lords. The passage
follows:—
‘Methinkis that zour services, and the lang amitie, having ye gude
will of ye Lordis, do weill deserve ane pardoun, gif above the dewtie
of ane subject yow advance yourself, not to constrane me, bot to
assure yourself of sic place neir unto me, that uther admonitiounis or
forane [foreign] perswasiounis may not let [hinder] me from
consenting to that, that ye hope your service sall mak yow ane day
to attene; and to be schort, to mak yourself sure of the Lordis and
fre to mary; and that ye are constraint for your suretie, and to be
abill to serve me faithfully, to use are humbil requeist, joynit to ane
importune actioun.
‘And to be schort, excuse yourself, and perswade thame the maist ye
can, yat ye ar constranit to mak persute aganis zour enemies.’
Now compare Mary’s excuses for her marriage, and for Bothwell’s
conduct, as written in Scots by Lethington, her secretary, in May,
1567, for the Bishop of Dunblane to present to the Court of France.
[366] First she tells at much length the tale of Bothwell’s ‘services,
and the lang amitie,’ as briefly stated in Letter VI. Later she
mentions his ambition, and ‘practising with ye nobillmen secretly to
make yame his friendis.’ This answers to ‘having ye gude will of ye
Lordis,’ in the Letter. In the document for the French Court, Mary
suggests, as one of Bothwell’s motives for her abduction, ‘incidentis
quhilk mycht occur to frustrat him of his expectatioun.’ In the Letter
he is ‘constrainit for his suretie, to carry her off.’ Finally, in the
Memorial for the French Court, it is said that Bothwell ‘ceased never
till be persuasionis and importune sute accumpaneit not the less
with force,’ he won Mary’s assent. In Letter VI. she advises him to
allege that he is obliged ‘to use ane humble requeist joynit to ane
importune action.’ Letter VI., in fact, is almost a succinct précis,
before the abduction, of the pleas and excuses which Mary made to
the French Court after her marriage. Could a forger have accidentally
produced this coincidence? One could: according to Sir John Skelton
the letter to her ambassador ‘is understood to have been drawn by
Maitland.’[367] The letter of excuses to France is a mere expansion of
the excuses that, in the Casket Letter which we are considering,
Mary advises Bothwell to make to the Lords. Either, then, this Letter
is genuine, or the hypothetical forger had seen, and borrowed from,
the Memorial addressed in May to the Court of France. This
alternative is not really difficult; for Lethington, as secretary, must
have seen, and may even (as Skelton suggests) have composed, the
Scots letter of excuses carried to France by the Bishop of Dunblane,
and Lethington had joined Mary’s enemies before they got
possession of the Casket and Letters. Oddly enough, the letter to the
ambassador contains a phrase in Scots which Lethington had used in
writing to Beaton earlier, Mary ‘could not find ane outgait.’[368] No
transcript of the original French, and no English translation, have
been found.

Letter VII
This Letter purports to follow on another, ‘sen my letter writtin,’ and
may be of Tuesday, April 22, as Mary reports that Huntly is anxious
about what he is to do ‘after to-morrow.’ She speaks of Huntly as
‘your brother-in-law that was,’ whereas Huntly, Bothwell not being
divorced, was still his brother-in-law. Huntly is afraid that Mary’s
people, and especially the Earl of Sutherland, will die rather than let
her be carried off. We do not know, from other sources, that
Sutherland was present. Mary implores Bothwell to bring an
overpowering force. No transcript of the original French, nor any
English translation, is known. Mary must have written two of these
letters (and apparently eleven sonnets also) while ill, anxious, and
busy, on the 22nd, at Stirling, with the third on the 23rd, either at
Stirling or Linlithgow. She could hardly get answers to anything
written as late as the 22nd, before Bothwell arrived at Haltoun, near
Linlithgow, on the night of April 23.

Letter VIII (III in Henderson)

