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Advanced
Materials

Edited by
Theo van de Ven and Armand Soldera
Editors
Prof. Theodorus van de Ven
Dept. of Chemistry
McGill University
Pulp & Paper Research Centre
3420 Rue University
Montreal, Québec H3A 2A7
Canada
[email protected]

Prof. Armand Soldera

Dept. of Chemistry
Faculty of Sciences
Université de Sherbrooke
2500 bld de l’université
Sherbrooke, Quebec, J1K 2R1
Canada
[email protected]

ISBN 978-3-11-053765-9
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e-ISBN (EPUB) 978-3-11-053779-6

Library of Congress Control Number: 2019949952

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© 2020 Walter de Gruyter GmbH, Berlin/Boston

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Preface
In 2006, RAND published a report on the Global Technology Revolution 2020
(https://www.rand.org/pubs/technical_reports/TR303.html). Among the 56 tech-
nologies identified as having profound impacts by 2020, 16 are at the top of the list
for their better chance of becoming established and for their social relevance.
Among them, nine are directly related to advanced materials. A year before the ref-
erence year of this report, we show that research carried out in our Center is per-
fectly aligned with the expected trends. This Centre, Quebec Centre for Advanced
Materials/Centre Québécois sur les Matériaux Fonctionnels (QCAM/CQMF), funded
in 2017, arises from a merge between two recognized centers: Center for Self-Assem-
bled Chemical Structure (CSACS), whose director was Prof. Theo van de Ven, and
CQMF, whose director was Prof. Armand Soldera. Conceptually, it is divided into
three fundamental themes devoted to advanced materials: self-assembly, polymer
science, and nanoscience; and three applied themes dedicated to functional materi-
als: energy, sustainable development, and biomedical applications. This book high-
lights the importance of research in materials in Quebec.
An advanced material can be defined as a material for which some properties
have been greatly improved, comparatively to more conventional materials. This
book contains the main trends regarding this topic from basic research to industrial
applications. The topics of this book fall mainly under TRL (Technology Readiness
Level) 1 to 5. It is also aimed at exposing research in advanced materials developed
by members of CQMF/QCAM. Moreover, it represents a follow-up of our previous
book entitled Functional Materials published by de Gruyter, which mainly repre-
sents a pedagogical treatment of these materials.
The guiding principle underlying the large development of advanced materials
is certainly the way their design is performed. This rational design is at the heart of
all the chapters of this book. All the aspects related to the design of advanced mate-
rials going from fundamental to applied research, or touching biomaterials to elec-
tronic structures, are thus inspected.
A very original design strategy has been envisioned by Rahbani and Sleiman
(Chapter 7): the origami approach. It provides an ideal tool to specifically position
functional objects and study their interactions at the nanoscale level. This way to
fashion DNA leads to the development of nanomechanical devices for applications
ranging from biomedicine to material sciences. The approach in designing biomate-
rials advocated by Hoesli et al. (Chapter 10) follows a different strategy. They pro-
pose to develop tailored functional materials in differentiating pancreatic cells for
cellular therapy of diabetes. For this, an interdisciplinary approach is required to
(1) design platforms to mimic pancreas development and (2) study developmental
biology in vitro. From a different perspective, Odette and Mauzeroll (Chapter 4) pro-
pose to use redox-sensitive lipid-based materials for applications in biological

https://doi.org/10.1515/9783110537734-202
VI Preface

systems. They find there a very new source for the development of clinically thera-
peutic systems.
Thanks to a fine-tuning of their constituting molecules, new and optimal prop-
erties emerge. Rondeau-Gagné (Chapter 3) proposes the development of self-healing
materials. This ability to regenerate spontaneously and autonomously has a strong
potential to revolutionize many areas such as advanced technologies or consumer
goods. The propensity of small molecules to form glass instead of the expected crys-
tals also leads to a great variety of applications, including pharmaceutical, pho-
tonic, and optoelectronic. Molecular glasses are also noteworthy materials that can
play an important role in such applications. However, their very understanding re-
mains a challenge. An overview of the progress made in the last 25 years, from their
design, synthesis, their characterization, and the simulation of their properties, is
described by Lebel and Soldera (Chapter 9).
To design new materials that will ultimately lead to interesting applications, self-
assembly remains a very stimulating avenue. van de Ven and Whitehead (Chapter 8)
propose alternate copolymers, where specific self-assembly driving monomers are in-
troduced to generate hollow nanotubes. Morphology transformation was triggered
differently by Yu and Zhao (Chapter 2). It is CO2 that plays this role, thanks to an ap-
propriate introduction of functional groups into polymers. Different CO2-responsive
functional groups are thus proposed. Control of solid-state assembly is exploited by
Schneider and Perepichka (Chapter 1) to regulate charge mobility in organic semicon-
ductors. Structure–property relationships are thus elaborated to better tackle charge
mobility. Achieving semiconducting properties from organic materials is actually
very challenging. To address this issue, Morin et al. (Chapter 13) review some of the
most important aspects regarding the synthesis, purification, and applications of two
highly praised carbon nanomaterials, namely carbon nanotubes and graphene nano-
ribbons. Nanoparticles are advanced materials where self-assembly can leverage
technological applications. Bayram and Blum (Chapter 12) present an overview of the
internal and external methods for directing this self-assembly of nanoparticles. Sta-
bility of such nanosystems, actually for nanoparticles as large as 100 nm, was shown
to greatly depend on the interface. The phase diagram of Au–Pt solid core–liquid
shells was thus revisited by Braidy (Chapter 11).
Designing is also uncovered in the way materials are prepared. The centrifugal
spinning is a novel efficient technique to prepare nanofiber. It consists in extruding
fibers through high speed, rotating polymer solution jets. The setup and the mathe-
matical model are discussed by Taghavi and Noroozi (Chapter 5).
Advanced materials have also a strong impact in designing fuel cells. Two stud-
ies reported in this book are concerned by improvement in this kind of application.
Sun et al. (Chapter 6) explore the chemistry of Fe/N/C electrocatalysts to replace
the rare and expensive platinum for the oxygen reduction reaction in polymer elec-
trolyte fuel cells. Outstanding nonprecious metal catalyst emerges from their lab.
Schougaard et al. (Chapter 14) survey researches on Li-ion batteries, revealing the
 Preface VII

importance in their modeling to incorporate such devices in numerous applications

like storage of renewable energy, electric vehicles, and energy recovery.
To foster the use of performing materials, chemists, physicists, biologists, engi-
neers, and numerical experimentalists must combine their skills to rationalize the
design of materials. This book reveals the powerful energy stemming from the re-
search in Quebec in the domain of materials in 2019. Great strides in this domain
are expected. This book, a follow-up of “Functional Materials” (de Gruyter), is cer-
tainly a concrete example.
Contents
Preface V

List of Contributors XI

Julia A. Schneider, Dmitrii F. Perepichka

1 Design Principles for Organic Semiconductors 1

Bing Yu, Yue Zhao

2 CO2-Controlled Polymer Self-Assembly and Application 51

M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz,

Simon Rondeau-Gagné
3 Self-Healing Materials: Design and Applications 87

William L. Odette, Janine Mauzeroll

4 Redox-Responsive Self-Assembled Amphiphilic Materials: Review and
Application to Biological Systems 113

Sooran Noroozi, Seyed Mohamad Taghavi

5 Ultrafine Nanofiber Formation by Centrifugal Spinning 143

Qiliang Wei, Gaixia Zhang, Shuhui Sun

6 Rational Design of Highly Efficient Non-precious Metal Catalysts for
Oxygen Reduction in Fuel Cells and Metal–Air Batteries 161

Janane F. Rahbani, Hanadi F. Sleiman

7 Toward the Assembly of Dynamic and Complex DNA Nanostructures 183

Theo G.M. van de Ven, M.A. (Tony) Whitehead

8 Alternating Copolymer Nanotubes 209

Olivier Lebel, Armand Soldera

9 Molecular Glasses: Emerging Materials for the Next Generation 239

Raymond Tran, Christopher Moraes, Corinne A. Hoesli

10 Production of Pluripotent Stem Cell-Derived Pancreatic Cells by
Manipulating Cell-Surface Interactions 261
X Contents

Nadi Braidy
11 Phase Diagram of an Au–Pt Solid Core–Liquid Shell Nanoparticle 285

Serene S. Bayram, Amy Szuchmacher Blum

12 Directing the Self-Assembly of Nanoparticles for Advanced Materials 307

Cyril Aumaitre, Anthony Jolly, Jean-François Morin

13 Toward Well-Defined Carbon Nanotubes and Graphene Nanoribbons 327

Danny Chhin, Md Sazzad Hossain, Steen B. Schougaard

14 Modeling of Lithium-Ion Batteries 353

Index 389
List of Contributors
Cyril Aumaitre Anthony Jolly
Département de chimie and Centre de Département de chimie and Centre de
Recherche sur les Matériaux Avancés Recherche sur les Matériaux Avancés
(CERMA) (CERMA)
Université Laval Université Laval
1045 Ave de la Médecine 1045 Ave de la Médecine
Québec Québec
Canada G1V 0A6 Canada G1V 0A6

Serene S. Bayram Olivier Lebel

Department of Chemistry Department of Chemistry and Chemical
McGill University Engineering
Montreal, QC Canada Royal Military College of Canada
Kingston, ON, Canada
Amy Szuchmacher Blum [email protected]
Department of Chemistry
McGill University Janine Mauzeroll
Montreal, QC, Canada Department of Chemistry
[email protected] McGill University
801 Sherbrooke Street West, Room 21
Nadi Braidy Montreal, Québec
Chemical and Biotechnological Engineering Canada H3A 0B8
Canada Research Chair in Synthesis and [email protected]
Charaterization in Multifunctional
Nanomaterials Christopher Moraes
Université de Sherbrooke Department of Chemical Engineering
2500, boul. Université McGill University
Sherbrooke, Québec J1K 2R1 Montreal, QC, Canada
Canada [email protected]
[email protected]
Jean-François Morin
Danny Chhin Département de chimie and Centre de
Université du Québec à Montréal Recherchesur les Matériaux Avancés (CERMA)
Case postale 8888, succursale Centre-ville Université Laval
Montréal, Québec H3C 3P8 1045 Ave de la Médecine
Canada Québec
[email protected] Canada G1V 0A6
[email protected]
Corinne A. Hoesli
Department of Chemical Engineering Sooran Noroozi
McGill University Laboratory of Complex Fluids Research
Montreal, QC, Canada Department of Chemical Engineering
[email protected] Université Laval, Québec
QC G1V 0A6, Canada
[email protected]

https://doi.org/10.1515/9783110537734-204
XII List of Contributors

Michael U. Ocheje Steen B. Schougaard

Department of Chemistry and Biochemistry Université du Québec à Montréal
University of Windsor Case postale 8888, succursale Centre-ville
Windsor, ON Montréal, Québec H3C 3P8
Canada Canada
[email protected] [email protected]

William L. Odette Hanadi F. Sleiman

Department of Chemistry Quebec Centre for Advanced Materials
McGill University Department of Chemistry
801 Sherbrooke Street West, Room 21 McGill University
Montreal, Québec Montreal QC Canada
Canada H3A 0B8 [email protected]
[email protected]
Armand Soldera
Dmitrii F. Perepichka Département de Chimie
McGill University Université de Sherbrooke
Department of Chemistry Sherbrooke, QC, Canada
801 Sherbrooke St. [email protected]
West Montréal, Québec H3A 0B8
Canada Shuhui Sun
[email protected] Institut National de la Recherche
Scientifique-Énergie Matériaux et
Janane F. Rahbani Télécommunications
Quebec Centre for Advanced Materials Varennes
Department of Chemistry QC J3X 1S2, Canada
McGill University [email protected]
Montreal, QC, Canada
[email protected] Seyed Mohamad Taghavi
Laboratory of Complex Fluids Research
Simon Rondeau-Gagné Department of Chemical Engineering
Department of Chemistry and Biochemistry Université Laval, Québec
University of Windsor QC G1V 0A6, Canada
Windsor, ON, Canada [email protected]
[email protected]
M. Nazir Tahir
Md Sazzad Hossain Department of Chemistry and Biochemistry
Université du Québec à Montréal University of Windsor
Case postale 8888, succursale Centre-ville Windsor, ON
Montréal, Québec H3C 3P8 Canada
Canada
[email protected] Raymond Tran
Department of Chemical Engineering
Julia A. Schneider McGill University
Fordham University Montreal, QC, Canada
Department of Chemistry [email protected]
441 E Fordham Rd,
Bronx NY 10458
[email protected]
 List of Contributors XIII

Theo G.M. van de Ven Kacper Wojtkiewicz

Pulp and Paper Research Centre and Department of Chemistry and Biochemistry
Quebec Centre for Advanced Materials University of Windsor
Department of Chemistry Windsor, ON
McGill University Canada
Montreal QC Canada [email protected]
[email protected]
Bing Yu
M.A. (Tony) Whitehead Département de chimie
Pulp & Paper Research Centre and Université de Sherbrooke
Quebec Centre for Advanced Materials Sherbrooke, Québec
Department of Chemistry Canada J1K 2R1
McGill University [email protected]
Montreal QC Canada
[email protected] Gaixia Zhang
Institut National de la Recherche
Qiliang Wie Scientifique-Énergie Matériaux et
Institut National de la Recherche Télécommunications
Scientifique-Énergie Matériaux et Varennes
Télécommunications QC J3X 1S2, Canada
Varennes
QC J3X 1S2, Canada Yue Zhao
Département de chimie
Université de Sherbrooke
Sherbrooke, Québec
Canada J1K 2R1
Julia A. Schneider, Dmitrii F. Perepichka
1 Design Principles for Organic
Semiconductors
Designing organic semiconductors--whether polymers or small molecules--involves
a myriad of synthetic choices. Every choice, from incorporating heteroatoms to sub-
stituents, effects the optoelectronic properties of the material, its morphology, and
its ultimate device performance. This chapter presents the reader with current de-
sign strategies and known structure-property relationships. For context, this chap-
ter also briefly discusses the history of the field, theories of charge transport, device
applications, and concludes with a selection of reported organic semiconductors.

