Review

pubs.acs.org/CR

Molecular Design of Benzodithiophene-Based Organic Photovoltaic

Materials
Huifeng Yao,†,‡ Long Ye,†,‡ Hao Zhang,†,‡ Sunsun Li,†,‡ Shaoqing Zhang,† and Jianhui Hou*,†,‡
†
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100190, P. R. China
‡
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

ABSTRACT: Advances in the design and application of highly efficient conjugated

polymers and small molecules over the past years have enabled the rapid progress in the
development of organic photovoltaic (OPV) technology as a promising alternative to
conventional solar cells. Among the numerous OPV materials, benzodithiophene
(BDT)-based polymers and small molecules have come to the fore in achieving
outstanding power conversion efficiency (PCE) and breaking 10% efficiency barrier in
the single junction OPV devices. Remarkably, the OPV device featured by BDT-based
polymer has recently demonstrated an impressive PCE of 11.21%, indicating the great
potential of this class of materials in commercial photovoltaic applications. In this
review, we offered an overview of the organic photovoltaic materials based on BDT from
the aspects of backbones, functional groups, alkyl chains, and device performance, trying
to provide a guideline about the structure-performance relationship. We believe more exciting BDT-based photovoltaic materials
and devices will be developed in the near future.

CONTENTS 5.2. Electron-Withdrawing Units used in the

Backbone of BDT-Based Photovoltaic Small
1. Introduction 7397 Molecules 7439
2. Synthesis of BDT Units 7398 5.3. Photovoltaic Small Molecules Based On BDT
3. Design Strategies Used in BDT-Based Photovoltaic Derivatives 7441
Materials 7400 6. Application of BDT-Based Polymer Donors in
3.1. Backbone Modulation 7400 Fullerene-Free PSCS 7441
3.1.1. D−A Combination 7400 7. Summary and Outlook 7444
3.1.2. π-Bridges 7403 Author Information 7445
3.1.3. Terpolymers 7406 Corresponding Author 7445
3.1.4. Regioregular Structures 7408 Notes 7445
3.2. Flexible Side Chains Optimization 7409 Biographies 7445
3.2.1. Alkyl Chain Configuration 7409 Acknowledgments 7445
3.2.2. Alkyl Chain Substitution Positions 7410 References 7445
3.2.3. Functional Side Chains 7410
3.3. Functional Substitutions 7410
3.3.1. Electron-Withdrawing Substitutions 7411
3.3.2. Electron-Donating Substitutions 7413 1. INTRODUCTION
3.4. Two-Dimensional Conjugated Benzodithio- Organic semiconductors have received considerable attention
phene (2D-BDT) 7413 from both the academic and industrial communities due to their
4. BDT-Based Photovoltaic Copolymers 7416 numerous applications, which include light-emitting diodes,
4.1. Copolymers Based On BDT and TT 7416 field-effect transistors, photodetectors, nonvolatile memory,
4.2. Copolymers Based On BDT and BT 7418 batteries, supercapacitors, solar cells and thermoelectric
4.3. Copolymers Based On BDT and TPD/BDD 7423 generators.1−3 In particular, organic solar cells or so-called
4.4. Copolymers Based On BDT and Qx 7427 organic photovoltaics (OPVs) have the potential for harnessing
4.5. Copolymers Based On BDT and DPP/IID 7429 low-cost solar energy due to their advantages in materials and
4.6. Copolymers Based On BDF or DTBDT 7430 manufacturing processes.4 The efficiency of converting the input
5. BDT-Based Photovoltaic Small Molecules 7437 solar power (Pin) to electric power is defined as the power
5.1. Side Chain Engineering of BDT-Based Photo- conversion efficiency (PCE) (PCE = VOC × JSC × FF/Pin), which
voltaic Small Molecules 7437
Received: March 15, 2016
Published: June 2, 2016