There are differences of opinion as to the date of this curious Letter,
and as to its place in the series. The contemporary transcript, made
probably for the Commissioners on December 9, 1568, is in the
Record Office. I translate the Letter afresh, since it must be read
before any inference as to its date and importance can be drawn.
‘Sir,—If regret for your absence, the pain caused by your
forgetfulness, and by fear of the danger which every one predicts to
your beloved person, can console me, I leave it to you to judge;
considering the ill fortune which my cruel fate and constant trouble
have promised me, in the sequel of sorrows and terrors recent and
long passed; all which you well know. But, in spite of all, I will not
accuse you either of your scant remembrance or scant care, and still
less of your broken promise, or of the coldness of your letters, I
being so much your own that what pleases you pleases me. And my
thoughts are so eagerly subject to yours that I am fain to suppose
that whatsoever comes from you arises not from any of the
aforesaid causes, but from such as are just and reasonable, and
desired by myself. Which is the final order that you have promised
me to take for the safety[369] and honourable service of the sole
support of my life, for whom alone I wish to preserve it, and without
which I desire only instant death. And to show you how humbly I
submit me to your commands, I send you, by Paris, in sign of
homage, the ornament’ (her hair) ‘of the head, the guide of the
other members, thereby signifying that, in investing you with the
spoil of what is principal, the rest must be subject to you with the
heart’s consent. In place of which heart, since I have already
abandoned it to you, I send you a sepulchre, of hard stone, painted
black, semé with tears and bones.[370] I compare it to my heart,
which, like it, is graven into a secure tomb or receptacle of your
commands, and specially of your name and memory, which are
therein enclosed, like my hair in the ring. Never shall they issue forth
till death lets you make a trophy of my bones, even as the ring is full
of them’ (i.e. in enamel), ‘in proof that you have made entire
conquest of me, and of my heart, to such a point that I leave you
my bones in memory of your victory, and of my happy and willing
defeat, to be better employed than I deserve. The enamel round the
ring is black, to symbolise the constancy of her who sends it. The
tears are numberless as are my fears of your displeasure, my tears
for your absence, and for my regret not to be yours, to outward
view, as I am, without weakness of heart or soul.
‘And reasonably so, were my merits greater than those of the most
perfect of women, and such as I desire to be. And I shall take pains
to imitate such merits, to be worthily employed under your
dominion. Receive this then, my only good, in as kind part as with
extreme joy I have received your marriage’ (apparently, from what
follows, a contract of marriage or a ring of betrothal), ‘which never
shall leave my bosom till our bodies are publicly wedded, as a token
of all that I hope or desire of happiness in this world. Now fearing,
my heart, to weary you as much in the reading as I take pleasure in
the writing, I shall end, after kissing your hands, with as great love
as I pray God (O thou, the only prop of my life!) to make your life
long and happy, and to give me your good grace, the only good
thing which I desire, and to which I tend. I have shown what I have
learned to this bearer, to whom I remit myself, knowing the credit
that you give him, as does she who wishes to be ever your humble
and obedient loyal wife, and only lover, who for ever vows wholly to
you her heart and body changelessly, as to him whom I make
possessor of my heart which, you may be assured, will never change
till death, for never shall weal or woe estrange it.’
The absurd affectation of style in this Letter, so different from the
plain manner of Letters I. and II., may be a poetical effort by Mary,
or may be a forger’s idea of how a queen in love ought to write. In
the latter case, to vary the manner so much from that of the earlier
Letters, was a bold experiment and a needless.
Mary, to be brief, sends to Bothwell a symbolic mourning ring,
enclosing her hair. It is enamelled in black, with tears and bones.
Such a ring is given by a girl to her lover, as a parting token, in the
Cent Nouvelles Nouvelles (xxvi.), a ring d’or, esmailée de larmes
noires.[371] She promises always to keep the ‘marriage’ (that is the
contract of marriage, or can it be a ring typical of marriage?) in her
bosom, till the actual wedding in public. Now she had a sentimental
habit of wearing love tokens ‘in her bosom.’ She writes to Norfolk
from Coventry (December, 1569), ‘I took the diamant from my Lord
Boyd, which I shall keep unseene about my neck till I give it agayn
to the owner of it and of me both.’[372]
As to the Contract of Marriage (if Mary wore that in her bosom[373]),
two alleged contracts were produced for the prosecution. One was a
‘contract or promise of marriage’ by Mary to Bothwell, in the Italic
hand, and in French; the hand was said to be Mary’s own. It was
undated, and a memorandum in the ‘Detection’ says, ‘Though some
words therein seme to the contrary, yet is on credible groundes
supposed to have been made and written by her befoir the death of
her husband.’ The document explicitly mentions that ‘God has taken’
Darnley. The document, or jewel, treasured by Mary would, of
course, be Bothwell’s solemn promise, or token of promise, the
counterpart of hers to him, published in Buchanan.[374]
Now there also existed a contract, said to be in Huntly’s hand, and
signed by Mary and Bothwell, of date April 5 (at Seton), 1567. But
this contract speaks of the process of divorce ‘intentit’ between
Bothwell and his ‘pretensit spouse.’ Now that suit, on April 5, was
not yet before the Court (though some documents had been put in),
nor did Lady Bothwell move in the case till after Mary’s abduction.
If Mary kept this contract, and if it be correctly dated, then Letter
VIII. is not of January-February, but of April, 1567.
If Mary regarded herself as now privately married, this pose would
explain the phrase ‘your brother-in-law that was,’ in Letter VIII. But
this is stretching possibilities.
Mr. Hosack has argued that the Letter just translated was really
written to Darnley, between whom and Mary some private
preliminary ceremony of marriage was said to have passed. In that
case the words par Paris, ‘I send you by Paris, &c.,’ are a forged
interpolation, as Paris was not in Mary’s service till January, 1567.
The opening sentence about the danger which, as every one thinks,