Keywords: organic electronics, organic semiconductor, photovoltaics, conjugated

polymer, donor-acceptor, morphology, charge transport

1.1 Introduction
Organic electronics encompass devices in which molecules or polymers serve as
the electrically active material. Notably, the properties of these organic materials
can be endlessly tuned through structural modifications. The ability to tailor a
semiconductor for a specific application is one of the most attractive aspects of
organic electronics. Additionally, solution-processable materials offer the possi-
bility of inexpensive, large area devices, via, for example, roll-to-roll or inkjet
printing. Solar cells produced in this way could potentially satisfy the world’s in-
creasing energy demands in a sustainable manner. Organic electronics made en-
tirely from biodegradable materials would help stem the accumulation of e-waste
in landfills. For organic electronics to become widely adopted and compete with
the existing inorganic materials, however, they need to demonstrate sufficiently
long lifetimes and competitive optoelectronic properties. Since the 1970s, this has
fueled a continuing quest for new high-performance, stable materials, as well as
extensive research into what factors dictate charge transport and how to control
them. The goal of this chapter is to contribute new design strategies for the syn-
thesis of organic semiconductors (OSCs) and to better our understanding of
structure–property relationships.
While some design strategies yield predictable results, many structure–
property relationships are still not well understood, especially as they relate to

Julia A. Schneider, Department of Chemistry, Fordham University, NY

Dmitrii F. Perepichka, Department of Chemistry, McGill University, Québec

https://doi.org/10.1515/9783110537734-001
2 Julia A. Schneider, Dmitrii F. Perepichka

supramolecular ordering. In the last three decades, a multitude of OSCs have

been synthesized, primarily by trial and error, with a material’s solid-state pack-
ing and associated device performance only discussed after the fact. This chapter
will introduce the reader to a number of electronically active molecules and pol-
ymers and will discuss the design strategies used to achieve certain characteris-
tics. These design strategies will then be discussed in terms supramolecular
ordering.
This chapter will cover four main topics: (1) the history of organic electronics,
discussing the theories of charge transport, and devices that employ OSCs; (2) design
principles for the synthesis of OSCs, along with an exemplifying case study; (3) design
strategies specifically geared to supramolecular ordering; and (4) a review of
representative reported OSCs that illustrate the current state of the field.

1.2 History of OSCs

Semiconductors are ubiquitous in modern technology: they can be found in the
transistors and diodes that all our electronic devices use. The first transistor de-
vice was invented in 1947 while Bardeen, Brattain, and Shockley were studying
surface states in a germanium crystal. Ever since, inorganic materials like silicon
or gallium arsenide have been predominantly used in our electronic components.
Conductive organic materials, however, had already been discovered, although
perhaps unbeknownst to the discoverer. In 1862, Letheby observed conductive and
electrochromic behavior in a unidentified “dirty blueish-black powder,” now
thought to be polyaniline [1]. Many small organic molecules were also known to
be conductive, such as tetrathiafulvalene (TTF) chloride salts, as shown by Wudl
in 1972 [2]. An enormous body of work then evolved around TTF complexes that
gave rise to the first organic metal and organic superconductor [3, 4]. Using dop-
ants to modulate the conductivity of an organic material was perhaps first de-
scribed in iodine-doped polypyrroles (PPy) by Bolto et al. in 1963 [5]. Their results
led them to conclude that the “orbital overlap between adjacent pyrrole rings in
PPy suffices to impart a relatively high level of conductivity.” The work that popu-
larized conjugated polymers for organic electronics, however, was the famous dis-
covery in 1977 by MacD iarmid and Heeger that thin films of polyacetylene
(synthesized by Shirakawa) show unprecedented (for organic materials) high elec-
trical conductivities when doped with halogens [6]. This discovery earned the trio
the 2000 Nobel Prize in chemistry [7]. Suddenly conductive materials could be
synthesized according to chemists’ designs. Synthetic strategies from organic
chemistry were married to charge transport theories from physics and the field of
organic electronics was born.
 1 Design Principles for Organic Semiconductors 3

Initially the impetus for organic electronics was to recreate the conducting
properties of inorganic materials, which led to extensive studies on the conductivity
of molecular crystals and conjugated polymers. The current prominence of the
field, however, came about due to breakthroughs in device fabrication. While work-
ing for Eastman Kodak in the early 1980s, Tang filed patents for the first heteroge-
neous organic solar cell and the first electroluminescent device, making him one of
the founders of organic electronics. His organic light-emitting diode (OLED) demon-
strated not only that organic material could produce light in response to an electri-
cal current, but also that organic materials could be used in commercially viable
electronic devices [8]. A few years later, the Friend group, working at the Cavendish
Laboratory, reported the first OLED based on a conjugated polymer, poly(phenylene
vinylene), paving the way for solution-processable devices [9].
In the late 1980s, Friend and others were also making breakthroughs in organic
field-effect transistors (OFET). An important contribution was the demonstration
that charge carriers could be introduced into conjugated polymers, such as polyace-
tylene, by using an electric field [10]. Also paramount in the advancement of the
field was Garnier’s work with oligothiophene-based OFETs [11]. Early measurements
of evaporated films of sexithiophene only displayed mobilities on the order of
10 − 4 cm2 =Vs, but the possibility of using OSCs in conventional electronics was
established.
Since these early discoveries, many OSCs – polymers and small mole-
cules – have been synthesized and tested in devices. Organic electronics ex-
hibit four key beneficial properties: flexibility, transparency, expendability,
and the potential to be processed at low-cost over large surfaces through solu-
tion printing techniques [12]. Because of these properties, organic electronics
can be advantageous for certain applications where inorganic materials would
not be appropriate, though they do often suffer from low conductivities and
poor operational stability. The incorporation of thin-film-printed OSCs in radio
frequency identification tags, for example, would lower the tag’s cost and im-
prove their mechanical properties, making them viable for tracking large in-
ventories, such as in supermarkets [13]. OSCs have also been heavily studied
as sensors, where cost, flexibility, and disposability can be important factors,
but fast switching speeds may not be necessary, for example, because the
sensing process is limited by biochemical reactions and adsorption rates [14].
The first commercial use of OSCs was in OLED displays, which are thinner and
use less energy than their inorganic analogues. The emission color of an OLED
can also be tuned by modifying the organic chromophore. Organic photovol-
taics (OPVs) are an example of devices that greatly benefit from the large-
scale printing processes available to OSCs. Solution-processable OPVs can be
light, flexible, and transparent, something that would be impossible in silicon-
based solar cells [15]. Complimentary circuits, which rely on a combination of
p- and n-type transistors, have also been made from OSCs, although their
4 Julia A. Schneider, Dmitrii F. Perepichka

development has been slow due in part to the relative scarcity of n-type semi-
conductors [16]. All these applications have made organic electronics one
of the most rapidly growing fields over the last several decades. Ongoing re-
search focuses on selectively tuning a material’s electronic properties, on in-
creasing solubility and stability, and on understanding and controlling
supramolecular assemblies.

1.3 Band Gap

OSCs are π-conjugated molecules or polymers, meaning they contain alternat-
ing single and double bonds such that their π-orbitals overlap and form a net-
work of delocalized electrons (Figure 1.1). These overlapping molecular orbitals
and the energy levels of the electrons within are referred to as bands. The bonding
molecular orbitals below the Fermi level form the valence band and the higher en-
ergy antibonding orbitals above the Fermi level form the conductance band. The
energy difference between these bands is called the band gap and, at the molecu-
lar level, corresponds to the difference between the highest energy occupied mo-
lecular orbital (HOMO) and the lowest energy unoccupied molecular orbital
(LUMO).

S
S
n
Anthracene Polythiophene

Figure 1.1: Conjugated molecules have alternating double and single bonds. Overlap between
π-orbitals causes electrons to be delocalized throughout the structure, giving rise to electron
density above and below the aromatic cores, as seen in the calculated electrostatic potential
surfaces.

In a material with no band gap, termed “metallic,” electrons can easily move into
the empty states of the conductance band, creating “free” charge carriers that
 1 Design Principles for Organic Semiconductors 5

provide high conductivities. Conversely, insulators exhibit low conductivities be-

cause their large band gap inhibits the movement of electrons into the conductance
band (or holes into the valence band).
Electrons need an open path to move through a material, that is, the bands
must be only partially filled. This is achieved when an electron moves from the full
valence band into the empty conductance band (or is removed from the material),
leaving a “hole” behind. A neighboring electron can then move over to the new
hole, leaving its own hole behind. In effect, the hole is acting as a positive charge
carrier moving through the valence band, while electrons move through the con-
ductance band. OSCs are ambipolar and can be used in p- or n-type transistors, in
which holes or electrons, respectively, are the charge carriers. All OSCs are “extrin-
sic semiconductors,” meaning that they must be doped to be conductive. Dopants
supply holes or electrons to the material and contract the band gap by creating in-
termediate states (Figure 1.2). A material can be chemically doped through oxida-
tion or reduction, photochemically doped by promoting an electron from the
valence band into the conductance band, or it can be doped via the injection
of charge carriers by an electric field.

Conduction p-type n-type

band
LUMO (empty states)

Eg Eg = 0
HOMO
Valence
band
(filled states)
Insulator Semiconductor Metal

Figure 1.2: Molecular orbitals make up the energy bands and the size of the band gap determines
the conductivity. p- and n-type doping of the band gap with respective charge accumulation is
shown in the semiconductor. (Electrons are filled and holes are unfilled circles).

1.4 Theoretical Models for Charge Transport

Before looking at the design strategies for synthesizing OSCs, it is useful to under-
stand, at least qualitatively, the theoretical models describing charge transport in
small molecules and polymers. Charge transport in OSCs is characterized by mea-
suring the charge mobility, or the time it takes for an electron or a hole to move
through the material under an electric field. OSCs encompass materials with a large
range of mobilities, making it hard for a single theoretical model to accurately
6 Julia A. Schneider, Dmitrii F. Perepichka

describe charge transport in all OSCs. Charge transport in an ultrapure crystal is dif-
ferent than that in an amorphous film, which will also be different from transport
in semicrystalline polymer films. Several theories were developed and expanded
upon to explain the observed characteristics of OSC devices, namely, temperature-
dependent, field-dependent, and film-thickness-dependent charge-carrier mobility.
Unfortunately, it is still hard to predict the effects of microstructures in inhomoge-
neous OSC films, such as crystalline domains in polymer films [17, 18]. The existing
theories are generally characterized as band theory, hopping theory, and hybrid
theories of the two.
Band theory is based on a model where charges are fully delocalized over sev-
eral molecular units and exist in bands (equivalent to the conductance and valence
bands introduced in Section 1.3). For band transport to occur, the interaction energy
between nearest neighbors, called the electronic coupling (t), must be greater than
disorder-induced energy barriers. Band transport is characterized by a decrease in
charge carrier mobility with increasing temperatures, a property common to crystal-
line inorganic semiconductors, but rarely seen in OSCs. Karl and coworkers mea-
sured the hole and electron transport in assiduously purified naphthalene crystals
at temperatures from 4 to 300 K, and proved that band transport can take place in
ultrapure OSC crystals below 300 K [19]. When measuring electron transport along
the three crystallographic directions of naphthalene crystals, a strong anisotropy
was observed that coincided with the electronic couplings acquired from DFT
calculations – a fact that emphasizes the dependence of band transport on crystal-
linity [20].
In amorphous OSCs, however, disorder effects become large and transport
through a single delocalized band is no longer feasible. Disorder effects can be dy-
namic, such as vibrational changes when a molecule (or “site”) becomes charged
(seen in crystalline OSCs as well) or static, such as pre-existing variations in site
energies and intersite distances [21]. In such an environment, a charge is localized
on a single site and must “hop” to another localized site for conductivity to be ob-
served. This process had been previously described by Marcus in the electron trans-
fer between identical molecules in solutions – a theory for which he was awarded
the 1992 Nobel Prize in chemistry [22, 23]. Hopping theory in OSCs was spearheaded
by, among others, Mott and Holstein, who developed small polaron-hopping theory
[24]. A polaron is the combination of a charge carrier and the lattice deformations
associated with that carrier’s movement. The distortions to the molecules and their
environment lead to an energetic cost to charge transfer called the reorganization
energy (λ). As a result, charge transfer is thermally activated and we observe an in-
crease in mobility as temperature increases. Holstein’s model for the rate of electron
transfer is a function of the electronic coupling (t), the polaron binding energy
(Epol ), and thermal energy (kB T) shown in eq. (1.1).
 1 Design Principles for Organic Semiconductors 7

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  
t2 π Epol
kET = exp − (1:1)

h 2Epol kB T 2kB T

The polaron-binding energy is defined as the relaxation energy of an ionized mole-

cule, while reorganization energy is the sum of the relaxation energies of the initial
neutral molecule and the resulting ionized molecule. Recognizing that the polaron-
binding energy is essentially equal to half the reorganization energy (Epol = λ=2), eq.
(1.1) is identical to the semiclassical Marcus equation. The simplicity of this model,
which relates transfer rates directly to electronic coupling (t) and reorganization en-
ergy (λ), has made it popular among chemists as a reasonable approximation for
charge transport in OSCs.
Neither band theory nor two-state hopping theories, however, address the de-
fects and static disorder present in the majority of OSC thin films, which are poly/
semicrystalline. Variations in site energies and intersite distances at these disorder
sites leads to asymmetric rates and therefore time-dependent mobilities. The Gauss-
ian disorder model assumes a Gaussian energy distribution of these variations and
takes into account the life-time of the charge carrier [25].
As device preparation techniques improved, OSCs started to show higher mea-
sured mobilities. Current theories therefore reconciled band-like and hopping trans-
port into trap-limited transport [26]. The multiple-trap-and-release model (MTR)
was first proposed by Shur and Hack to describe hydrogenated amorphous silicon
[27]. The model assumes band-like charge transport occurs through delocalized
states, but that trap states capture injected charge carriers, where they may be fur-
ther excited into the conduction band (Figure 1.3). This model describes materials
with a large range of mobilities, since the mobility is affected by the ratio of free to
trapped charges. Horowitz successfully applied the MTR model to OSCs when ex-
plaining the changing temperature and field dependence of mobilities observed in
polycrystalline films of sexithiophene [28].

Hopping Band MTR

Figure 1.3: Theoretical charge transport models. On the left is the hopping method where only
localized states exist. In the middle is band theory where all charges travel through the conductance
band. On the right is the MTR model in which trapped charges can still move into the conductance
band. (Note that these figures depict n-type transport).
8 Julia A. Schneider, Dmitrii F. Perepichka

In the context of molecular design for OSCs, maximizing nearest neighbor inter-
actions and minimizing reorganization energy are crucial to increased charge mobi-
lities. In the end, though, charge transport is often limited by the number of trap
states. The efficacy of a trap depends on its energy level relative to the HOMO or
LUMO, for hole or electron trapping, respectively [29]. Trapping sites can either be
structural faults or chemical impurities. A commonly seen trap is oxygen or oxida-
tion products, but not all such impurities need to act as traps. If the energy level of
the potential trap lies above or below the material’s band gap, the trap remains in-
effective. The nature of the traps present, especially oxidation products, depend on
the OSC and can sometimes be predicted and avoided.

1.5 OSC Devices

OSCs have been used in a wide range of electronics. While OSCs exhibit lower mobi-
lities than their inorganic counterparts, their tunability and processing versatility
give them a strong advantage for light-weight or one-time-use applications. OSCs
can be printed from solution onto practically any surface, including flexible plastics
[30] and paper [31]. This is advantageous for medical applications, such as elec-
tronic skin or biocompatible sensors [32]. This section will give a brief overview of
three types of OSC devices.