© 2016 American Chemical Society 7397 DOI: 10.1021/acs.chemrev.6b00176

Chem. Rev. 2016, 116, 7397−7457
Chemical Reviews
Figure 1. Schematic of a typical OPV and the basic relationships between material properties and photovoltaic parameters.
is directly proportional to three parameters: open-circuit voltage
(VOC), short-circuit current density (JSC), and fill factor (FF)
under standard solar irradiation (AM 1.5G 100 mW/cm2). In
1986, Tang et al. demonstrated the first breakthrough in the OPV
field by inventing bilayer OPV devices.5 Until 1995, Heeger and
Friend demonstrated the bulk heterojunction (BHJ) concept in
OPVs using polymer:fullerene and polymer:polymer blends,
respectively, in which the donor/acceptor interface area was
considerably enlarged and nanoscale pathways for charge
generation and transport could be formed.6,7 In a typical BHJ
OPV device, a heterojunction consisting of a p-type organic
donor and an n-type organic acceptor is the photoactive part for
converting solar light to electricity (Figure 1). Thus far, the PCEs
of single, double, and triple heterojunction OPV devices using
conjugated polymers as the donors and fullerene derivatives as
the acceptors have surpassed 10.5%,8−13 11%,14 and 11.5%,15,16
respectively. The design, synthesis, and application of novel
organic materials with superior photovoltaic properties play vital
roles in improving the PCEs of these OPV devices.
For a highly efficient BHJ OPV, its active layer should possess
the following intrinsic features: (a) a broad absorption spectrum
with a high extinction coefficient to utilize more solar photons;
(b) a bicontinuous network with nanoscale phase separation to
facilitate exciton diffusion and charge separation; (c) a suitable
molecular energy level alignment between the highest occupied
molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) levels to afford a sufficient driving
force for efficient charge separation with minimum energy loss;
and (d) a high charge mobility to facilitate charge transport.17−25
On the basis of these requirements, the chemical structures
and distinct properties of the organic molecules should be finely
tuned. In 2008,26 the benzo[1,2-b:4,5-b′]dithiophene (BDT)
unit was first used in the synthesis of photovoltaic polymers and
became one of the most successful building blocks in the
synthesis of highly efficient photovoltaic materials, which have
been proven to match the above requirements well.27−29 The
rigid and planar conjugated structure of BDT makes it attractive
for achieving highly tunable molecular energy levels and optical
band gaps as well as high hole mobilities. In recent years,
hundreds of photovoltaic polymers and small molecules have
been developed using BDT or its analogues as building blocks.
Although there is still a lack of standard procedures for the
fabrication and measurement of OPV devices,30−34 OPV devices
with BDT-based materials achieved several record PCEs certified
by the National Renewable Energy Laboratory (NREL) or other
well-recognized institutes. As illustrated in Figure 2, the
photovoltaic performance of OPV devices with BDT-based
small molecules or polymers kept pace with the development in
the field of OPVs. Therefore, summarizing the critical achieve-
ments in BDT materials will provide a general guideline for the
7398
Review
Figure 2. Advances in the PCEs of single junction OPVs based on BDT
polymers (red line/red ●) and small molecules (blue line/blue ■)
reported in the literature over the past few years; the black line/▲
signifies the data from the NREL Web site showing the cell efficiency
records for OPVs based on all types of organic materials.
molecular design strategies of high-performance photovoltaic
materials.
In this review, we aim to summarize the molecular design
strategies, chemical structures, and photovoltaic properties of
BDT-containing conjugated polymers and small molecules
developed over the past few years. First, the general synthesis
routes of BDT units and polymers are presented. Second, the
design strategies, including backbone modulation, side chain
optimization, and functional substitutions, are summarized and
discussed with several representative examples. Third, a wide
range of BDT-based polymers and small molecules are
introduced by category, and certain representative materials are
highlighted in detail. Then we present a short review about the
versatile application of BDT-based polymers, particularly the
emerging fullerene-free PSCs. Lastly, after a brief summary of the
developments in all aspects, several fundamental challenges and
future prospects of this class of materials are proposed.
2. SYNTHESIS OF BDT UNITS
In the early 1980s, BDT-based molecules had already been
synthesized and their electrical conducting properties had been
studied.35,36 Afterward, several organic molecules containing