menaces her correspondent, might refer to Darnley. But the tone of
remonstrance against indifference, suspicion, and violated promises,
is the tone of almost all the Casket Letters, and does not apply to
Darnley—before his public marriage.
As to the ‘heart in a ring,’ Mary, as Laing notes, had written to
Elizabeth ‘Je vous envoye mon cœur en bague.’ The phrase in the
Letter, seul soutien de ma vie, also occurs in one of the Casket
Sonnets.
To what known or alleged circumstances in Mary’s relations with
Bothwell can this Letter refer? The alternatives are (1) either to her
receipt of Bothwell’s answer to Letter II., which Paris (on our scheme
of dates) gave to Mary on January 25, at Glasgow; (2) to the
moment of her stay at Callendar, where she arrived, with Darnley, on
January 27, taking him on January 28 to Linlithgow, whence, on
January 29, ‘she wraytt to Bothwell.’ She had learned at Linlithgow,
on January 28, by Hob Ormistoun, that Bothwell was on his way
from Liddesdale.[375] Or (3) does the letter refer to Monday, April 21,
when she was at Stirling till Wednesday, April 23, when she went to
Linlithgow, Bothwell being ‘at Haltoun hard by,’ and carrying her off
on April 24?[376]
Taking first (1)—we find Mary acknowledging in this letter the receipt
of Bothwell’s ‘marriage.’ If this is a contract, did Bothwell send it in
the letter which, according to Paris, he wrote on January 24,
accompanying it with a diamond? ‘Tell the Queen,’ said Bothwell,
‘that I send her this diamond, which you are to carry, and that if I
had my heart I would send it willingly, but I have it not.’ The
diamond, a ring probably, might be referred to in Bothwell’s letter as
a marriage or betrothal ring (French, union). In return Mary would
send her mourning ring; ‘the stone I compare to my heart.’
This looks well, but how could Mary, who, ex hypothesi, had just
received a ring, a promise or contract of marriage, and a loving
message, complain, as she does, of ‘the coldness of your letters,’
‘your violated promise,’ ‘your forgetfulness,’ ‘your want of care for
me’? Danger to Bothwell, in Liddesdale, she might fear, but these
other complaints are absolutely inconsistent with the theory that
Bothwell had just sent a letter, a ring, a promise of marriage, and a
loving verbal message. We must therefore dismiss hypothesis 1.
(2) Did Mary send this Letter on January 29 from Linlithgow? She
had no neglect to complain of there; for, according to her accusers,
she was met by Hob Ormistoun, with a letter or message. Paris says
this was at Callendar, where she slept on January 27.[377] In that
case Bothwell was yet more prompt. Again, Mary had now no fear of
danger to Bothwell’s person, as she had just learned that Bothwell
had left perilous Liddesdale. Here, once more, there is no room,
reason, or ground for her complaints. Again, in the Letter she says
that she sends the mourning ring ‘by Paris.’ But, if we are to believe
Paris, she did not do so. He gave her Bothwell’s letter, received from
Bothwell’s messenger, at Callendar, January 27. She answered it at
bedtime, gave it to Paris to be given to Bothwell’s messenger,
enclosing a ring, and the messenger carried ring and letter to
Bothwell. She could not write, ‘I have sent you by Paris’ the ring, if
she did nothing of the sort. Later, according to Paris, she did send
him, with the bracelets, from Linlithgow to Edinburgh, where he met
Bothwell, just mounting to ride and join Mary and Darnley on their
return. The Letter, then, does not fit the circumstances of one
written either at Callendar, January 27 (Paris), or at Linlithgow,
January 29 (‘Cecil’s Journal’).
(3) That the ring, and the lamentations, were carried, by Paris, from
Linlithgow to the neighbouring house of Haltoun, where Bothwell lay,
on the night of April 23, the night before he bore Mary off to Dunbar,
is not credible. Nothing indicates her receipt of token or contract of
marriage at that date. The danger to Bothwell was infinitesimal. He
was not neglecting Mary, he was close to her, and only waiting for
daylight to carry her off. He wrote in reply, Paris says, and verbally
promised to meet her, ‘on the road, at the bridge.’[378]
To a man who was thus doing his best to please her, a man whom
she was to meet next day, Mary could not be writing long, affected
complaints and lamentations. She would write, if at all, on details of
the business on hand. No ring was carried by Paris, according to his
own deposition.
Thus the contents of the Letter do not fit into any recorded or
alleged juncture in Mary’s relations with Bothwell, after January 21,
1567, when Paris (whom the Letter mentions) first entered her
service. Laing places the Letter last in the series, and supposes that
the ring and letter were sent from Linlithgow, to Bothwell hard by (at
Haltoun), the night before the ‘ravishment.’ But he does not make it
plain that the contents of the Letter are really consistent with its
supposed occasion.[379] When was Bothwell absent from Mary, cold,
forgetful, and in danger, between the return from Glasgow, and the
abduction? The Letter does not help the case of the prosecution.
We have exhausted the three conceivable alternatives as to the date,
occasion, and circumstances of this Letter. Its contents fit none of
these dates and occasions. Mr. Froude adds a fourth alternative. This
Letter ‘was written just before the marriage’[380] when Bothwell
(whose absence is complained of) was never out of Mary’s company.
There is not, in short, an obvious place for this Letter in the recorded
circumstances of Mary’s history, though the lack of obviousness may
arise from our ignorance of facts.
 XVI
THE CASKET SONNETS
When the ‘Detection’ of Buchanan was first published, La Mothe
Fénelon, French ambassador in England, writing to Charles IX.,
described the Sonnets as the worst, or most compromising, of all the
evidence. They never allude to Darnley, and must have been written
after his death. As is well known, Brantôme says that such of Mary’s
verses as he had seen were entirely unlike the Casket Sonnets,
which are ‘too rude and unpolished to be hers.’ Ronsard, he adds,
was of the same opinion. Both men had seen verses written hastily
by Mary, and still ‘unpolished,’ whether by her, or by Ronsard, who
may have aided her, as Voltaire aided Frederick the Great. Both
critics were, of course, prejudiced in favour of the beautiful Queen.
Both were good judges, but neither had ever seen 160 lines of
sonnet sequence written by her under the stress of a great passion,
and amidst the toils of travel, of business, of intense anxiety, all in
the space of two days, April 21 to April 23.