1.5.1 Organic Light-Emitting Diodes

In terms of the commercialization of OSCs, OLEDs are undoubtedly leading the

way. OLED-based displays can be found in a myriad of smartphone screens, includ-
ing Samsung’s Galaxy series, Google’s Pixel, and Apple's iPhoneX, as well as in
some tablets, television displays, and solid-state lighting panels [33].
An OLED device consists of an emissive layer and a transport layer, made of
organic molecules or polymers. These layers are sandwiched between two electro-
des and when a voltage is applied across the electrodes, electrons are injected into
the emissive layer. The electrons drift to the interface with the transporting layer
where the recombination with holes found there causes radiative emission. Since
OLED devices directly generate light, there is no need for a backlight as in LCD dis-
plays, and creating true black is easily achieved by switching off the emitting pixel.
OLED displays are therefore thinner and more energy efficient than LCD displays.
OLEDs can be patterned into pixel-sized devices (much smaller than inorganic LED
devices; Figure 1.4) or printed into large sheets for solid-state lighting [34]. Histori-
cally, blue OLEDs have trailed behind red and green emitting devices in terms of
efficiency and life-times, but recent research is closing this gap [35].
 1 Design Principles for Organic Semiconductors 9

Figure 1.4: A 200× magnification of Google’s Nexus

One AMOLED screen shows the Red-Green-Blue
arrangement of OLED pixels. Photograph by Matthew
Rollings, distributed under a CC-BY 3.0 license.

1.5.2 Solar Cells

OPVs, though still tailing silicon-based solar panels in terms of efficiency, can be
printed into lightweight, flexible, and transparent solar cells. These qualities are
important mechanistic and aesthetic features when incorporating solar windows
into urban architecture [36]. The solution processability of materials for roll-to-roll
printing is especially important for OPVs due to the large-scale nature of this
application.
OPVs produce electricity through the photoelectric effect illustrated in Figure 1.5
for a simple p–n junction. A p–n junction describes the interface between a p-type
(donor) and n- type (acceptor) semiconductor. Incident light excites an electron into
the conductance band of the donor or acceptor material, leaving a hole behind, thus
creating an “electron–hole pair” or “exciton.” This exciton must diffuse to the p–n
junction where the charges can be separated: the hole into the p-type donor material
and the electron into the n-type acceptor material. The charges are then channeled to
their respective electrodes and produce an electric current.

LUMO

hv

HOMO

Hole

Electron

Figure 1.5: Once an exciton is generated (left) it must diffuse to the p–n junction before undergoing
charge separation (right).
10 Julia A. Schneider, Dmitrii F. Perepichka

Efficient solar cells are constructed with a few key factors in mind.
– First, the active layer should have a broad absorbance spectrum that captures a
majority of the sun’s energy. This calls for a semiconductor with a small band
gap (
1.5 eV). The band gap cannot be too small, however, to avoid large en-
ergy loss from exciton thermalization and the HOMO–LUMO offset of the cell
[37].
– The lifetime of an exciton is on the order of nanoseconds and its diffusion
length only
10 nm, necessitating small, regularly spaced domains of donor
and acceptor phases to minimize exciton recombination.
– The driving force for charge separation at the p–n junction (the electropotential
drop from the LUMO of the donor to the LUMO of the acceptor) needs to be
greater than the exciton binding energy to drive exciton dissociation.
– The charge mobilities of the donor and acceptor materials should be reasonably
high ( > 10 − 4 cm2 /Vs). They should also be balanced to avoid a build-up of elec-
trons or holes, which leads to accelerated charge recombination.

Controlling the morphology of the donor and acceptor domains is an integral part
of fabricating efficient devices. The most common practice is to dissolve the two
materials in a common solvent and to create a blended active layer called a bulk
heterojunction (BHJ) (Figure 1.6). Annealing and adding solvent additives can alter
how each material crystallizes and thus affect the resulting domain sizes.
The power efficiency of a solar cell is defined by three parameters: the short-
circuit current (ISC ), the open-circuit voltage (VOC ), and the fill factor (FF). These pa-
rameters are calculated from the current–voltage relationship of the device plotted
in an I–V curve (Figure 1.7). The short-circuit current is the largest current that may
be drawn from the solar cell and occurs when the bias across the cell is zero. While
in the open-circuit state, charge carriers generated under illumination accumulate
at the anode and cathode. When this growing potential difference cancels out the
built-in potential, the current is zero and the measured open-circuit voltage is the
maximum voltage the solar cell can provide to an external circuit [38]. In OPVs
 
the VOC is limited by the “band gap” of the cell, or LUMOAcceptor − HOMODonor  (Fig-
ure 1.6), but empirically, large voltage losses are always observed due to the recom-
bination of charges [39].
Power is the product of the current and voltage (P = I × V), with the maximum
power of the cell (PMax ) representing the point of peak efficiency. The fill factor (FF)
is the ratio of the area bound by the ISC and VOC to the area bound by the current
and voltage at PMax as seen in eq. (1.2) and Figure 1.7. FF is often described as the
“squareness” of the I–V curve, with an ideal value of 1.

IMax VMax
FF = (1:2)
ISC VOC
 1 Design Principles for Organic Semiconductors 11

Anode

Cathode

Donor

Acceptor
Anode VOC
Donor phase

Acceptor phase

Cathode

Figure 1.6: On the left is a simplified depiction of a bulk heterojunction showing the blended
donor and acceptor domains. On the right is shown the VOC as it relates to the HOMO of the donor
and the LUMO of the acceptor, that is, the band gap of the cell.

Voltage (V)

Open circuit
voltage
(Voc)
Fill factor
(FF)
Current (A)

PMax
Short circuit
current (Isc)

Figure 1.7: A characteristic I–V curve for an irradiated solar cell showing the VOC , ISC , and PMax . The
FF is the ratio between the two shaded areas.

The overall power efficiency of the cell is then defined as

PMax FFðISC VOC Þ

PCE = = (1:3)
PIn PIn
12 Julia A. Schneider, Dmitrii F. Perepichka

How do these parameters relate to the design of OSCs? Lowering the band gap
of the donor material means more light is harvested, which has a direct bene-
ficial impact on the ISC . Unfortunately, if shrinking the band gap increases the
HOMO level of the donor material, this will limit the VOC ; therefore, simultaneously
lowering the band gap and the HOMO level of the material is extremely desirable.
Chen et al. observed that for each 0.1 eV drop in the HOMO level of differently
substituted poly(benzodithiophene-thieno[3, 4-b]thiophene), they increased the
VOC by 0.07 V [40].
Both the ISC and VOC are limited by charge recombination as well. Exciton disso-
ciation and charge recombination both occur at the donor–acceptor interface. It is
therefore important to augment charge mobility with ordered films while maintain-
ing adequate domain sizes for exciton dissociation. Efficient charge extraction at
the electrodes will also help reduce recombination loss.
Polymers have been extensively tested as donor materials for BHJ solar
cells, and a key property that influences the morphology of the films is molec-
ular weight [41]. Larger molecular weight polymers show a propensity to form
nanofibrillar morphologies and exhibit higher charge mobilities. For example,
batches of poly(dioctylfluorene-dithienylbenzothiadiazole) displayed higher ISC s
with increasing MWs, though the VOC s stayed constant [42]. Too large an MW, how-
ever, may decrease the mobility due to entanglement, which hinders intrachain
transport [43].
To ensure the solution processability of high MW-conjugated polymers, solubi-
lizing side chains are required, which will affect film morphology as well. The posi-
tion, length, and bulkiness of alkyl side chains affects the π–π interactions between
polymer chains. Increased π–π interactions lead to higher mobilities and ISC s, but
may have a detrimental effect on the film blends [44]. More examples of side chain
engineering is discussed in Section 1.6.4

1.5.3 Field-Effect Transistors

A field-effect transistor (FET) is an electronic switch that uses an electric field to

control the conductivity of a semiconductor. In our group, OFETs are routinely
used to test the electrical properties of novel polymers and small molecules.
Owing to the flexible nature of many OSCs, OFETs can be fabricated on a variety
of substrates, including poly(ethylene terephthalate) films [45] or paper [46, 47].
Devices can also be made in several different architectures, but the most common
and reproducible device is the “bottom-gate, top-contact” silicon wafer device de-
scribed here.
OFETs consist of an active semiconductor layer, an insulating layer, and three
contacts: the source, the drain, and the gate (Figure 1.8). The substrate for the de-
vice typically doubles as the gate electrode, as is the case with silicon wafers.
 1 Design Principles for Organic Semiconductors 13

Above the gate is an insulating layer, called the gate dielectric layer, for example,
SiO2. When an electric field is applied to the gate charges accumulate in the dielec-
tric layer. This causes an accumulation of complementary charges in the semicon-
ductor at the semiconductor-dielectric interface. Once turned “on” by the electric
field, the semiconductor becomes conductive and charges can migrate along the
narrow transistor channel. Since charge migration occurs only at the semiconduc-
tor–dielectric interface, any defects can easily limit charge mobilities. “Smoothing”
the dielectric layer, with polystyrene, for example, has been shown to greatly im-
prove mobilities [48].

Organic semiconductor
Vd

Transistor channel
Source Drain
+ Insulator
+ + + + + + + + + + + + +

Gate

Figure 1.8: Schematic diagram of a bottom-gate, top-contact OFET showing the gate-induced charge
transport channel. Reprinted by permission from Macmillan Publishers Ltd: Nature Materials [49],
copyright 2010.

In the case of poorly soluble small molecules, films are deposited using vacuum
vapor deposition, but for polymers or soluble small molecules, solution-processing
techniques, such as spin-coating, are used. A single crystal can also be used as the
active layer, enabling the measurement of mobilities specific to that packing archi-
tecture. The physical morphology of the OSC plays an important part in device per-
formance, and so the method used to deposit the material can vastly affect charge
mobility. This is starkly evident in the case of pentacene thin films, which are prac-
tically insulating (μh
10 − 9 cm2 =Vs) as amorphous films deposited at low temper-
atures, but display high mobilities in ordered films deposited at room temperature
(μh
1 cm2 =Vs) [50].
The charge mobility of an OFET is determined by recording the drain-source
current (IDS ) as a function of drain-source bias (VDS ) at different gate voltages (VG ).
When a small drain-source voltage VDS is applied (smaller than the gate voltage
minus the threshold voltage, <(VG −VT )) the device operates in the linear regime. As
drain-source voltage increases and surpasses (VG −VT ) the device operates in a
14 Julia A. Schneider, Dmitrii F. Perepichka

–80 V

Linear Saturation
regime regime
–60 V

IDS1/2 (A1/2)
IDS (mA)

IDS (A)
–40 V VT

–20 V
0V
0 –10 –20 –30 –40 –50 –60 10 0 –10 –20–30–40–50–60

Figure 1.9: Typical electrical characteristics of a p-channel OFET device: (left) output curve and
(right) transfer curve.

saturation regime (Figure 1.9). Charge mobilities can be calculated from either re-
gime. In the saturation regime, drain current is independent of drain-source volt-
age, but rather varies as the square of the gate voltage as given in eq. (1.4):

W
IDS = − Ci μðVG − VT Þ2 (1:4)
2L

where W and L are the channel width and length and Ci is the capacitance of the
dielectric. The threshold voltage, VT , is the minimum gate voltage that is needed to
generate the transistor channel. The field-effect carrier mobility, μ, can thus be de-
termined from the slope of the curve plotting the square root of the saturation cur-
rent as a function of gate voltage according to eq. (1.5):
 pffiffiffiffiffiffi2
2L 1 δ IDS
μ= (1:5)
W Ci δVG

It must be pointed out, however, that these equations are approximations. Equation
(1.5) assumes that the mobility is independent of the gate voltage, which is not the
case for several reasons. For example, at low gate voltages charges will be trapped by
localized traps, limiting mobility [51, 52]. The charge mobility in eq. (1.5) is also not
corrected for contact resistance at the metal/organic interface, which is a common is-
sues in OFETs. Contact resistance can occur due to an energy level mismatch between
the electrode metal and the OSC or disorder in the OSC film at the interface.
 1 Design Principles for Organic Semiconductors 15

1.6 Molecular Design Strategies

The most attractive aspect of OSCs from a chemist’s point of view is the opportu-
nity to rationally design and synthesize a desired material. By altering the molec-
ular structure of a material and testing its electronic properties, structure–
property relationships can be defined and the factors affecting charge transport in
OSCs illuminated. Charge transport in OSCs is highly dependent on the solid-
phase morphology of the material and not solely on the molecule’s electronic
properties and since structure–property relationships encompass both the indi-
vidual molecules’ characteristics and the characteristics of the bulk material, it
can be very difficult to ascertain if a modification is responsible for an observed
property. In this chapter we try to divorce molecular structure from morphological
aspects and study both separately, so as to better delineate structure–property re-
lationships in OSCs.
Depending on its final application, an OSC can be designed to have vastly differ-
ent properties. Will it be used for p- or n-type transport? Does it need to be soluble?
Should it form amorphous films or be highly crystalline? Is broad absorption impor-
tant or is strong emission at a specific wavelength required? The molecular design of
an OSC will naturally reflect these sought-after properties, though the toolbox of de-
sign strategies available to realize them remains the same.
The first requirement for an OSC is a finite band gap. Since the 1980s, many
strategies for controlling the band gap have been established. In an OSC the en-
ergy bands are made of overlapping π-orbitals, so that manipulating these energy
levels is all about maintaining conjugation and expanding electron delocalization.
There are four main factors (depicted in Figure 1.10) that influence band gap: (1) pla-
narity, (2) bond-length alternation (BLA), (3) aromaticity, and (4) the electronic effect
of substituents. A single design choice can easily affect all of these factors, so it is
easier to consider specific strategies and discuss the affects on these factors as they
apply.

1.6.1 Extending Conjugation with Spacer Groups

The most basic and prevalent unit in conjugated molecules is the benzene ring. The
benzene ring contains six electrons in delocalized π-orbitals, but its ring structure
gives it more resonance stabilization than linear hexatriene. Benzene is a very small
conjugated system, so its HOMO–LUMO gap is large (ca. 5.5 eV).
To shrink the band gap, there are two ways of expanding the conjugation. The
first is to connect multiple benzene or aromatic rings together with C–C single
bonds, forming an oligomer or a polymer. This method preserves the aromatic sta-
bility of each ring, but planarity is lost due to steric hindrance between the benzene
rings. The short distance between benzene rings will not accommodate the C–H
16 Julia A. Schneider, Dmitrii F. Perepichka

Substitution

Bond length alternation

Aromaticity
θ°
S
S S

Figure 1.10: Factors that influence band gap labeled on polythiophene (PT). Reprinted with
permission from Roncali [53]. Copyright 2007 John Wiley & Sons, Inc.

bonds on each ring, requiring the backbone of the polymer to twist (Figure 1.11a).
When larger substituents need to be added, steric hindrances can cause serious tor-
sional twists, interrupting the orbital overlaps between rings. A simple solution to
planarize the polymer is to introduce a spacer group between each ring. The spacer
group must also be conjugated and, in effect, it will “dilute” the aromaticity of the
benzene rings. This promotes delocalization of electrons along the entire polymer,
not just within nodes of the aromatic rings. Examples of such conjugated spacers are
vinylene (Figure 1.11b) and ethynylene. The ethynylene spacer has no hydrogen
atoms to contribute to sterics and therefore produces rod-like, planar polymers [54].
The disadvantage comes in the form of increased BLA, caused by the large difference
in lengths between the C–C single bond and the much shorter C ≡ C triple bond.