BDT units were developed and applied in organic field effect
transistors (OFETs). For example, in 1997, Dodabalapur and co-
workers reported a dimer-BDT molecule and achieved a hole
mobility of 0.04 cm2 V−1 s−1 in an OFET device.37 Xu et al.
improved the hole mobility of a BDT-based polymer to 0.25 cm2
V−1 s−1 in 2007, which was one of the top values for polymer-
based OFETs.38
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Chemical Reviews
Figure 3. BDT units with different substitutions.
Scheme 1. Common Synthetic Procedures for the BDT Monomers: (i) Oxalyl Chloride; (ii) Diethylamine; (iii) n-Butyllithium
then Water; (iv) Alkyne Lithium; (v) SnCl2, HCl; (vi) Pd/C, H2; (vii) Zn, NaOH, H2O; (viii) Bromoalkane, TBAB; (ix) Aromatic
Lithium; (x) n-Butyllithium, Chlorotrimethylstannane or 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; and (xi) Pd-
Catalyst
In 2008, Hou and Yang et al. first introduced BDT units in the
design of photovoltaic polymers, and the optical and electronic
properties of the BDT-based polymers could be easily tuned,
suggesting that BDT was a promising unit for conjugated
photovoltaic polymers.26 Over the years of investigations, a series
of BDT units have been developed by incorporating different
substituents in the central benzene core, such as alkyl, tri-iso-
propylsilylethynyl, alkoxy, alkylthio, aromatic groups, etc.
(Figure 3), and different synthetic routes were developed in
various studies.27,39,40 In this section, the general synthesis
methods of the commonly used alkyl-, alkoxy-, and aromatic-
substituted BDT units are introduced.
As depicted in Scheme 1, the intermediate of benzo[1,2-b:4,5-
b′]dithiophene-4,8-dione played a vital role in the synthesis of
BDT units with different substitutions, which could be easily
prepared in three steps. Starting with thiophene-3-carboxylic
acid, thiophene-3-carbonyl chloride could be obtained using
either thionyl chloride or oxalyl chloride. Then, the amino
compound could be prepared through an amination reaction
with diethyl amine, and the product could be purified by
distillation. Subsequently, the benzo[1,2-b:4,5-b′]dithiophene-
4,8-dione was obtained via a reaction between the amide and n-
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butyllithium in tetrahydrofuran (THF) at 0 °C followed by
recrystallization from acetic acid. The yield of the first two steps
was approximately 90%, and the last step yielded 75%.
Alkyl-substituted BDT units could be synthesized in three
steps from benzo[1,2-b:4,5-b′]dithiophene-4,8-dione. First, the
dione was reacted with alkynyl lithium or alkynyl magnesium
halide to form the diol compound, which could be reduced by
SnCl2 to produce alkynyl-substituted BDT. Subsequently, the
alkyl-substituted BDT could be obtained via catalytic hydro-
genation with the assistance of Pd. When the alkynyl lithium was
replaced by aromatic lithium, similar procedures were performed
to prepare the aromatic-substituted BDT units. The alkoxy-
substituted BDT could be synthesized by a one-pot two-step
reaction. First, the dione compound was reduced to diol using
zinc in a sodium hydroxide solution. Then, an excessive amount
of alkyl bromide was added along with a small amount of KI
(potassium iodide) and tetrabutylammonium bromide (TBAB),
which was used as a catalyst. The alkoxy-substituted BDT could
be easily purified by recrystallization or silica gel column
chromatography at a yield of approximately 70%−90%. Stille
coupling and Suzuki coupling were the two most popular
reactions used to prepare the conjugated photovoltaic materials;
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Chemical Reviews
hence, BDT boronic acid ester compounds and stannanes were
needed for reactions with n-butyllithium followed by the addition
of chlorotrimethylstannane or 2-isopropoxy-4,4,5,5-tetramethyl-
1,3,2-dioxaborolane.
3. DESIGN STRATEGIES USED IN BDT-BASED
PHOTOVOLTAIC MATERIALS
The development of a highly efficient OPV device has always
been accompanied by innovations in device architecture, fine-
tuning of blend morphology, and application of interface
engineering. In addition to the methods mentioned above, the
design of new photovoltaic materials is one of the driving forces
to improve the PCE to over ∼10%. Because the three parameters,
VOC, JSC, and FF, of OPV devices have close relationships with
each other, to obtain a high PCE, molecular design strategies
should be carefully considered to achieve a simultaneous
improvement in these parameters. Over the past few decades,
thousands of organic conjugated materials have been developed
and applied in OPVs. Subtle variations in the molecular
structures of conjugated molecules lead to significant changes
in the photovoltaic properties. Therefore, understanding the
relationship between molecular structure and photovoltaic