Plate A
 Larger Image

TWO SONNETS FROM THE CAMBRIDGE MS.

The hand somewhat resembles that of Mary in early youth,

and that of Mary Beaton
The copyist is unknown

That the most fervent and hurried sonneteer should write eleven
sonnets in such time and circumstances is hard to believe, but we
must allow for Mary’s sleepless nights, which she may have beguiled
by versifying. It is known that a distinguished historian is occupied
with a critical edition of these Sonnets. We may await his decision as
to their relations with the few surviving poems of the Queen. My
own comparison of these does not convince me that the favoured
rhymes are especially characteristic of Mary. The topics of the Casket
Sonnets, the author’s inability to remove the suspicions of the
jealous Bothwell; her protestations of submission; her record of her
sacrifices for him; her rather mean jealousy of Lady Bothwell, are
also the frequent topics of the Casket Letters. The very phrases are
occasionally the same: so much so as to suggest the suspicion that
the Letters may have been modelled on the Sonnets, or the Sonnets
on the Letters. If there be anything in this, the Sonnets are probably
the real originals. Nothing is less likely than that a forger would think
of such a task as forging verses by Mary: nor do we know any one
among her enemies who could have produced the verses even if he
had the will. To suspect Buchanan is grotesque. On the theory of a
literary contest between Mary and Lady Bothwell for Bothwell’s
affections, something is to be said in the following chapter.
Meanwhile, I am obliged to share the opinion of La Mothe Fénelon,
that, as proof of Mary’s passion for Bothwell, the Sonnets are
stronger evidence than the Letters, and much less open to suspicion
than some parts of the Letters.
 XVII
CONCLUSIONS AS TO THE LETTERS AND THE
POSSIBLE FORGERS
A few words must be said as to a now obsolete difficulty, the
question as to the language in which the Letters were originally
written. That question need not be mooted: it is settled by Mr.
Henderson’s ‘Casket Letters.’ The original language of the epistles
was French.
I. The epistles shown at Westminster were certainly in French, which
was not (except in the first one or two sentences) the French later
published by the Huguenots. That French was translated from the
Latin, which was translated from the Scots, which was translated
from the original French. Voluminous linguistic criticisms by Goodall,
Hosack, Skelton, and others have ceased, therefore, to be in point.
II. Many phrases, whether as mirrored in the Scots and English
translations, or as extant in contemporary copies of the original
French, can be paralleled from authentic letters of Mary’s. Bresslau
proved this easily, but it was no less easily proved that many of the
phrases were conventional, and could be paralleled from the
correspondence of Catherine de’ Medici and other contemporary
ladies. A forger would have ample opportunities of knowing Mary’s
phrasing and orthography. It would be easy for me to write a letter
reproducing the phrasing and orthography, which is very distinctive,
of Pickle the Spy. No argument against forgery can be based on
imitations of peculiarities of phrase and spelling which the
hypothetical forger was sure to know and reproduce.
But phrasing and spelling are not to be confounded with tone and
style. Now the Letters, in tone, show considerable unity, except at
one point. Throughout Mary is urging and spurring an indifferent
half-hearted wooer to commit an abominable crime, and another
treasonable act, her abduction. Really, to judge from the Letters, we
might suppose Bothwell to be almost as indifferent and reluctant as
Field-Marshal Keith was, when the Czarina Elizabeth offered him her
hand. Keith put his foot down firmly, and refused, but the Bothwell
who hesitated was lost. It is Mary who gives him no rest till he
carries her off: we must blame Bothwell for not arranging the
scheme before parting from Mary in Edinburgh; to be sure,
Buchanan declares in his History that the scheme was arranged. In
short, we become almost sorry for Bothwell, who had a lovely royal
bride thrust on him against his will, and only ruined himself out of
reluctance to disoblige a lady. It is the old Irish tale of Diarmaid and
Grainne over again.
But, on the other hand, Letter II. represents Mary as tortured by
remorse and regret. Only to please Bothwell would she act as she
does. Her heart bleeds at it. We must suppose that she not only
grew accustomed to the situation, but revelled in it, and insisted on
an abduction, which even Lethington could only explain by her
knowledge of the apices juris, the sublimities of Scots law. A pardon
for the abduction would, in Scots law, cover the murder.
Such is the chief difference in tone. In style, though the fact seems
to have been little if at all noticed, there are two distinct species.
There is the simple natural style of Letters I., II., and the rest, and
there is the alembicated, tormented, precious, and affected style of
Letters VIII. (III.) and IV. Have we any other examples, from Mary’s
hand, of the obscure affectations of VIII. (III.) and IV.? Letter VIII.,
while it contains phrases which recur in the Casket ‘Sonnets,’ is really