(a) (b)

n n
Poly(p-phenylene) Poly(phenylene vinylene)
Eg = 3.4 eV) Eg = 2.4 eV

θ = 36.8° θ = 0.5°

Figure 1.11: Simple polyphenylene has a twisted backbone (a) leading to a large band gap, which
can be lowered by introducing a vinylene spacer, such as in poly(phenylene vinylene) (b). DFT
calculations of the dihedral angles performed using B3LYP, 6-31G(d).
 1 Design Principles for Organic Semiconductors 17

BLA is defined as the averaged differences in length of adjacent carbon–carbon

bonds. Conjugated molecules can be thought to contain two competing resonance
structures: the aromatic and the quinoidal (Figure 1.12), both containing alternating
single and double (or triple) bonds. In a structure with a nondegenerate ground
state, like polyphenylene or polythiophene (PT), where the aromatic form is pre-
ferred, the BLA is proportional to the band gap and decreases with increasing qui-
noidal character [55]. Even polyacetylene, a polymer with a degenerate ground
state, has a BLA of 0.08 Å as a consequence of Peierls’ distortion. In a 1D crystal
lattice a net energy gain is brought about by distorting the periodicity of the lattice
into “dimers,” or if the 1D lattice is a carbon chain, into double and single bonds
[56, 57].

Figure 1.12: Two resonance structures of polyphenylene.

An early approach to minimize BLA is to design a monomer unit that contains an

aromatic cycle when the polymer backbone is in its quinoidal form. This counter-
balances the aromaticity of the polymer core and favors delocalization, lowering
the band gap and BLA. This approach was pioneered by Wudl in the synthesis of
poly(isothianaphthene), which exhibits a very low band gap of 1.0 eV (Figure 1.13)
[58]. A more recent example can be seen in polymer 1 (also known as PTB7), well
known for achieving 9% efficiencies in OPVs [59]. In the thieno[3,4-b]thiophene
unit, the fused thiophene ring is in its aromatic form when the backbone thiophene
ring is its quinoidal form and vice versa (Figure 1.13) [60].
Besides acting as a measure for electron delocalization through the balance of
aromatic and quinoidal character, BLA is extremely important as it relates to the
polarizability of the molecule. Polarizability is the measure of electron cloud dis-
placement (or induced dipole moment) in the presence of an electric field and it is
inversely related to the polaron binding energy. As was described in Section 1.4, the
polaron-binding energy is one of the key parameters affecting the rate of charge
transfer in OSCs. The relationship between BLA and polarizability was experimen-
tally proven by measuring the polarizability and non-linear hyperpolarizability of a
series of donor–acceptor polyenes with end groups of increasing acceptor strength,
thus having a range of BLAs from 0.11 Å for decatetraene to
0 Å for cyanine
(Me2 N + =CH(CH=CH)3 –NMe2 ). The results indicated that molecular polarizability (α)
is maximized as BLA approaches zero [61–63].
18 Julia A. Schneider, Dmitrii F. Perepichka

S n S n
Poly(isothianaphthene)

O OR O OR

OR S F OR F
S
S S

S S n S S n
OR OR

Figure 1.13: Both isothianaphthene and thieno[3,4-b]thiophene contain a fused aromatic ring when
the polymer is in quinoidal form.

A method to planarize aromatic rings and reduce BLA is to use a spacer group
that impedes torsional twisting. The most well-known example of this is fluorene,
which is essentially two benzene rings fused by a C–C single bond and an sp2 car-
bon. Fusing the rings not only ensures better π-orbital interactions, but also short-
ens the C–C linking bond and elongates the C–C bonds within the five-membered
rings, thus reducing the BLA (Figure 1.14). Polyfluorenes, therefore, are extremely
popular OSCs, exhibiting good stability, interesting liquid–crystalline properties, as
well as being excellent blue-light emitters [64]. In many other π-conjugated sys-
tems, such as PTs, the rigidification of molecules has proved to be a useful ap-
proach toward low-band gap materials [65, 66].

04
1.5 1.386
1.3
1.39

85

1.507
7
1.3

5
76

1.38

1.472
7

1.3
2

1.3

1.416
87

1.390

Figure 1.14: The fused spacer group in fluorene lowers BLA as compared to biphenyl. Averaged
bond lengths (Å) reported in [67] for biphenyl and reported in [68] for fluorene.
 1 Design Principles for Organic Semiconductors 19

1.6.2 Fusing Rings: Polycyclic Arenes

A different approach toward molecular rigidification, which does not require a

spacer group, is fusing aromatic rings together. Multiple fused rings will share
π-orbitals so that electrons are delocalized throughout the molecule, lowering the
band gap of the molecule and raising the HOMO levels. In acenes, however, extend-
ing the conjugation linearly leads to increased biradical or “open-shell” character,
making it vulnerable to oxidation (Figure 1.15). Hexacene is the longest acene that
is stable under ambient conditions [69]. Higher order acenes form biradicaloids that
are prone to intermolecular dimerization and oxidation [70].

Benezene Eg = 6.8 eV
HOMO = –6.7 eV

Naphthalene Eg = 4.8 eV
HOMO = –5.8 eV

Anthracene Eg = 3.6 eV
HOMO = –5.2 eV

Pentacene Eg = 2.1 eV
HOMO = –4.6 eV

Migrating sextet

Pentacene
biradicaloid

Localized double bond

Aromatic sextet “Empty” ring

Phenanthrene Triphenylene

Figure 1.15: A drop in band gap and a raising of HOMO levels can be observed with the expansion
of linear acenes. Below are nonlinear PAHs illustrating Clar’s classification of six-membered rings.
20 Julia A. Schneider, Dmitrii F. Perepichka

Nonlinear polycyclic aromatic hydrocarbons (PAHs) exhibit higher band

gaps and lower HOMO levels than their linear counterparts. Phenanthrene, for
example, has a HOMO–LUMO gap
0.3 eV larger than its linear analogue anthra-
cene. This lowering in HOMO levels (and thus increased oxidative stability) is ex-
plained by Clar’s rule: the more aromatic sextets present in a molecule, the more
stable that molecule will be. This is also the rationalization behind the formation of
open-shell species. Clar’s rule classifies six-membered rings in PAHs into four
types: aromatic sextets, migrating sextets, empty rings, and rings with localized
double bonds (Figure 1.15). Fusing linear acenes can yield molecules with two
aromatic sextets, such as “bistetracene” (Figure 1.15). “Bistetracene” (substituted
with triisopropylsilyl acetylene groups) contains eight fused rings, but its HOMO
level is only −5.1 eV, allowing for air-stable FET devices and high mobilities
(μh = 6.1 cm2 =Vs) [71]. Picene, the “zigzag” analogue of pentacene, contains three
aromatic sextets and shows better environmental stability in p-channel FETs than
pentacene [72]. Thermally deposited thin films of alkylated-picene have, like penta-
cene, shown extremely high mobilities (up to μh = 20 cm2 =Vs), but are stable under
atmospheric conditions [73].
Extending the conjugation does more than affect energy levels: it also lowers the
BLA (as discussed previously) and lowers the reorganization energy. As was dis-
cussed in Section 1.4 when a neutral molecule becomes charged it undergoes geome-
try modifications at an energy cost called the reorganization energy, an important
factor in charge transport. Figure 1.16 shows how reorganization energy decreases as
the number of rings increase in a series of molecules with different fused geometries.
Reorganization energy is also affected by heteroatoms, which are discussed next.

1.6.3 Heteroatoms

Another design strategy in organic electronics is the use of heteroaromatics. In-

serting heteroatoms into a polycyclic system will have a large impact on the struc-
ture and the electronic properties of the molecule or polymer. The work presented
in this chapter focuses on two heteroatoms: sulfur and nitrogen. Sulfur and nitro-
gen both have lone electron pairs that can contribute to the aromaticity of a cycle,
thus making aromatic five-membered rings possible (Figure 1.17). These five-mem-
bered rings, thiophene and pyrrole, are smaller and exhibit less torsional twisting in
polymers than benzene rings Thiophene and pyrrole are less aromatic than benzene
(according to thermodynamic stabilization), and thus PTs and polypyrroles (PPy)
have stable quinoidal forms, leading to more delocalized electrons and smaller
band gaps than poly(p-phenylene) (PPP) (theoretical Eg PT = 2.0 eV, PPy = 2.9 eV,
PPP = 3.8 eV) [75].
Although PPy were among the first conductive organic materials studied [76,
77], it is PT and other thiophene-containing molecules that predominate the field of
 1 Design Principles for Organic Semiconductors 21

250
Reorganization energy

200

150
Energy (meV)

100

50

0
0.00 0.02 0.04 0.06 0.08 0.10 0.12

Figure 1.16: Molecular reorganization energies computed for (oligo)acenes (black triangles),
phenacenes (green squares), circum(oligo)acenes (blue circles), and (oligo)perylenes (red diamonds),
as a function of the inverse of the total number of carbon atoms NC . Reprinted from Malloci et al.
[74], Copyright 2014 with permission from Elsevier.

..
N
.. .. ..
S
.. N S
.. N
H ..

Figure 1.17: Pictured are several heteroaromatic structures. Electrons participating in the
aromaticity are labeled in red.

organic electronics. Poly(3-hexylthiophene) (P3HT) for example, has become the

benchmark donor material for bulk heterojunction solar cells, though its efficiency is
limited by a relatively large band gap (Eg = 1.9 eV) and high HOMO level (−5.1 eV)
[78]. Yet thiophenes present many advantages [79], not the least of which is their
well established and versatile chemistry. Derivatives of thiophene can be synthesized
by selective substitution via lithiation chemistry. Thiophene monomers are easily ox-
idized, either electrochemically or chemically, to form radical cations that polymer-
ize. If thiophene is substituted unsymmetrically, this method produces to a
regiorandom polymer. Brominated thiophenes can be polymerized through transition
22 Julia A. Schneider, Dmitrii F. Perepichka

metal-catalyzed cross-coupling reactions to give regioregular homopolymers or to

make copolymers [80]. Thiophenes are electron rich and chemically stable, making
them good for p-type transport, and they self-assemble with close π–π stacks. Fur-
thermore, the increased polarizability of the sulfur atom compared to carbon helps
lower reorganization energies and can lead to intermolecular sulfur–sulfur interac-
tions. These interactions are described in more detail in Section 1.7.
Nitrogen heteroatoms can be incorporated into OSCs in five- or six-membered
rings. In five-membered pyrroles, the lone pair on nitrogen contributes to the aroma-
ticity of the ring making the heterocycle electron rich. Conversely, in six-membered
pyridine, the lone pair is perpendicular to the π-orbitals of the ring and therefore
does not contribute to the aromaticity, but rather enhances basicity. In this case,
the electronegativity of the nitrogen atom makes the ring electron poor and lowers
the HOMO–LUMO levels of the molecule. As a result OSCs containing nitrogen have
been shown to be p-type, ambipolar, or n-type. (See examples in Figure 1.35.)
Thiazoles are five-membered rings containing both sulfur and nitrogen heteroa-
toms (Figure 1.17). They belong to the azole family of molecules, along with oxa-
zoles and imidazoles. Thiazole is slightly less aromatic than thiophene [81, 82], with
sulfur’s lone pair contributing to the aromaticity of the ring, while the nitrogen
atom is electron withdrawing. This makes thiazole an overall electron-deficient het-
erocycle in OSCs. (See examples in Figure 1.34.)

1.6.4 Substituents

Introducing substituents is a convenient way to tune the properties of a molecule or

polymer since they provide an enormous potential for structural and electronic vari-
ation (Figure 1.18). They are also necessary for solution-processable materials. Sub-
stituents can affect the energy levels of a material, as well as impact planarity, and
reorganization energy.
Long alkyl chains are commonly used to impart solubility to a polymer or large
polycyclic molecule. The nature of that chain, linear or branched, and its location,
will have an impact on the solid-state packing of the material [44]. In polymers, a
large part of the reorganization energy comes from the rotation of the interring di-
hedral angles between the neutral and charged species. This rotational energy is
greatly impacted by the size and type of substituent present on the polymer back-
bone. Using substituents that form noncovalent interactions that “lock” the conforma-
tion of the polymer backbone is advantageous for this reason. One recent example
is the use of alkoxy or fluorine substituents on benzotriazole in a benzotriazole–
thiophene copolymer (Figure 1.19). The authors attribute tight interchain ordering
and improved carrier mobilities on the noncovalent interactions between thiophene’s
sulfur and the substituents [83]. A computational study on through-space interac-
tions performed by Jackson et al., however, warns that while S–S, O–S, N–S, and
 1 Design Principles for Organic Semiconductors 23

R
N
O C10H21 R N N
S

S S S S n
n
R F F
2 3

S S O O
N N
S S S S
n S
S n

S 4 5

Figure 1.18: A selection polymers illustrating different substituents.

R1 R2 R1
N N N
H N N H N N H N N
0° 10° 0°

n n n
S S S
H H OR2 OR2 F F
PTBTz PTBTz-OR PTBTz-F
μh = 0.007 cm2/(Vs) μh = 0.019 cm2/(Vs) μh = 1.9 cm2/(Vs)

Figure 1.19: Varying the benzotriazole substituents in these copolymers did not affect the band
gap, but led to tighter interchain ordering and higher mobilities. Reprinted with permission from
Yum et al. [83]. Copyright 2014 American Chemical Society.

F–S interactions all have some stabilizing influence, their noncovalent binding ener-
gies might be too low to provide a conformational “lock” in polymers. That study
concludes that only hydrogen-bonding interactions, such as CH–N and CH–O, have
high enough binding energies (
2 kcal/mol) to act as “locking” mechanisms [84].
Electron-donating or -withdrawing substituents are often used to fine-tune the
HOMO and LUMO energy levels of a material. Replacing the hexyl chain in P3HT
with an alkoxy chain (see polymer 2) results in a 0.3 eV increase in the HOMO level,
shrinking the band gap of the polymer (1.6 eV compared to 1.9 eV for P3HT) [85].
24 Julia A. Schneider, Dmitrii F. Perepichka

Fluorine is a popular electron-withdrawing substituent because its van der Waals

radius is not much larger than hydrogen’s (135 pm vs 120 pm) and therefore does
not significantly increase torsional twisting when placed on a monomer unit, such
as on benzotriazole in polymer 3 [86].
Aromatic substituents can also be used to extend the conjugation pathway or-
thogonal to the core of the molecule or polymer. Polymer 4 is an example of this
strategy. Huo et al. found that when alkylthienyl substituents were used in place of
alkoxy groups on benzodithiophene, the resulting material had a smaller band gap,
higher hole mobilities, and performed better in BHJ solar cells [87]. Although some-
times improperly called “2D” polymers, polymers with orthogonal aromatic sub-
stituents exhibit high molecular ordering with strong π–π stacking and wider
absorption bands [88].
Finally, a substituent can be designed to be removable [89], as in polymer 5.
A thermally cleavable ester substituent was used by Fréchet and then Krebs as a sac-
rificial solubilizing group [90, 91]. Once the material has been solution processed, the
ester functionality can be removed to give insoluble, but planar, poly(thiophene).