performance remains a challenge. In this section, we will use
BDT-containing polymers as an example to summarize the
molecular design strategies for polymer solar cell (PSC)
applications, such as backbone modulation, side chain
optimization, and functional substitutions. Additionally, creating
BDT with two-dimensional side groups can be considered a
feasible and efficient method to optimize the photovoltaic
performance of the resulting conjugated polymers. Thus, the
correlation between the molecular structure of the conjugated
molecule and the photovoltaic performance of the OPV device
can be determined.
3.1. Backbone Modulation
The conjugated backbone (Figure 4) of the copolymer
determines the fundamental properties of the resulting polymer,
Figure 4. Typical molecular structure of a photovoltaic polymer.
such as the absorption spectra and the molecular energy levels.
Over the past decade, photovoltaic polymers based on different
donor−acceptor (D−A) combinations have been developed to
realize well-balanced broad absorption spectra and appropriate
energy levels. In addition, π-bridges, such as thiophene, furan,
thieno[3,2-b]thiophene, etc., have been widely used to further
optimize the backbone conformation for better photovoltaic
performance, and extended π systems were also designed for the
same purpose. Recently, terpolymers (i.e., ternary component
polymers) with three components were developed by
researchers for a broad absorption spectrum and a higher
photovoltaic efficiency.41 Furthermore, the regioregularity of the
D−A polymers with asymmetric units played important roles in
effecting their photovoltaic performance.42−44
3.1.1. D−A Combination. In early studies on photovoltaic
polymers, researchers focused their attention on homopolymers,
such as MEH-PPV45 and P3HT,46 which played significant roles
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in the development of polymer solar cells. However, these
materials typically delivered relatively low PCEs, and further
improvement was limited by their poor absorption properties
and fixed HOMO levels, which restricted the JSC and VOC of the
solar cell devices. D−A copolymerization is one of the most
successful methods for designing high-efficiency photovoltaic
polymers because the optical and electronic properties can be
tuned easily by controlling the intermolecular charge transfer
(ICT) from the donor to the acceptor.47 The D−A alternating
approach is also called push−pull method, and the electron
density of the polymer always has a rearrangement from D to A.
This class of polymer often demonstrates a resonance form
between −D−A− and −D+−A+−, increasing the double-bond
character of the single bonds in the polymer backbone, thus
affecting the absorption and molecular energy properties.3 The
narrowed bandgap of D−A copolymer can be easily understood
using molecular orbital theory (Figure 5). The initial orbitals of
Figure 5. Molecular orbital hybridization of the D−A copolymer.
the donor and acceptor experience a rearrangement during the
formation of the covalent bond between the two moieties. The
energy level of one of the of the newly occupied molecular
orbitals is higher than the initial HOMO level, and the energy
level of one of the unoccupied molecular orbitals is lower than
the LUMO level before combination, which results in a narrowed
bandgap. In 2003, Andersson and co-workers reported an
alternating copolymer based on benzothiadiazole and fluorene,
which exhibited a considerable PCE of 2.2%.48 Afterward,
numerous photovoltaic polymers with D−A structures were
designed and applied in polymer solar cells, and a few of the D−A
copolymers achieved milestone PCEs in the development of
PSCs.
In 2008, a series of copolymers based on BDT unit were
synthesized by copolymerizing with different acceptors.26 As
depicted in Figure 6, the new BDT-containing polymers with
different acceptor units provide an excellent example of the
optimization of the polymer backbone via varied D−A
combinations. When different acceptors, such as thiophene,
benzothiadiazole (BT), thieno[3,4-b]pyrazine (TPz), etc., were
used in the copolymers, the bandgaps and molecular energy
levels of these BDT-based polymers were tuned effectively. The
absorption edges of these polymers ranged from 600 to 1100 nm,
the corresponding optical bandgaps ranged from 2.1 to 1.1 eV,
and the HOMO levels could be tuned from −4.56 to −5.16 eV
(Table 1). Although the PCEs of the PSC devices based on
fullerene derivates (without special instructions, the PSC devices
were fabricated by fullerene derivates) were very low, this study
provided an effective method to modulate the bandgap and the
molecular energy level of the photovoltaic polymer by selecting
different D−A combinations.
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Chemical Reviews Review