more contorted and symboliste in manner than the verses. These
‘fond ballads’ contain, not infrequently, the same sentiments as the
Letters, whether the Letters be in the direct or in the affected style.
Thus, in Letter II., where Lady Bothwell and Mary’s jealousy of her
are the theme, we read ‘Se not hir’ (Lady Bothwell) ‘quhais feinzeit
teiris should not be sa mekle praisit or estemit as the trew and
faithful travellis quhilk I sustene for to merite her place.’ Compare
Sonnets ii. iii.:
Brief je feray de ma foy telle preuve,
Qu’il cognoistra sans faulte ma constance,
Non par mes pleurs ou fainte obeyssance
Comme autres font, mais par divers espreuve.
In both passages the writer contrasts the ‘feigned tears,’ ‘feigned
obedience’ of Bothwell’s wife with her own practical proofs of
devotion: in the Sonnet using ‘them’ for ‘her’ as in Letter IV.
A possible, but unexpected explanation of the extraordinary diversity
of the two styles, I proceed to give. We have briefly discussed the
Sonnets, which (despite the opinion of Ronsard) carry a strong
appearance of authenticity, though whether their repetitions of the
matter and phrasing of the Letters be in favour of the hypothesis
that both are authentic might be argued variously. Now from the
Sonnets it appears that Lady Bothwell was endeavouring to secure
her bridegroom’s heart in a rather unlooked-for manner: namely, by
writing to him elaborately literary love letters in the artificial style of
the age of the Pleiad. As the Sonnets say, she wooes him ‘par les
escriptz tout fardez de sçavoir.’ But Mary maintains that Lady
Bothwell is a mere plagiarist. Her ingenious letters, treasured by
Bothwell, and the cause of his preference for her, are
empruntés de quelque autheur luisant!
We have already tried to show that Bothwell was not the mere
‘brave stupid strong-handed Border noble,’ ‘the rough ignorant moss-
trooper,’ but a man of taste and culture. If the Sonnets be genuine,
there was actually a contest in literary excellence between Bothwell’s
wife and his royal mistress. This queer rivalry would account for the
style of Letter VIII., in which Mary labours to prove to Bothwell, as it
were, that she is as capable as his wife of writing a fashionable,
contorted, literary style, if she chooses: in poetry, too, if she likes.
We naturally feel sorry for a man of action who received, at a
moment when decisive action was needful, such an epistle as Letter
VIII., and we naturally suppose that he never read it, but tossed it
into the Casket with an explosion of profane words. But it is just
conceivable that Bothwell had a taste for the ‘precious,’ and that, to
gratify this taste, and eclipse Lady Bothwell, Mary occasionally wrote
in the manner of Letter VIII. or quoted Jason, Medea, and Creusa.
This hypothesis, far-fetched as it may seem, at all events is naturally
suggested by Sonnet VI. On the other hand, it is difficult to imagine
that a dexterous forger would sit down to elaborate, whether from
genuine materials or not, anything so much out of keeping with his
Letter II. as is his Letter VIII. Yet Letter VIII., as we saw, cannot be
connected with any known moment of the intrigue.
While the Letters thus vary in style, in tone of sentiment they are all
uniform, except Letter II. We are to believe that the forger
deliberately laid down a theory of this strange wooing. The Queen
throughout is much more the pursuer than the pursued. Bothwell is
cold, careless, breaks promises, is contemptuously negligent, does
not write, is suspicious, prefers his wedded wife to his mistress.
Contemporary gossip averred that this, in fact, was his attitude.
Thus, after Mary had been sent to Loch Leven, Lethington told du
Croc that ‘Bothwell had written several times to his first wife, Lady
Bothwell, since he lay with the Queen, and in his letters assured
Lady Bothwell that he regarded her as his wife, and the Queen as
his concubine.’ Lethington reported this to Mary herself, who
discredited the fact, but Lethington relied on the evidence of
Bothwell’s letters.[381] How could he know anything about them? The
belief in Bothwell’s preference of his wife was general, and,
doubtless, it may be urged that this explains the line taken by the
forger.
The passion, in the Letters, is all on the side of Mary. By her eternal
protests of entire submission she recalls to us at once her eager
service to Darnley in the first days of their marriage, and her
constant promises of implicit obedience to Norfolk. To Norfolk, as to
Bothwell (we have already shown), she expresses her hope that ‘you
will mistrust me no more.’[382] ‘If you be in the wrong I will submit
me to you for so writing, and ax your pardon thereof.’ She will beg
pardon, even if Norfolk is in the wrong! Precisely in the same tone
does Mary (in Letter VIII.), after complaining of Bothwell’s
forgetfulness, say, ‘But in spite of all I will not accuse you, either of
your scant remembrance or scant care, and still less of your broken
promise, seeing that what pleases you pleases me.’
This woman, whose pride is said to be in contradiction with her
submission, as expressed in the Casket Letters, writes even to
Elizabeth, ‘Je me sousmetray à vos commandemants.’[383] In Letter
VIII. Bothwell is congratulated on ‘votre victoire et mon agreable