1.6.5 Donor–Acceptor Strategy

Finally, possibly the most widely explored design strategy for manipulating the band
gap of a material is the donor–acceptor strategy, which calls for combining electron-
deficient units with electron-rich units. When these units are in conjugation, their
orbital splitting results in a narrower band gap with lower HOMO–LUMO levels (Fig-
ure 1.20a). This strategy is widely used in polymers for OPVs where broad absorption
is desired, but raising the HOMO would be detrimental to the VOC . Using D–A units,
the band gap of a material can be fine-tuned, either by altering a unit or by altering
its ratio relative to other units. The “push–pull system” in D–A polymers has other
benefits as well. As was introduced in Section 1.6.1, BLA can be decreased and po-
larizability increased by increasing the strength of the donor and acceptor moieties.
This has been extensively studied in polyenes [92], as well as other conjugated sys-
tems [93, 94]. As a result of their high polarizability, materials with D–A structures
can exhibit nonlinear optical properties, such as two-photon absorption [95, 96].
Electron-rich and -deficient aromatics are well known to assemble in a face-to-
face manner [98, 99]. The “push–pull” behavior of D–A units promotes intra-
molecular charge transfer between units, leading to intramolecular dipoles.
Thus, the dipole–dipole interactions between polymer chains lead to smaller in-
terchain distances and therefore better charge transport between polymer back-
bones (Figure 1.20b). Indeed, short π–π distances are frequently observed in X-ray
diffraction experiments of D–A polymer films [100, 101]. D–A polymer PTB7, shown
in Figure 1.13, has been used in OPVs with PCEs exceeding 9%. Yet when Yu’s
group attempted to make a similar polymer with a D–A–A structure, their highest
 1 Design Principles for Organic Semiconductors 25

a) LUMO
LUMO
Eg
HOMO
HOMO
D A
b) D–A

Donor
Acceptor

Figure 1.20: (a) The orbital splitting of donor and acceptor units results in a smaller band gap
without raising HOMO levels. Reproduced from Ref. [97] with permission of The Royal Society of Chem-
istry. (b) Tight interchain packing in D–A polymers is favored by alternating donor–acceptor π-stacks.

PCE was only 2%. By using two acceptor units, they lowered the local dipole mo-
ment causing charge localization in the A–A unit, and as a result observed faster
recombination rates and lower ISC s [102].
Examples of oft-used donor and acceptor units are shown in Figure 1.21. While
common in polymer design, the D–A strategy is equally applicable to oligomeric
molecules and unimolecular rectifiers, and can be utilized simply through the
choice of substituents as well. Examples of D–A copolymers using different build-
ing blocks are shown in Figure 1.22. All have shown excellent properties in OPVs or
OFETs. Bronstein et al. combined thieno[3,2-b]thiophene (TT) and diketopyrrolopyr-
role, two particularly well-studied units known for forming crystalline films with
good mobilities, in polymer 6. Although as-spun films of 6 showed no signs of crys-
tallinity in X-ray diffraction or differential scanning calorimetry studies, their
charge mobilities were among the highest for polymer FETs (μh = 1.95 cm2 =Vs). Poly-
mer/PC71 BM OPV devices gave a max PCE of 5.4% [103]. Higher charge mobilities
and PCE values have since been realized in many other diketopyrrolopyrrole co-
polymers [104]. With polymer 7, Chen et al. present a heptacyclic unit where the
benzodithiophene core is covalently rigidified by two flanking thiophene units. This
monomer was copolymerized with thienopyrrolodione. FET devices of 7 exhibited
modest mobilities (μh = 6.8 × 10 − 2 cm2 =Vs), but OPV devices with PC71 BM gave PCEs
of 6.6%, a vast improvement compared to the unrigidified analogue with a PCE of
0.2% [105]. Osaka et al. also utilized a fused ring approach with their D–A polymer
8, which features naphthodithiophene and naphthobisthiadiazole. The first itera-
tion of 8 had no solubilizing chains on the naphthodithiophene units (R′ = 2-decyl-
tetradecyl, R″ = H) and displayed an edge-on orientation with a π-stack distance of
26 Julia A. Schneider, Dmitrii F. Perepichka

Donors Acceptors
Weak
N S S N

N S N N S
R R R Benzobisthiazole Bithiazole
Fluorene Carbazole R R
R R R N O N O
N N
S S
S S S
R R R Benzotriazole Thienopyrrolodione
Benzodithiophene Indacenodithiophene R
O N
R R S
N N
S
Strong N O
S S S
R
Thienothiophene Cyclopentadithiophene Diketopyrrolopyrrole Benzothiadiazole

Figure 1.21: A selection of electron-donating and -accepting monomers that have been used
in D–A copolymers.

C8H17
C10H21 C8H17O OC8H17
O N O
C8H17

S N O S S
S
S S S

N S S S
O
C8H17
C8H17O OC8H17
C10H21

6 7

S
Rʹ N N
Rʺ
S
S
S
S
N N Rʹ
Rʺ S

Figure 1.22: Shown are three examples of D–A copolymers with impressive properties in OFET or
OPV devices.
 1 Design Principles for Organic Semiconductors 27

3.43 Å. This polymer yielded high performing FET and polymer/PCBM OPV devices
(μh = 0.5 cm2 =Vs, PCE = 5.2%). Adding linear dodecyl chains to naphthodithiophene
changed the orientation of the polymer films to have face-on π-stacks with a dis-
tance of 3.51 Å. The improved solubility led to even higher PCEs of 8.0% while only
lowering mobilities to μh = 0.1 cm2 =Vs [106]. Recent years have seen continued prog-
ress in the device performance of D–A polymers and small molecules. New materi-
als and processing techniques have led to OPV efficiencies of 10–12% [107–109] and
charge mobilities nearing 5 cm2 =Vs [110–112].

1.6.6 Case Study: Band Gap Control of Conjugated Polymers via

Alkylsulfanyl Substituents
The design strategies discussed earlier are all utilized in the following study, in
which the electronic properties of thienothiophene vinylene polymers are tuned for
use as OPV donor polymers. As we have seen from previous examples, thiophene-
based conjugated polymers are important semiconducting materials with wide-
spread applications in OLEDs, OFETs, and OPVs [79, 113].
Since P3HT, thiophene-based polymers have been tirelessly modified to create
new high-performance materials. The dominant approach has followed the donor–
acceptor strategy discussed earlier. This, however, requires the synthesis of two
different monomer units, complicates the structure–property relationships, and
creates a polarization along the conjugation backbone. Rather than altering the
backbone, we tune the polymers’ energy levels directly through substituents, a
method that is underutilized in conjugated polymer chemistry.
In the past, substituents such as fluorine [114], fluoroalkyl [115], thienyl [116],
dicyanoethene [117], alkoxy groups [118], nitro groups [119], and esters [120] have
been explored in PTs. We chose to study alkylsulfanyl substituents for several rea-
sons: the van der Waals radius of sulfur (0.18 nm) is smaller than that of –CH2
(0.20 nm), which slightly reduces steric strain compared to alkyl substituents [121];
they impart solubility to the polymer; and, in PTs, they can act as mild electron
acceptors, lowering the HOMO levels [122, 123]. Furthermore, their electron with-
drawing effect can be tuned by changing the oxidation state of sulfur from sulfanyl
(–SR) to sulfoxyl (–SOR) or sulfonyl (–SO2 R).
In our comparative analysis of the effect of alkylsulfanyl and alkylsulfonyl sub-
stituents on the electronic properties and behavior of conjugated polymers, we
chose poly(thieno[3,2-b]thiophene vinylene) as the conjugated backbone. Thieno-
thiophene’s (TT) fused unit fosters electron delocalization by reducing the BLA
(compared to simple thiophene) [124] and its coupling geometry (180 vs
150 for
thiophene) leads to linear rod-like structures, which reduces disorder and increases
charge mobilities [125, 126]. A vinylene spacer reduces the twist caused by repul-
sions between substituents and “dilutes” the aromatic nature of the TT moieties.
28 Julia A. Schneider, Dmitrii F. Perepichka

Both of these effects promote electron delocalization and shrink the band gap of
the polymer.
Our study led us to report the synthesis and the spectroscopic, structural, and
device characterization of poly(3,6-dialkylsulfanylthieno[3,2-b]thiophene vinylene),
S-PTTV, its oxidized derivative poly(3,6-dialkylsulfonylthieno[3,2-b]thiophene
vinylene), SO2 -PTTV, and the random copolymer incorporating both sulfanyl and
sulfonyl units, S/SO2 -PTTV (Figure 1.23) [127].

R
R O R S S
S S S S R
O O
S S
O S S O
S S S S R n
R n R O n O
S S
R O m

Figure 1.23: Polymer structures discussed in this case study, where R=2-ethylhexyl.

As was discussed earlier, the rigidity of the conjugated backbone is an important

factor defining the material properties of PTs and related structures [28]. In our pol-
ymers, DFT calculations predict a very shallow rotation barrier (
1.5 kcal/mol) for
both TT–TT and SO2 TT-V connections (Figure 1.24). This means that nonplanar
S-PTT could planarize due to solid-state packing forces (as was in fact observed
[121]). Similarly, SO2-PTTV, predicted to be nearly planar in the gas phase, could
adopt a twisted conformation under external factors. In fact, the energy penalty for
twisting the TT/vinylene dihedral angle in SO2 -PTTV by 50 is smaller than RT

8
Relative energy (kcal/mol)

6 S-2TTV

SO2-2TTV
2

0 20 40 60 80 100 S-2TT

Figure 1.24: Energy barrier of rotation of thiophene/vinylene dihedral angles in model dimers
S-2TTV (blue dot), SO2 -2TTV (red square), and S-2TT (green diamond).
 1 Design Principles for Organic Semiconductors 29

(0.6 kcal/mol at room temperature). In contrast, a much larger rotation barrier

against twisting (7.9 kcal/mol per TT/vinylene connection) is predicted for S-PTTV.
This can be attributed to the smaller size of the alkylsulfanyl group and perhaps to
weak attractive S  H interactions between the substituents and vinylene protons
(the calculated S  H distance is 2.80 Å).
The UV–vis absorption spectra of the polymer thin films (Figure 1.25) dis-
played broad absorption spectra. The absorption of solid S-PTTV, λedge = 765 nm
(Eg = 1.62 eV), is red-shifted from analogous alkyl-substituted poly(3,6-dihexyl)
thieno[3,2-b]thiophene vinylene C6 -PTTV, which showed a band edge at 700 nm
(1.77 eV) [129] and from poly(3,6-dioctylsulfanylthieno[3,2-b]thiophene), SC8 -PTT,
whose band edge appears at 713 nm (1.74 eV) [121]. Evidently, both the sulfanyl sub-
stituents and the vinylene spacer play a part in shrinking the band gap. Replacing
sulfanyl sides chains with sulfonyl (SO2 -PTTV) results in a
0.1 eV increase of the-
optical band gap (720 nm, 1.72 eV). This increase should in part be attributed to the
lower molecular weight of the SO2 -PTTV polymers, although its lower rigidity (Fig-
ure 1.24) should also play a role. Copolymer S/SO2 -PTTV-1:1 shows a lowered band
gap of 1.53 eV, which can be attributed to the donor–acceptor interactions between
sulfanyl and sulfonyl-substituted units. The balance between the latter appears im-
portant as the increased amount of –SO2 substituted TT units in S/SO2 -PTTV-1:2
increases the band gap (1.64 eV), possibly not only due to disrupted solid-state
packing, but also due to a lower MW.

SO2-PTTV
1 S/SO2-PTTV-1:2
S-PTTV
0.8 S/SO2-PTTV-1:1
Absorbance

0.6

0.4

0.2

0
400 500 600 700 800 900
Wavelength (nm)

Figure 1.25: Absorption spectra of polymers as thin films on glass. The inset shows the highly
reflective, metallic luster of a film of S-PTTV.

The effect of the substituents was further analyzed via the redox behavior of the
synthesized polymers, as studied by cyclic voltammetry for thin films drop-cast on
Pt electrodes (Table 1.1). Compared to the alkyl-substituted C6 -PTTV [129], the sul-
fanyl substituents show a moderate electron withdrawing effect, shifting the
30 Julia A. Schneider, Dmitrii F. Perepichka

Table 1.1: Redox potentials,a HOMO–LUMO levels,b and band gapsc of polymers determined by
cyclic voltammetry of thin films.

Ered (V) Eox (V) LUMO (eV) HOMO (eV) EgCV (eV)

C6 -PTTV [129] –. . –. –. .

S-PTTV –. . –. –. .
SO2 -PTTV –. . –. –. .
S/SO2 -PTTV-1:1 –. . –. –. .
S/SO2 -PTTV-1:2 –. . –. –. .
a
All potentials reported versus Fc/Fc + in 0.1 M Bu4 NPF6 /propylene carbonate.
b
Calculated from the onset of the oxidation and reduction potentials, assuming HOMO of Fc at
−4.8 eV [130].
Eg = HOMO – LUMO.
c CV

oxidation and reduction of S-PTTV by 0.08 and 0.20 eV, respectively. A much
larger shift is observed for sulfonyl-substituted polymer, SO2 -PTTV (0.67 and
0.63 V shifts for oxidation and reduction, respectively). The random copolymers S/
SO2 -PTTV-1:1 and S/SO2 -PTTV-1:2 show the electronic effects of both their mono-
mer units with reduction and oxidation onsets between those of S-PTTV and SO2 -
PTTV, giving them the smallest electrochemical gaps at 1.87 and 1.88 eV,
respectively.
A rather low hole mobility in thin-film transistors of
1 × 10 − 5 cm2 =Vs was
measured for S-PTTV, and no further improvement was achieved upon annealing.
A likely reason for the poor transistor characteristics of these materials lies in the
rotational disorder of the polymer chain and the resultant poor packing, caused by
the out-of-plane protrusion of the alkylsulfanyl substituents.
In bulk-heterojunction solar cell devices from polymer:PC70 BM blends S-PTTV
displayed slightly higher open-circuit voltages (VOC = 0.68 V) than reported for C6 -
PTTV (VOC = 0.60 V), as is expected due to its lower HOMO level. The trend contin-
ues for S/SO2 -PTTV-1:1, which has the lowest HOMO level and a high VOC of
0.80 V. Thus, we were able to directly tune the open-circuit voltage of the devices
by controlling the ratio of the substituents. The performances of both the S-PTTV
and S/SO2 -PTTV-1:1 devices were limited, however, by low short-circuit currents
(ISC ) and FF. Poor mobilities mean more chances for recombination at the interface
before holes and electrons can diffuse away, as well as an increase in the serial
resistance, resulting in low FFs [131, 132].
In conclusion, the sulfanyl and sulfonyl substituents show moderate and strong
electron-withdrawing effects and their combination in random copolymers is a
means to fine-tune optoelectronic properties and achieve low band gap polymers
(1.5 eV) without affecting the uniformity of the conjugated backbone. This method
can be a welcome alternative to designing more complex donor–acceptor motifs for
new polymeric semiconductors.
 1 Design Principles for Organic Semiconductors 31

1.7 Supramolecular Solid-State Assembly

Although design strategies can be used to tune the energy levels and reorganization
energy of a material, the electronic coupling will be dictated by the solid-state as-
sembly of that material. It is the sum of intermolecular π-orbital interactions in
three dimensions that will determine the efficacy of charge transport. Most molecu-
lar semiconductors display one of four main packing-motifs, shown in Figure 1.26.
Close packing that favors strong π–π overlap is beneficial for charge transport, but
strong anisotropy may yield poor mobilities in the bulk material, where π–stacks
may not align with the direction of current measurement or else be interrupted by
point defects or grain boundaries. As a result, 1D π-stacking of coparrallel mole-
cules (such as in Figure 1.26b, c) rarely leads to efficient semiconductors. Rather,
2D herringbone packing (Figure 1.26a) is common for many high mobility semicon-
ductors, despite limited π-overlap of nonparallel molecules.