perte.’ To Elizabeth Mary writes ‘Vous aurés fayt une profitable
conqueste de moy.’
That any forger should have known Mary so well as to place her,
imaginatively, as regarded Bothwell, in the very attitude which we
see that, on occasion, she chose later to adopt in fact, as regarded
Norfolk, is perhaps beyond belief. It may be urged that she probably,
in early days, wrote to Darnley in this very tone, that Darnley’s
papers would fall into his father’s hands, and that Lennox would
hand them over as materials to the forger. But ‘it is to consider too
curiously to consider thus.’
Such are the arguments, for the defence and the attack, which may
be drawn from internal evidence of style. To myself this testimony
seems rather in favour of the authenticity of considerable and
compromising portions of the papers.
Letter VIII. (intended to prove a contract of marriage with Bothwell)
remains an enigma to me: the three Letters proving Mary’s
eagerness for the abduction are not without suspicious traits. The
epistle about bringing Lord Robert to kill Darnley in a quarrel is
involved in the inconsistencies which we have shown to beset that
affair. The note about the waiting-woman was hardly worth forging,
compromising as it is. Letter I. seems to me certainly authentic, if
we adopt the scheme of dates suggested, and reject that of ‘Cecil’s
Journal,’ which appears to be official, and answers to Lennox’s
demands for dates. It may be merely Lennoxian, but no other
scheme of chronology is known to have been put in by the accusers.
Letter I., if our dates are admitted, implies the existence of a letter
answering to Letter II., which I have had to regard as, in some parts
at least, genuine. If forgery and tampering were attempted (as I
think they certainly were in the letter never produced, but described
by Lennox and Moray, and perhaps in other cases), who was the
criminal?
My reply will have been anticipated. Whoever held the pen of the
forger, Lethington must have directed the scheme. This idea, based
on we know not what information, though I shall offer a conjecture,
occurred to Elizabeth, as soon as she heard the first whisper of the
existence of the Letters, in June-July, 1567. On July 21, de Silva
mentioned to her what he had heard—that the Lords held certain
Letters ‘proving that the Queen had been cognisant of the murder of
her husband. She told me it was not true, though Lethington had
behaved badly in the matter.’[384] The person from whom Elizabeth
thus early heard something connecting Lethington, in an evil way,
with the affair must have been Robert Melville. His position was then
peculiar. He was first accredited to Elizabeth, on June 5, 1567, by
Mary, Bothwell, and Lethington.[385] Melville left Scotland, for Mary,
on June 5, returned to Scotland, and again rode to London on June
21, as the envoy of some of her enemies. Now June 21 was the day
of the opening of the Casket, and inspection of its contents. A
meeting of the Privy Council was held on that day, but Lethington’s
name is not among those of the nobles who attended it.[386] The
minutes of the Council say not a word about the Casket, though the
members attending Council were, with several others, present, so
Morton declared, at the opening of the Casket. Though not at the
Council, Lethington was at the Casket scene, according to Morton.
And on that very day, Lethington wrote a letter to Cecil, the bearer
being Robert Melville, who, says Lethington, is sent ‘on sudden
dispatch.’[387] Melville, in addition to Lethington’s letter, carried a
verbal message to Cecil, as the letter proves. We may glean the
nature of the verbal message from the letter itself.
We know that the Lords, in December of the same year, publicly and
in Parliament, and with strange logic, declared that the ground of
their rising and imprisonment of Mary was her guilt as revealed in
letters written by her hand, though these were not discovered when
the Lords imprisoned Mary. Now Lethington, in his dispatch to Cecil,
carried by Melville the day of the Casket finding, says that the
bearer, Mr. Robert Melville, ‘can report to you at length the ground of
the Lords’ so just and honourable cause.’ Presently that ‘ground’ was
declared to be the evidence of the Casket Letters. Melville then
would verbally report this new ‘ground’ to Cecil and Elizabeth. He
was dispatched at that very date for no other reason. The Lords
were Melville’s employers, but his heart was sore for Mary. Elizabeth,
on June 30, tells Mary (Throckmorton carried her letter) that ‘your
own faithful servant, Robert Melville, used much earnest speech on
your behalf.’[388] What Elizabeth knew about Lethington’s bad
behaviour as to the Letters, and spoke of to de Silva, she must have
heard from Robert Melville. She did not, as far as we are aware,
mention her knowledge of the subject till de Silva introduced it on
July 21, but only from Melville could she learn whatever she did
learn about Lethington. Throckmorton, her envoy to Scotland, did
not mention the Letters till July 25, four days after Elizabeth spoke
to de Silva. ‘Jhone a Forret,’ whom the Lords sent through London
on July 8 to bring Moray, was not exactly the man to blame
Lethington and discredit the Letters: for he was probably John