(a) (b)

Figure 1.26: The four common packing motifs are

(a) herringbone, (b) cofacial herringbone, (c)
1D lamellar “slipped stacks,” and (c) 2D lamellar
(c) (d) “brickwork” packing. Directions of preferred
charge transfer are shown by arrows. Reprinted with
permission from Schweicher et al. [21]. Copyright
2014 John Wiley & Sons, Inc.

It is important to remember that the conductance and valence bands are formed by
molecular orbital interactions, so not only must the molecules be closely packed,
but also their frontier molecular orbitals should be aligned as well. Figure 1.27
maps the electron coupling (t) of two cofacial pentacene molecules with respect to
long axis displacement. The molecular overlap is at its maximum when the mole-
cules are perfectly aligned and decreases in an oscillatory pattern that correlates
with the nodes of the HOMO orbitals. The electronic coupling (t) in a material can
be calculated from the crystal structures. In symmetric systems, t can be approxi-
mated by the energy splitting of the frontier orbitals in a dimer (for example, ΔE =
(HOMO – HOMO-1)/2 for hole transport) [133]. This approximation, called the en-
ergy-splitting-in-dimer approach (ESID), assumes both molecules in the dimer have
the same site energies, which will not be the case if the molecules inhabit different
environments in the crystal lattice. The energy-splitting-in-dimer method is, there-
fore, not reliable for extended systems where polarization effects of the crystal envi-
ronment on the site energies should be taken into account [134]. A better
calculation of t is the direct-coupling method, which calculates t from the wave
function of each molecule according to eq. (1.6)
32 Julia A. Schneider, Dmitrii F. Perepichka

300 Displacement
HOMO
LUMO 3.74 Å
200

100
t (meV)

–100

–200
0 2 4 6 8 10 12 14

Figure 1.27: Evolution of the HOMO and LUMO intermolecular electronic coupling (t) as a function
of displacement for two tetracene molecules with a π-stacking distance of 3.74 Å. The dotted line
indicates the magnitude of long-axis displacement found in rubrene crystals. Reprinted with
permission from Da Silva Filho al [135]. Copyright 2005 John Wiley & Sons, Inc.

J − 21 ðε1 + ε2 ÞS
t= (1:6)
1 − S2

where J is the charge transfer integral, S is the orbital overlap, and ε1 and ε2 are the
site energies of the molecules.
While predicting exact packing motifs is not generally possible, and the chance
of polymorphism is likely, morphological changes can be induced through molecu-
lar design. A few recent reviews have addressed this subject as it applies to poly-
mers and small molecules [136, 137]. What follows are a few examples of design
strategies based on noncovalent intermolecular interactions.
The solid-state packing of molecules is controlled by noncovalent effects,
namely, van der Waals and coulombic interactions. For example, in pentacene,
electron density lies in the π-orbitals above and below the plane of the molecule
and slightly positively charged hydrogen atoms lie along the periphery of the penta-
cene backbone. This generates a quadrupole moment, represented as a partial posi-
tive charge density sandwiched between two partial negative charge densities
(Figure 1.28a). Pentacene has many polymorphs [138], but all of them adopt a her-
ringbone arrangement to maximize electrostatic interactions between its partially
negative “face” and partially positive “edge.” (Figure 1.28a). This face-to-edge pack-
ing still allows for high electronic coupling between the different molecular dimers,
leading to high mobilities in pentacene films (μh
1 cm2 =Vs) [139] and single crys-
tals (μh
40 cm2 =Vs) [140].
 1 Design Principles for Organic Semiconductors 33

(a)

(b)

Figure 1.28: (a) Pentacene’s herringbone face-to-edge packing is due to its quadrupole moment.
(b) In perfluoropentacene the herringbone packing is orthogonal with tighter π–π stacks. Section (b)
reprinted with permission from Sakamoto et al. [141]. Copyright 2004 American Chemical Society.

There are several ways to disrupt these electrostatic CH–π interactions and get
tighter π–π stacks. One way is to replace the hydrogens with heteroatoms. Per-
fluoropentacene, for example, has an inverse electron density distribution to pen-
tacene and is a well-known OSC for n-type transport due to the electron-
withdrawing nature of fluorine. The fluorine atoms affect the packing of the mole-
cules, in which CH–π interactions are replaced by F–F interactions between nearly
perpendicular molecules (Figure 1.28b). The CF–π interactions between molecules
of the same π-stack also greatly reduce their short-axis displacement (3.15 Å vs
5.34 Å in pentacene), thereby increasing the electronic coupling between cofacial
molecules [141, 142].
The use of bulky substituents is another oft-used strategy for controlling crys-
tal packing. Trialkylsilylethynyl groups have been extensively studied as substitu-
ents on oligoacenes because their size can be easily controlled. Anthony et al.
34 Julia A. Schneider, Dmitrii F. Perepichka

found that with smaller alkylsilyl groups (e.g., SiMe3 ), pentacene derivatives as-
semble into slipped stacks, but if the size of the substituent is approximately half
the length of the acene backbone, then a lamellar “brickwork” arrangement is ob-
served [145]. This type of packing in crystals of bis(triisopropylsilylethynyl)penta-
cene (TIPS-pentacene) leads to good electronic coupling between overlapping
pentacene cores (54 and 65 meV) and high mobilities (μh = 1.8 cm2 =Vs) (Figure
1.29a) [146, 147].
Okamoto et al. designed aryl and perfluoroaryl substituted tetracene as another
way to induce face-to-face packing of the acene core. Here, aromatic–fluoroaromatic

F
(a) (b)
F F

F F
Si Si

a
3.30 Å
0 3.35 Å

Figure 1.29: (a) Brickwork packing of TIPS-pentacene induced through bulky substituents.
Reprinted with permission from Anthony et al. [143]. Copyright 2001 American Chemical Society.
(b) Aromatic donor–acceptor interactions between substituents gives a lamellar brickwork assem-
bly in 5-perfluorophenyl-11-phenyltetracene. Reprinted with permission from Okamoto et al. [144].
Copyright 2011 American Chemical Society.
 1 Design Principles for Organic Semiconductors 35

(quadrupole) interactions between the substituents of coplanar tetracenes causes la-

mellar packing and close π–π distances between tetracene layers (Figure 1.29b)
[144]. Without such interactions, bis(phenyl)tetracene adopts a herringbone confor-
mation with no π–π stacks.
Alkyl chains placed along the long axis of the molecule, on the other hand, do
not disrupt the packing of the molecules, but rather bring them closer together
through van der Waals interactions. Inoue et al. studied the crystal packing of phe-
nyl–benzothieno[3,2-b]benzothiophene with increasing lengths of alkyl chain sub-
stituents [148]. They found that increasing chain length (n = 10) strengthens
attractive dispersion forces between the chains, leading to much higher electronic
couplings.
CH–π interactions can also be weakened by replacing carbon with heteroatoms
along the periphery of the molecule. OSCs containing sulfur, a larger and more po-
larizable atom than carbon, may benefit from intermolecular interactions through
S  S contacts. For such contacts to be useful to hole transport, however, there
must be large HOMO orbital coefficients on the sulfur atoms [149]. Even without
short S  S distances, having high orbital coefficients over the sulfur atoms can
lead to better electronic coupling. Figure 1.30 shows several thiophene containing
OSCs, their HOMO orbital contours, and hole transport mobilities in FETs [150, 151].
The intensity of orbital coefficients on sulfur varies with structure. Notably, [5]thie-
noacene has virtually no orbital coefficients on its sulfurs, so that its HOMO orbital
does not extend along its periphery. This explains its relatively low mobility [152].
In DNT-V (μh = 1.1 cm2 =Vs), on the other hand, the HOMO coefficients reside heavily
on the central sulfur atom [153]. Unfortunately, other factors may affect charge mo-
bilities. For example, the low lying HOMO of BBBT (−5.6 eV) is thought to cause a
large hole injection barrier and limit its mobilities (μh = 0.01 cm2 =Vs) [154, 155].
Some heteroatoms, like O or N, can partake in hydrogen bonding, which could
compete for morphological control. The self-assembly of well-defined supramolecu-
lar structures requires high-fidelity intermolecular interactions that lead to revers-
ible association and provide predictable intermolecular geometries. In this regard,
H-bonding is arguably the most far-reaching interaction for supramolecular control,
yet has received surprisingly limited attention in OSCs. Our group has demon-
strated efficient charge transport in H-bonded materials, namely, between dipyrrolo-
pyridine donors and imide-functionalized acceptors (Figure 1.31) [156, 157]. The
H-bonding interaction not only provides a handle for solid-state structural con-
trol, but also leads to electronic perturbation due to H-bonding-mediated charge
redistribution in the π-conjugated systems. This affords a stronger D–A pair, en-
hanced π–π interactions, and facilitates CT interactions between H-bonded complexes.
In Figure 1.32 we see how changes in the linearity of a molecule affect preferen-
ces for face-to-edge CH–π interactions versus face-to-face π–stacking. Dinaphtho
[2,3-b:2ʹ,3ʹ-f]thieno[3,2-b]thiophene (DNTT) is an excellent p-type semiconductor,
due in part to its acene-like structure and electronic coupling in several directions
36 Julia A. Schneider, Dmitrii F. Perepichka

S S S S

S S S

[5]Thienoacene Dinaphthothienothiophene (DNTT)

μh = 0.045 cm2/Vs μh = 3.0 cm2/Vs

S
S

S
S S
Dithienobenzodithiophene (DTBDT) Dinaphthothiophene (DNT-V)
μh = 1.7 cm2/Vs μh = 1.1 cm2/Vs

S
S

S S
Benzobisbenzothiophene (BBBT) Anthradithiophene
μh = 0.01 cm2/Vs μh = 0.3 cm2/Vs

Figure 1.30: Calculated HOMO orbital contours (B3LYP/6-31G(d)) and hole transport mobilities for
several thiophene-containing OSCs.

[80, 158]. “Bent” structural isomers of DNTT, however, exhibit much lower charge
mobilities due to 1D electronic coupling or electronic coupling between isolated
dimers. In addition, of the three isomers, only DNTT shows HOMO orbital coeffi-
cients on the sulfur atoms.
Finally, processing techniques can have a huge impact on the morphology of
the material [159]. The same molecule will display vastly different electronic proper-
ties depending on whether it was drop cast, spin coated, evaporated, annealed, or
grown as a single crystal. New solution-processing techniques like solution shear-
ing, in which a top wafer is dragged across the evaporating OSC solution, have suc-
ceeded in forming oriented crystalline thin films by physically straining the
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(under the new covenant) are to continue till Christ’s coming in his
manhood, I Cor. 11, 26, and then they will cease also.
 “ADVERTISEMENT.”
John Rogers, Sr.

Whereas there is a printed law in her Majesty’s Colony of

Connecticut, entitled only “Heriticks,” in the preface to it they say “To
prevent the danger persons are in of being poisoned in their
judgments and principles by hereticks,” etc.
Which said law the queen by advice of her council hath
condemned, repealed and declared it void and of none effect, it
being contrary to their charter. And indeed there is a good hand of
God in the Queen’s act, for I know of no sect worse poisoned in their
judgments and principles by gross heresy than the Church of New
England; and it is very evident that hereticks have ever persecuted
the true church under abusive titles, as deceivers, hereticks,
Quakers, and the like abusive titles, which they themselves are guilty
of; for erroneous persons, principles and practices are condemned
by the scriptures of truth; so that they have no other way to cloak
themselves, under their delusion and heresy, but by casting such like
odious titles on the children of God, and so persecute them and burn
their books; for Satan’s design in making use of these deluded
persons, thus to act, is to suppress truth under pretense of heresy;
as for instance I shall begin with the master of the house, whom
they called Beelzebub, the prince of devils, Mat. 12, 24. He went by
the name of “deceiver,” Mat. 27, 63. Paul by the name of heretick,
Acts 24, 14. Luther’s books were burnt under pretense utterly to
suppress heresy; the worthy martyrs in Queen Martyr Mary’s time
suffered death under the name of hereticks; and those worthy
martyrs in Boston in New England under the name of Quakers and
hereticks; and my books by this law now repealed have been
condemned and burnt, under pretense of heresy, though I have
made fair proffers at their General Court to reward any person well
for their time and pains that would endeavor to show me any one
error in them, but none have yet publickly appeared.
 FOLLOWING FROM ACCOUNT OF SAMUEL
BOWNAS OF HIS “CONVERSATION
WITH JOHN ROGERS,” 1703.
He (John Rogers) spoke very much of his satisfaction and unity
with George Fox, John Stubbs, John Burnyeat and William
Edmundson as the Lord’s servants, with sundry others of the first
visitors of that country, that he knew them to be sent of God, and
that they had carried the reformation further than any of the
Protestants ever did before them, since the general apostacy from
the purity both of faith and doctrine; first the church of England they
did nothing in the end but made an English translation of the Latin
service used before, the Presbyterians they dissented and the
Independants, but came not to the root of the matter; the Baptists
dissented from the other three, but went not through. Upon which,
though I could not wholly agree with him in his assertions, I queried
if he thought that all these several steps of the English church from
Popery, the Presbyterians and Independants from the English
church, and the Baptists from all three of them, had not something
of good in them, viz. I mean whether the first concerned in
dissenting from Popery, though they afterwards rested too much in
the form of worship in the Episcopal way, had not the aid of Christ’s
spirit to assist them in their dissent? And so for all the rest. This he
did readily grant to be a great truth; and so allowing that the first
reformers actuated by divine light, and being faithful to what was
made known to them, had their reward; and their successors sat
down in that form their predecessors had left them in, but did not
regard that Power and Life by which they were actuated, and so
became zealots for that form, but opposed the Power. “And this,”
said he, “is the true cause of the several steps of dissent one from
another; and the reason why there is so little Christian love, and so
much bitterness and envy one against another, is their sitting down
contented, each in their own form without the Power, so that they
are all in one and the same spirit, acting their part in the several
forms of worship in their own wills and time, not only opposing the
Spirit of Truth, but making it the object of their scorn and those who
adhere to it the subject of their reproach, contempt and envy; and
this is the foundation of persecution” said he....
 FROM REPLY TO J. BACKUS.
John Rogers, 2d.

... Here I think he (Backus) does the government no honor by

informing the world that they have made laws to debar such as
differ from them in matters of religion the liberty of the king’s
highway to pass to their own meetings, since our lord the king hath
granted equal liberty of conscience to all dissenters to hold their
meetings and serve God according to their consciences....
In his 13th page he gives a record (of his own making) relating to
John Bolles, which record declares that J. Bolles acknowledged that
he came from New London, and was going to Lebanon, and that he
knew it was contrary to our law, and that they did it in defiance of
the law.
To which I answer, “That God’s three children were cast into the
fiery furnace for declaring their defiance to the king’s law, which was
made to force men’s consciences in matters of religion; and all the
prophets and apostles suffered for opposing those laws which were
set up to force people’s consciences in matters of worshipping God;
And all the martyrs which have suffered the flames and other
tortures ever since, it has been for manifesting their defiance to such
laws as have been set up by the worldly government to uphold false
worship, or to restrain them from worshipping God according to their
consciences. Now for as much as God has justified all those sufferers
above-mentioned, for their bold defiance of such laws as were set
up by man to prevent people serving God according to their
consciences, well may we have confidence that God will justify us for
the same thing. We have also further to plead in our own
justification in this matter than those sufferers above-mentioned
had, inasmuch as our lord the king has granted us the same liberty
to meet together and worship God according to our consciences as
he has given to our persecutors: So that in the consideration of what
is here expressed, I think J. Bolles and his brethren are highly
commendable for their faithfulness to God, in manifesting their
defiance against such laws as would restrain them from worshipping
God according to their consciences.
... In his 14th chapter, he charges the sufferers to be most daring
and malicious offenders, utterly disregarding those Scriptures, Rom.
13, Tit. 3, I Pet. 2, etc.
In the first place I shall fully grant from those Scriptures, and
many more that might be mentioned, that the worldly government is
set up of God, and are God’s ministers to act in worldly matters
between man and man, and that the law that God hath put into their
hands is good, if they use it lawfully;... according to what is written,
I Tim. 1, 8, 9, 10. And while the worldly government act within their
commission, God is with them and has put such carnal weapons in
their hands as is sufficient to rule all carnal persons, which are
stocks, fines, prisons, whip and gallows, which above-named
weapons are sufficient to conquer and subdue all carnal and guilty
persons, so that rulers are a terror to evil-doers.
And forasmuch as we acknowledge the worldly government to be
set up by God, we have always paid all public demands for
upholding the same; as town rates, county-rates and all other
demands, excepting such as are for the upholding hireling ministers
and false teachers which God has called us to testify against. Now
when the worldly rulers take upon themselves to make laws relating
to God’s worship, and thereby force men’s consciences, and so turn
their sword against God’s children, they then act beyond their
commission and out of their jurisdiction; and are so far from being
God’s ministers that they are fighters against God and his church;
and God is so far from making them a terror to his church that he
gives his church and people faith and boldness to withstand them to
their faces....
... Here I think he (Backus) does the government no honor by
informing the world that they have made laws to debar such as
differ from them in matters of religion the liberty of the king’s
highway to pass to their own meetings, since our lord the king hath
granted equal liberty of conscience to all dissenters to hold their
meetings and serve God according to their consciences.
 FROM ANSWER TO A PAMPHLET BY
COTTON MATHER.
By John Rogers, 2d.

... A travelling ministry are sent from town to town and from city
to city, and from country to country, and over sea, so that they are
not only taken from their own employment, but are also sent upon
charges; their state and condition is like a man that is prest a soldier
and sent away from his own living on charges and therefore
maintained at the king’s charge. And hath not this man power to
forbear work? though he tarry some days at a place, must he
therefore maintain himself by his own labor? is not this the very
state of a travelling ministry of the gospel?...
... I have thus proved by Scripture that a traveling ministry of the
Gospel hath power to forbear work. And secondly that the churches
ought to relieve them: And thirdly have shewed their differing state
from settled elders.
... In the second place, I shall now prove by Scripture that settled
elders are commanded to work with their hands and thereby to
support the weak; by being givers rather than receivers.—We find
that the apostle sends for the elders of the church.—He saith to
them, I have coveted no man’s silver or gold, or apparel; ye
yourselves know that these hands of mine have ministered unto my
necessities and to them that were with me; I have showed you all
things, how that so laboring, ye ought to support the weak, and to
remember the words of the Lord Jesus, how he said, it is more
blessed to give than to receive....
... And 3rdly Whereas Christ, upon sending them forth to preach
the gospel, forbids them making any provision for their journey,
requiring them to expect their meat and reward from his hands....
... From hence we may see by Scripture that Christ’s ministers,
whom he calls and sends to preach the Gospel, are so well provided
for by Him that they have no need to be hired by the children of the
world; for in so doing they would reproach their Lord and Master
and shew themselves not only faithless, but wickedly covetous, in
practising contrary to this doctrine of Christ, and to come under the
condemnation of this great sin so much condemned in Scripture,
“The priests whereof teach for hire, and the prophets whereof divine
for money, yet they will lean upon the Lord, and say, is not the Lord
among us; none evil can come upon us. Therefore shall Zion for
your sakes be plowed as a field, and Jerusalem shall become heaps,
and the mountains of the house as the high places of the forest ...
yea they are greedy dogs, which can never have enough, they are
shepherds that cannot understand; they all look to their own way,
every one for his gain from his quarter.”... Christ calls them hirelings
and ravening wolves.
And though the nameless authors of the said Pamphlet are
pleased to call such (as join with Christ and his shepherds, to testify
against these hirelings) by the name of wolves, yet these hirelings,
or at least their shearers, the collectors, have always taken them for
sheep, especially about shearing time.... Now we that join with
Christ and the true shepherds to testify against these hirelings, we
come under the blessing of Christ ... Blessed are ye when men shall
revile you and persecute you, for so persecuted they the prophets
which were before you; yea this must we suffer all the time that
these hireling prophets are under this curse of Christ. Wo unto you
when all men shall speak well of you, for so did their fathers to the
false prophets.
... In page 8, they assert ... “That he be given to hospitality” and
say they, “how is it possible for him to be so, if you be given to
covetousness, and given to dishonesty and cheat him of his
maintainance?”
To which I answer If it be the people’s gift, its their hospitality and
not the ministers: the churl may be liberal, if other men’s purses
make him so. But the ministers of the Gospel are given to hospitality
of that which their own hands have ministered to them, and are
obedient to their Master’s words, who hath said unto them, “It is
more blessed to give than to receive.”
 ... And it is a shame for you to tell of the galling of your hands
with inferior labor for the getting of bread; it is your duty to do so,
and if the people be the cause, as you say, of your laboring with
your hands, they are worthy of praise in causing you to do your
duty, and you ought to have done it without their causing you to do
it, and therefore you proclaim your shame. For you ought to have
taken the holy prophets, and Christ and his apostles for your
example, to have labored with your hands, and not the false
prophets and false teachers, who sought to live upon the people,...
Christ shews that such stewards as those could not dig for their
living, and to beg they were ashamed....
And the true prophets, and Christ with his apostles have set us
better example.... Here you may see that Elijah was plowing ... here
Elisha went to Jordan with the sons of the prophets and cut down
wood.... Amos was a husbandman and a gatherer of wild figs....
Christ was a carpenter.... Paul was a tayler or tent-maker and
worked at it tho’ he were a travelling minister of the gospel,—and so
did the rest of the apostles, as is to be seen.... These examples, with
that apostolical command (to the elders of the church) Acts 20, 34,
35, ought to be attended by Christ’s ministers....
 FROM REPLY TO PETER PRATT.
John Rogers, 2d.

As it has ever been allowed that the defaming of the dead is a

mark of the most unmanly and base spirit of a coward and ought to
be abhorred by all persons who bear the image of man; then how
much more abominable is it of P. P. to sport himself with his own lies
over a man in his grave? And I think no person of common reason
will expect any apology of me on account of this my undertaking,
since my silence in this matter would have rendered me very
unmanly....
... If John Roger’s books contain “but few of his principles” then
how comes P. P. to know what his principles are, several years after
his death? except the same spirit which once deceived him in the
matter of longitude has again deceived him concerning J. R.’s
principles; and we have as much reason to question the truth of
what he tells us of J. R.’s principles (since he has no better proof
than his own bare word) as the General Assembly had to question
the truth of longitude, which soon after proved a delusion of
Satan....
Now by these foolish and vain pretended reasons, the reader may
plainly see that he only wanted an excuse to evade J. R.’s books,
that he might take his full swing to bely and abuse him at his
pleasure; because he well knew that if he had quoted his books,
they would have discovered his falsehoods....
But I should not have enlarged so much upon this head, were it
not that I am sensible that there are many thousands of grown
persons in this Colony that for want of opportunity to be informed in
the principles of other sects remain so ignorant that they know no
difference between the Church of England and the Papists, nor
between the Quakers and the Baptists, but esteem each couple to
be alike. And now is it possible that such persons should be able to
discern the ignorance of P. P.?...
... Now how marvellous is it that P. P., who knew himself to be a
man so inconstant and changeable, not only in his worldly concerns
from his very childhood, but also in matters of religion since he has
arrived to riper years, should presume to put out a book only on his
bare word, without any proof at all. Surely he might reasonably have
thought that all who knew him would expect better proof from such
an inconstant person than from any other man....
 FROM ANSWER TO MR. BYLES, BY JOHN
AND JOSEPH BOLLES.
Considerable light is thrown upon the “Outbreak” of 1764-66 by a
Rogerene pamphlet (of about 1759), which appeared in several
editions, sometimes ascribed on the title-page to John Bolles,
sometimes to his son Joseph, and probably the joint work of father
and son, written out by the latter; thus having a style noticeably
different from that of John Bolles, although equally clear-cut and
forcible. John Bolles, being at the date of this work eighty-two years
of age, may be supposed to have welcomed the aid of his son
Joseph, both as collaborator and amanuensis. The following is from
a copy of this work to be found in the New London Public Library:—

An Answer to A Book entitled The Christian Sabbath, explained

and vindicated in a discourse on Exodus XX. 8.[192] Jan. 14, 1759,
upon a particular occasion, by Mather Byles, pastor of “The First
Church of Christ” (as he saith) in New London, written by Joseph
Bolles, in behalf of the rest which suffer persecution for breaking
said pretended sabbath.
In page 5 of Mather Byles sermon, he says: The Christian Sabbath
has of late been publickly attacked; and those who observe it have
been challenged to show any scripture warrant for the practice.
Ans.
We have been imprisoned 23 at a time, 8 of us about 7 months,
and some of the best of our cattle and horses and other goods taken
away, and 3 of us cruelly whipped, near 20 stripes apiece, for doing
the business of our ordinary calling on the 1st day of the week,
which he calls the Sabbath, all within 9 months. And in these
persecutions we have continually desired our persecutors to show
any Scripture warrant for their practice; we have also sent forth
advertisements promising ten pounds reward to any person that
could show us one word in the Bible that forbids labor on this
pretended Sabbath; which we suppose he calls “a challenge;” and
because he cannot find a word in the Bible that forbids labor on his
pretended Sabbath he has preached a sermon instead thereof, and
though he calls it the Christian Sabbath, it is not called so in
Scripture; by which it is evident it was not the Christian Sabbath in
the apostles time; for if it had been they would have called it so.
Also his text is part of the commandment to labor six days and rest
the seventh; so that his own text that he builds his Sabbath upon
requires labor on his pretended Sabbath. For it says six days shalt
thou labor; and we know that this pretended Sabbath is the first of
the six days....
... In page 18 he says, “And lastly to assign a reason why there is
no command for this Sabbath in the New Test.;” and in his next
page he says, “The apostles left it to after discoveries,” which will be
answered in its place. But neither God nor man require us to keep a
Sabbath without a law, “For where no law is, there is no
transgression.” Rom. IV. 15. And sin is not imputed when there is no
law: And the “Confession of Faith” of this Colony requires a
command for all the worship we perform to God, in page 7, and
there is no discovery of this pretended Sabbath in the Bible; for he
says, “the apostles left it to after discoveries,” and the first command
that we have discovered for this pretended Sabbath was more than
300 years after Christ by Constantine the emperor, recorded in “Fox’s
Acts and Monuments,” Vol. I. p. 134, in these words: “The Sunday
he commanded to be kept holy by all men and free from all judiciary
causes, from markets, marts, fairs and other manual labors, only
husbandry excepted.” Here we may observe no husbandry labor is
forbidden, in this “after discovery.”
Also king Inas, who reigned in England, in the year of our Lord
712, commanded that infants should be baptised within 30 days,
and that no man should labor on Sunday. “Fox’s Acts etc.” Vol. I, P.
1016. Observe in this after discovery all labour is forbidden; as
popish darkness increased, this Sabbath strengthened and infant
baptism was also “discovered.”
Also king Edgar, who began his reign in England in the year of our
Lord 959, he ordained that Sunday should be kept holy from
Saturday noon till Monday morning, and he ordained and decreed
for holy days and fasting days. “Fox’s Acts,” Vol. I. P. 1017. Observe
this “after discovery” being in midnight popish darkness, this
Sabbath was kept more strict and they also discovered half a day
more, and holy days and fasting days to be observed. Also king
Canutus, who began to reign in England in the year 1016, he
commanded celebration of the Sabbath from Saturday noon till
Monday morning. This king “discovered” it by the name of
“Sabbath”; but the other three “discovered” it by the name of
“Sunday.”
Also in our Colony there is an ample “after discovery” of it by the
name of Sabbath or Lord’s day, which exceeds the four other “after
discoveries;” with a famous law to torture the bodies of them that
break this pretended Sabbath, by whipping, not exceeding 20 stripes
if they refuse to pay a fine; and doubtless there has been more
“after discoveries” by express commands, for this pretended
Sabbath, in Rome, France and Spain. Therefore if M. B. will preach
up this pretended Sabbath, which he says the apostles left to “after
discoveries,” he ought to have taken his text out of the
forementioned “after discoveries,” where there are express
commands to build their Sabbath upon; but, as he builds it on God’s
commandment, which commands labor on his pretended Sabbath, it
has no foundation to stand upon, and therefore stands upon
nothing. No “after discovery,” neither this pretended Sabbath, infant
baptism, nor the mass nor purgatory, ought to be built on any text in
the Bible. But whoever preaches up any of these “after discoveries”
they ought to take a text out of the law book, where they are
instituted and commanded, and not out of the Bible where they are
not “discovered.”