Wood, later a chief enemy of Mary.
Suspicions of Lethington, later, were not confined to Elizabeth alone.
In Mary’s instructions to her Commissioners (Sept. 9, 1568) she
says, ‘There are divers in Scotland, both men and women, that can
counterfeit my handwriting, and write the like manner of writing
which I use [the ‘Roman’ or Italic] as well as myself, and principally
such as are in company with themselves,’[389] as Lethington then
was.
Lesley stated the matter thus: ‘There are sundry can counterfeit her
handwriting, who have been brought up in her company, of whom
there are some assisting themselves’ (the Lords) ‘as well of other
nations as of Scots, as I doubt not both your highness’ (Elizabeth)
‘and divers others of your Highness’s Court, has seen sundry letters
sent here from Scotland, which would not be known from her own
handwriting.’[390]
All this is vague, and Mary’s reference to women, Lesley’s reference
to those ‘brought up in her company,’ glance, alas! at the Queen’s
Maries. Mary Livingstone, wedded to John Sempil, was not on the
best terms with Queen Mary about certain jewels. Mary Fleming was
Lethington’s wife. Mary Beaton’s aunts were at open feud with the
Queen. A lady, unnamed, was selected as the forger by the author of
‘L’Innocence de la Royne d’Escosse’ (1572).
To return to Lethington. In 1615, Camden, writing, as it were, under
the eye of James VI. and I., declared that Lethington ‘had privately
hinted to the Commissioners at York, that he had counterfeited
Mary’s hand frequently.’[391] There is nothing incredible, a priori, in
the story. Between October 11, 1568 (when Norfolk, having been
privately shown the Letters, was blabbing, even to his servant
Bannister, his horror of Letter II.), and October 16, when Lethington
rode out with Norfolk, and the scheme for his marrying Mary struck
deep root, something may have been said. Lethington may have told
Norfolk that perhaps the Letters were forged, that he himself, for
amusement, had imitated Mary’s hand. As a fact, the secretaries of
two of the foremost of contemporary statesmen did write to the
innumerable bores who beset well-known persons, in hands hardly
to be distinguished from those of their chiefs. Norfolk, as Laing says,
did acknowledge, at his trial, that Lethington ‘moved him to consider
the Queen as not guilty of the crimes objected.’ Lethington appears
to have succeeded; possibly by aid of the obvious argument that, if
he could imitate Mary’s hand for pastime, others might do it for evil
motives. Nay, we practically know, and have shown, that Lethington
did succeed in making Norfolk, to whom, five days before, he had
offered the Letters as proofs of Mary’s guilt, believe that she had not
written them. For, as we have seen, whereas Mary at this time was
making a compromise with Moray, Norfolk persuaded her to abandon
that course. Thus Lethington, on October 11, 1568, made Norfolk
believe in the Letters; on October 16, he made him disbelieve or
doubt.
We are not to suppose Lethington so foolish as to confess that he
was himself the forger. Even if Lethington did tell Norfolk that he had
often imitated Mary’s hand, he could not have meant to accuse
himself in this case. His son, in 1620, asked Camden for his
authority, and we know not that Camden ever replied. He never
altered his statement, which meant no more than that, by the
argument of his own powers of imitating Mary’s handwriting,
Lethington kept urging the Duke of Norfolk to doubt her guilt.[392]
Lethington’s illustration of the ease with which Mary’s writing could
be imitated is rather, if he used it, a proof that he did not hold the
pen which may have tampered with the Casket Letters. Our reasons
for suspecting him of engaging, though not as penman, in the
scheme are:
1. Elizabeth’s early suspicion of Lethington, and the probability that
Robert Melville, who had just parted from Lethington, inspired that
suspicion.
2. The probability, derived from Randolph’s letter, already cited, that
Lethington had access to the Casket before June 21, 1567, but after
Mary’s capture at Carberry.
3. Of all men Lethington, from his knowledge of Mary’s disgust at his
desertion, ingratitude, and ‘extreme opposition’ to her, in her darkest
hour, and from his certainty that Mary held, or professed to hold,
documentary proof of his own guilt, had most reason to fear her,
and desire and scheme her destruction.
4. Kirkcaldy of Grange, on April 20, 1567, months before the Letters
were discovered, wrote to Cecil that Mary ‘has said that she cares
not to lose (a) France, (b) England, and (c) her own country’ for
Bothwell.[393]
Compare, in the Lennox version of the letter never produced (p.
214)—
(a) The loss of her dowry in France.
(b) Her titles to the crown of England.
(c) The crown of her realm.
Unless this formula of renunciations, in this sequence, was a
favourite of Mary’s, in correspondence and in general conversation,
its appearance, in the letter not produced, and in Kirkcaldy’s letter
written before the Casket was captured, donne furieusement à
penser.
5. Another curious coincidence between a Casket Letter (VII.) and
Mary’s instructions to the Bishop of Dunblane, in excuse of her
marriage, has already been noticed. We may glance at it again.

Instructions Letter VII.

We thocht his Gif abone the dewtie
continuance in the of ane subject yow
awayting upon us ... had advance yourself.
procedit onelie upoun the
ackawlegeing of his
dewtie, being our borne
subject.
The persuasionis quhilk That uther
oure friendis or his admonitiounis or
unfriendis mycht cast out forane persuasiounis
for his hinderence ... may not let me from
consenting ...
Sa ceased he nevir till be To use ane humbil
persuasionis and requiest joynit to
 importune sute, ane importune
accumpaneit nottheles action.
with force.

The whole scheme of excuse given in Letter VII. is merely expanded

into the later Instructions, a piece of eleven pages in length. ‘The
Instructions are understood to have been drawn by Lethington,’ says
Sir John Skelton; certainly Mary did not write them, as they stand,
for they are in Scots. ‘Many things we resolved with ourselves, but
never could find ane outgait,’ say the Instructions. ‘How to be free of
him she has no outgait,’ writes Maitland to Beaton. If Lethington, as
Secretary, penned the Instructions, who penned Letter VII.?
6. We have already cited Randolph’s letter to Kirkcaldy and
Lethington, when they had changed sides, and were holding the
Castle for the Queen. But we did not quote all of the letter.
Lethington, says Randolph, with Grange, is, as Mary herself has said,
the chief occasion of all her calamities, by his advice ‘to apprehend
her, to imprison her; yea, to have taken presently the life from her.’
This follows a catalogue of Lethington’s misdeeds towards Mary,
exhaustive, one might think. But it ends, ‘with somewhat more that
we might say, were it not to grieve you too much herein.’ What
‘more’ beyond arrest, loss of crown, prison, and threatened loss of
life, was left that Lethington could do against Mary? The
manipulation of the Casket Letters was left: ‘somewhat more that we
might say, were it not to grieve you too much herein.’[394]
Randolph had been stirring the story of Lethington’s opening the
coffer in a green cover, in the autumn of 1570. Charges and counter-
charges as to the band for murdering Darnley had been flying about.
On January 10, 1571, Cecil darkly writes to Kirkcaldy that of
Lethington he ‘has heard such things as he dare not believe.’[395]
This cannot refer to the declaration, by Paris, that Lethington was in
the murder, for that news was stale fifteen months earlier.
As to the hand that may have done whatever unfair work was done,
we can hope for no certainty. Robert Melville, in 1573, being taken
out of the fallen Castle, and examined, stated that ‘he thinkis that
the lard of Grange’ (Kirkcaldy) ‘counterfaitit the Regentis’ (Moray’s)
‘handwrite, that was sent to Alixr Hume that nycht.’ But we do not
accuse Kirkcaldy.
There is another possible penman, Morton’s jackal, a Lord of
Session, Archibald Douglas. That political forgery was deemed quite
within the province of a Scottish Judge, or Lord of Session, in the
age of the Reformation, we learn from his case. A kinsman of
Morton, one of Darnley’s murderers, and present, according to
Morton, at the first opening of the Casket, Archibald was accused by
his elder brother, William Douglas of Whittingham, of forging letters
from Bishop Lesley to Lennox, the favourite of James VI., and others
(1580-1581).[396] Of course a Lord of Session might bear false
witness against his brother in the flesh, and on the Bench. But
perhaps Archibald himself, a forger of other letters, forged the
Casket Letters; he had been in France, and may have known French.
All things are conceivable about these Douglases.
It is enough to know that experts in forgery, real or reputed, were
among Mary’s enemies. But, for what they are worth, the hints
which we can still pick up, and have here put together, may raise a
kind of presumption that, if falsification there was, the manager was
Lethington. ‘The master wit of Lethington was there to shape the
plot,’ said Sir John Skelton, though later he fell back on Morton, with
his ‘dissolute lawyers and unfrocked priests’—like Archie Douglas.
I do not, it will be observed, profess to be certain, or even strongly
inclined to believe, that there was any forgery of Mary’s writings,
except in the case of the letter never produced. But, if forgery there
was, our scraps and hints of evidence point to Lethington as
manager of the plot.

Plate A B
 Larger Image

EXAMPLES OF MARY’S HAND

One of these two is, in part, not genuine, but imitated

Plate B A
 Larger Image

EXAMPLES OF MARY’S HAND

In one some parts are not genuine, but imitated

The text is Mary to Elizabeth, B. Museum, Calig. C.I. Number 421 in
Bain. Calendar II. p. 659 (1900)

As to problems of handwriting, they are notoriously obscure, and the

evidence of experts, in courts of justice, is apt to be conflicting. The
testimony in the case of Captain Dreyfus cannot yet have been
forgotten. In Plates BA, AB the reader will find a genuine letter of
Mary to Elizabeth, and a copy in which some of the lines are not her
own, but have been imitated for the purpose of showing what can
be done in that way. ‘The puzzle is’ to discover which example is
entirely by the Queen, and which is partly in imitation of her hand.
In Plate F is an imitation of Mary’s hand, as it might have appeared
in writing Letter VIII (Henderson’s Letter III.). An imitator as clever
as Mr. F. Compton Price (who has kindly supplied these illustrations)
would easily have deceived the crowd of Lords who were present at
the comparison of the Casket Letters with genuine epistles of Mary
to Elizabeth.
Scotland, in that age, was rich in ‘fause notaries’ who made a
profession of falsification. In the Burgh Records of Edinburgh, just
before Mary’s fall, we find a surgeon rewarded for healing two false
notaries, whose right hands had been chopped off at the wrists.
(Also for raising up a dead woman who had been buried for two
days.) But these professionals were probably versed only in native
forms of handwriting, whereas that of Mary, as of Bothwell, was the
new ‘Roman’ hand. An example of Mary Beaton’s Roman hand is
given in Plate C. Probably she had the same writing-master as her
Queen, in France, but her hand is much neater and smaller than that
of Mary, wearied with her vast correspondence. Probably Mary
Beaton, if she chose, could imitate the Queen’s hand, especially as
that hand was, before the Queen had written so much. The ‘Maries’
of Mary Stuart, Mary Beaton, and Mary Flemyng are all very similar.
But to a layman, Mary Beaton’s hand seems rather akin to that of
the copyist of the Sonnets in the Cambridge MSS. (Plate A). The
aunts of Mary Beaton, Lady Reres and the Lady of Branxholme,
were, after April 1567, on the worst terms with the Queen, railing at
her both in talk and in letters. But that Mary Beaton forged the
Casket Letters I utterly disbelieve.
Kirkcaldy, whose signature is given, could not have adapted fingers
hardened by the sword-hilt to a lady’s Roman hand. Maitland of
Lethington, whose signature follows Kirkcaldy’s, would have found
the task less impossible, and, if there is any truth in Camden’s
anecdote, may perhaps have been able to imitate the Queen’s
writing. But if any forged letters or portions of letters were exhibited,
some unheard-of underling is most likely to have been the actual
culprit.

Plate C

Larger Image

HANDS OF MARY BEATON, KIRKCALDY, LETHINGTON, AND MARY FLEMING

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