How fully Mr. Byles had endeavored to stir up the authorities to

take the offenders strenuously in hand will be inferred from the
following, from the same pamphlet.

... He calls us deluded, blind, obstinate, because we suffer

persecution for breaking a Sabbath which he says the apostles left to
“after discoveries.” But it is this sort of ministers that preach to our
General Court to suppress or persecute them that walk by the
apostle’s doctrine, for not observing this Sabbath which he says the
apostles left to “after discoveries.”

He further says:

“Take away the Sabbath and what will be the consequence?”

Ans. He speaks like the idolaters of old. Judges XVIII. 24. “Ye
have taken away my gods which I made, and the priests,—and what
have I more?” Here we may see the idolaters speak all with one
voice; their heart is after their idols and their priests more than after
God.
Next he says: “Errors in doctrine and corruption in practice would
break in upon us like a flood, immorality would triumph without
control.”
Ans.
It is such a time now, for there are errors in doctrine, manifest
errors indeed, in this and other sermons; and corruption in practice
is already broken in upon us like a flood, and immorality triumphs
almost without control among the people, who are encouraged to it
by the example of their priests, which live immoral lives in
covetousness, pride, fulness of bread and abundance of idleness....
Also the observers of this pretended Sabbath do allow that there is
more immorality amongst themselves than there is among us who
do not observe it. Immorality triumphs in a high degree, even in
gathering money for the priests of many poor people to whom there
is more need to give, and casting some into prison to force them
against their conscience to pay money to maintain such priests in
idleness,[193] which they know God hath not sent to teach them.
 EXTRACTS FROM “LOOKING GLASS FOR
THE PRESBYTERIANS OF NEW LONDON.”
John Rogers, 3d.

To see their Worship and worshippers Weighed in the balance and

Found Wanting.—With a true account of what the people called
Rogerenes have suffered in that town, from the 10th of June 1764 to
the 13th of December 1766. Who suffered for testifying, That it was
contrary to Scripture for ministers of the gospel to teach for hire.
That the first day of the week was no Sabbath by God’s
appointment. That sprinkling infants is no baptism and nothing short
of blasphemy, being contrary to the example set us by Christ and his
holy apostles. That long public prayers in synagogues is forbidden by
Christ. Also for reproving their church and minister for their great
pride, vain-glory and friendship of the world they lived in.—With a
brief discourse in favour of women’s prophesying or teaching in the
church.—Written by John Rogers, New London. Providence N.E.
Printed by the author 1767.
June 10, 1764. We went to the meeting house at New London,
and some of our people went into the house and sat down, others
tarried without and sat upon the ground some distance from the
house. And when Mather Byles their priest began to say over his
formal, synagogue prayer, forbidden by Christ, Mat. VI. 5 etc., some
of our women began to knit, others to sew, that it might be made
manifest they had no fellowship with such unfruitful works of
darkness. But justice Coit and the congregation were much offended
by this testimony, and fell upon them in the very time of prayer and
pretended divine worship; also they fell upon all the rest of our
people that were sitting quietly in the house, making no difference
between them that transgressed the law and them that transgressed
not; for they drove us all out of the house in a most furious manner;
pushing, kicking, striking etc., so that the meeting was broken up for
some considerable time and the house in great confusion: Moreover,
they fell upon our friends that were sitting abroad, striking and
kicking both men and women, old and young, driving all of us to
prison in a furious and tumultuous manner.
... The authority and minister and some of the people were greatly
offended at our opposing their false worship; for they carried on
their worship in such pride, and so contrary to the Holy Scriptures
that they could no ways defend it by the Scriptures and therefore
took another way to defend it never practised by Christ or any of his
followers. For justice Coit did continually fall upon us when we came
among them and drive us to prison, in an angry and furious manner;
sometimes twenty sometimes thirty in a day, striking and kicking
both men and women, pulling off women’s caps and bonnets and
tearing them to pieces with their hands, setting an example to the
rest of the people; also he made no difference between them that
spoke at the meeting house against their worship and those that did
not speak; for his constant practice was to fall upon all our friends
that came to the meeting house and all that he could see in sight of
the house and drive them to prison, he and his company, in a most
furious and tumultuous manner, stopping their mouths when they
went to speak, choking them etc. Also he doubled our
imprisonments every time we came among them; but this method
he took added no peace to them, for some of our friends were
always coming out of prison, as well as going in, ... However, this
was the method they took, and after this manner they celebrated
their Sabbaths from the 10th of June to the 12th of August.
... February 16. Some of our friends were sitting quietly in the
meeting house, between meetings, and Col. Saltonstall[194] came in
and laid hold of an old man that had the numb palsy, aged 73 years,
and with great violence hauled him out of the seat, setting an
example to others, who fell upon them and drove them out of the
house and to the court house, in a furious manner, and carried them
up through a trap door into a dark garret and locked them in, and at
night a company of their base men got together, among which were
... This base company went into the court house and shut
themselves in and took our friends out of the attic and offered
shameful abuse to our women in the dark.... Now after this shameful
abuse to the women, they took two men and stripped off their
clothes and tied them to a post in the court house and whipped
them in a most unmerciful manner, especially one of them, which
they struck unmerciful blows with a staff and with bunches of rods
on his back, till it was like a jelly, also they rubbed tar into their
wounds and whipped upon the tar, forcing it into their flesh, also
they rubbed tar in the mouths of the men and women when they
went to speak. When these two men were first tied to the post they
sang praises to God, and in the time of their torment they called
upon God to strengthen them. After this, they laid hold on these two
men and forced them to run down near to the town wharf and threw
them into the water several times; also they took their hats and
threw water on them for some considerable time. Moreover, they
threw the women into the water. And after this the sheriff’s eldest
son and another man with him took a poor weakly woman, forty odd
years of age, and forced her to run through the streets till she
dropped down, and then they left her....
Now the next first day of the week, after Col. Saltonstall shut our
friends up in the court house and set his son Dudley and others to
abuse us, it being the 23d of February, we were coming to the
meeting house again, but as soon as we appeared in sight, Col.
Saltonstall run out and met us, and a great company with him, and
fell upon us in a very angry manner, before we had spoke one word,
to drive us to the court house, as he did the week before, when our
friends were sitting quietly in the house between meetings. But as
soon as they fell on us, we spoke and made a great noise, and
refused to go with them, telling them we chose to be killed publickly
before the people, rather than to be murdered privately in the court
house.
Now the tumult grew very great, so that the meeting was broken
up for some considerable time, and they dragged both men and
women on the ground to the court house;[195] some by their hands,
some by their legs, and some by the hair of their heads, striking
them with their fists, kicking them, striking and punching them with
staffs and tearing the clothes from their backs, and they dragged
them into the court house and hauled both men and women up two
pair of stairs, and hauled them up through a trap door into that dark
loft that they had shut our friends up in the week before, and they
locked them in. In this tumult an aged woman was so overcome that
she fainted away and they left her lying on the ground. Now there
were present in this riot justice ——, justice ——, justice ——, the
high-sheriff and Col. ——, besides constables and grandjurymen:
There was also a deacon among them, which makes us write as
follows.
The deacon and the justices
Were busy in this fray,
Church members and grandjurymen
Forgot their Sabbath day.

After the tumult was over, these church members remembered

their Sabbath, and returned to their pretended worship again: But as
soon as that was over, the authority consulted together at the
meeting house, and sent the high-sheriff, who came with a company
of men and took down ten women out of that dark loft that the
authority had shut them up in (two of these women had young
children with them and another was big with child)[196] and
committed them to prison, leaving near twenty small children
motherless at their homes. Now as the high-sheriff was going from
the meeting house, to commit these women to prison, some of the
people of the town asked him what they were going to do with our
friends; the sheriff answered that the women were to be committed
to prison, but he said the men were to be delivered up to Satan to
be buffetted. So the authority kept the men locked up in that dark
garret till night, and then they were delivered up to the authority’s
children and a rude company of young men, who came and
unlocked the trap door and abused our friends in the manner
following: They took down one man first out of this dark loft and
brought him down into the lower room of the court-house, and tied
his hands round a post, also they tied another line to his hands and
hoisted him up by a tackle, then they brought his knees round the
post and tied them with a line, and stripped his clothes up over his
head and tied them also; then they whipped him in a very barbarous
manner by the light of a candle. And when they had done torturing
him, they let him down and shut him up in one of the court house
chambers. They then brought down another out of the garret, and
tortured him after the same manner as they did the first, and then
shut him up also, pretending they would whip them all over again,
except they would recant and promise not to come among them any
more. There were twelve whippers that took turns at the whip, and
commonly three or four to whip one man, one after another. They
pretended to give those men thirty nine stripes each, but they used
several sorts of whips, especially one unmerciful instrument made of
cow-hide, also they whipped them with large rods tied together,
some of which had ten in a bunch, so that they far exceeded thirty
nine stripes, for they struck each person thirty nine times with that
cruel instrument, except one man, which after they had struck him
thirty unmerciful blows, one of the spectators ran and untied him,
telling the whippers he was an old man and they ought to use some
discretion towards him. Nine men were thus used this night, all
heads of families, some of which were elderly men that had great
families of children.
This whipping was executed in a very barbarous manner, for the
rods were trimmed, and long sharp fangs left on them, to tear the
flesh of the sufferers, also these men that whipped our friends
struck them in such a violent manner with these heavy bunches of
rods that they beat and bruised their flesh till it was like jelly.
Moreover some of their wrists were so cut and their sinews so much
hurt with the line they hung by, that several of their hands were
numb for more than two months after. Also the two men that had
been so unmercifully whipped by this company in the court house
the week before, and otherwise abused, were of these men that
suffered that night: And they struck one of these men, he that had
been the most abused the week before, forty three cruel blows on
his old sores, and ten or twelve of these blows were after he had
swooned away. Our persecutors cut these rods upon their Sabbath,
and fitted them at the court house, and Colonel Saltonstall was at
the court house among them when they were preparing the rods....
When their persecutors heard them praying and calling on Christ for
strength, they would threaten them, and whip them with all their
might, endeavoring to make them promise to renounce their
testimony against their worship, but were not able to make one of
them renounce their testimony, or make any promise at all. But the
sufferers told them to this effect, that what they did against their
worship was for no other end but to please God and keep a good
conscience, and that if they should promise to renounce their
testimony God would renounce their souls forever. Also when some
of the men that had suffered this cruel whipping were shut up in the
court house chamber, they prayed earnestly to God to strengthen
their brethren that were to suffer, also they prayed for their
persecutors, for God gave them more than a common love to those
that were tormenting them.
So after these nine men had suffered, they were set at liberty.
Their persecutors threatened them to double their whipping every
time they came to the meeting house among them. And no doubt
they would have gone further, had not God prevented them by
making a division among the people; the neighboring towns crying
out against such barbarous and unlawful behavior; also it was a
common saying among the people that they were sorry their rulers
had resigned up their authority to a company of boys and set them
to defend their worship....

The above is but a small part of such blood-curdling accounts,

filling a good-sized pamphlet. Portions will be found in the “History
of New London,” not quoted here. Near the end is something less
thrilling.

Sept. 14, 1766. Some of our people went and sat down some
distance from the priest’s house, and when he came out to go to
meeting, they walked with him and endeavored to have some
friendly discourse with him concerning the things of God; But the
priest would not talk with them about the things of God. However,
they walked with him and talked to him, but before they came to the
meeting house, justice Coit began to kick them in a furious manner,
especially the women. Also one of the townsmen fell upon them,
punching both men and women with a staff in a cruel manner, so
they were driven by some of the people to the upper end of the
town.

The next first day of the week, being the 21st of Sept., as some of
us were setting by the side of a house, between meetings, about
four or five rods from the priest’s house, saying nothing to any
person, the high-sheriff came, with some assistants and took us and
sent for justice Coit, who came and committed eight men of us to
prison. And on the 26th day of the same month, justice Coit came to
the prison, and we were taken out and brought before him, and he
charged us with disturbing the minister’s peace. We told him we had
no thought of doing the minister any hurt. Justice Coit answered,
that he did not suppose that we intended to strike him or wrestle
with him, nor did he suppose we intended to hurt a hair of his head,
but he supposed that we intended, when the minister came out, to
go along by his side and talk with him. So when justice Coit had
confessed that he did not suppose we intended to hurt a hair of the
priest’s head, he fined us five shillings each, and required bonds of
good behavior towards all his majesty’s subjects; but especially
towards the priest. But we refused to give such bonds, looking upon
the judgment to be very absurd, and that justice Coit’s supposing
that we intended to talk with the priest was not breach of the peace
in us, so he committed seven of us to prison again, all heads of
families, one of which men was in his 75th year. Four of these men
were kept in prison till the 13th of December following, and two
were set at liberty about the 28th of November, and one within a
few days after we were committed to prison.
Now after these men were committed to prison, our friends that
were at liberty thought it necessary that some of our people should
go on the first days of the week and set in the priest’s sight and not
fear them that persecute the body. But when the priest saw them
sitting in sight, if it were but a few women, he would not come out
of his house to go to meeting.... Also this behavior of the priest
occasioned much trouble to his poor flock, for sometimes the bell
would ring and the people sit waiting for their priest till it was time
for meeting to be half done: And then justice Coit, or some of the
rest of his sheep, were obliged to come and move the women out of
the priest’s sight, and guard their shepherd to the meeting house,
lest these women should speak to him of the things of God.
It was almost every day of the first days of the week for the whole
time of this imprisonment, which was near three months, that this
shepherd was kept in his house by the sight of our friends, and
sometimes only at the sight of a few women, and he never ventured
to come out till some of his sheep came and drove the women away.
But justice Coit committed no more of our friends to prison under
bonds of good behavior because he supposed they intended to talk
with the priest, after these men above mentioned. But the 23rd of
November, one of our men told the priest, after he was come out of
the meeting house, that he came to put him in mind how they kept
God’s children in prison, and that their worship was upheld by
cruelty. The priest answered to this effect, that they could uphold it
in no other way. Then the man replied it must certainly be of the
devil, if there was no other way to uphold it but by cruelty. But the
sheriff struck him twice on the head, and punched him with his staff
to prevent his speaking with the priest. And he and three women
were committed to prison, but at night they were set at liberty....
God said, Jer. 1, 7,—“Thou shalt go to all that I shall send thee, and
whatsoever I command thee thou shalt speak.” Also the apostle Paul
exhorteth us to be followers of him as he was of Christ, I Cor. XI. 1.
And Paul spent much time in going from place to place, disputing in
the synagogues on the Sabbath days, as appears in the Acts of the
Apostles. And no doubt they built their synagogues, and thought, as
our neighbors do, that they had a natural right to worship in them
and that the apostle had no right to oppose them in their worship,
for they were as much offended at the apostle as our neighbors are
at us, for they called him a pestilent fellow, and said he was a mover
of sedition throughout the world, Acts XXIV. 5. Also speaking of Paul
and Silas they said, Acts XVII, “These that have turned the world
upside down, are come hither also.”
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