Figure 6. D−A copolymers P1−P8 based on BDT and varied acceptor units.

Table 1. Summary of the Optical and Electronic Properties as well as the Device Performances of P1−P8
polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P1 2.13 −5.16 − − − − 26
P2 2.03 −5.07 0.56 1.16 38 0.25 26
P3 2.06 −5.05 0.75 3.78 56 1.60 26
P4 1.97 −4.56 0.37 2.46 40 0.36 26
P5 1.63 −4.78 0.60 1.54 26 0.23 26
P6 1.70 −5.10 0.68 2.97 44 0.90 26
P7 1.05 −4.65 0.22 1.41 35 0.11 26
P8 1.52 −4.88 0.55 1.05 32 0.18 26

Figure 7. Molecular structures of P9−P14.

Table 2. Optical, Electronic, and Photovoltaic Performances of P9−P14

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P9 1.6 −5.15 0.74 14.5 68.97 7.4 55
P10 1.75 −5.45 0.92 14.5 64 9.4 70
P11 1.8 −5.56 0.85 9.81 66 5.5 73
P12 1.8 −5.23 0.86 10.68 72.27 6.67 76
P13 1.73 −5.35 0.90 13.52 70.07 8.55 82
P14 1.44 −5.30 0.73 14.0 65 6.6 86

Combined with various acceptors, the BDT-containing
polymers with suitable absorption spectra and molecular energy
levels possess the potential to obtain high-efficiency PSC devices,
and many impressive PCEs have been achieved by several
research groups. Figure 7 summarizes the copolymers based on
BDT units and some acceptor units, and their basic optical and
electronic properties as well as photovoltaic performances are
listed in Table 2.
Thieno[3,4-b]thiophene (TT) units are known for their
stabilized quinoidal structures, which have wide applications in
designing low bandgap polymers.49−52 Yu et al. developed the
7401
ester-substituted TT unit and used it as an acceptor building
block to copolymerize with the BDT units, thus preparing a
series of copolymers based on BDT and TT.53,54 TT units with
fluorine atom modification have become popular units in high-
performance polymers. P9 (known as PTB7) was one of the
most studied donor materials developed in 2010, and numerous
impressive device results were achieved using this polymer. P9
has a strong absorption from 550 to 750 nm, and the cyclic
voltammetry (CV) measurement indicated that the introduction
of the fluorine atom in PTB7 decreased its HOMO and LUMO
to −5.15 and −3.31 eV, respectively.55,56 Using [6,6]-phenyl C61
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Chemical Reviews
butyric acid methyl ester (PC61BM) or [6,6]-phenyl C71 butyric
acid methyl ester (PC71BM) as the acceptor material in BHJs,
they fabricated conventional solar cell devices with an ITO/
PEDOT:PSS/P9:PCBM/Ca/Al structure to investigate their
photovoltaic properties, and either dichlorobenzene (DCB)/
diiodooctane (DIO) or chlorobenzene (CB)/DIO was used as
processing solvents comparatively for a better BHJ morphology.
After optimization of the devices, the device using PC71BM as an
acceptor material and CB/DIO as a processing solvent yielded an
impressive PCE of 7.4% with a VOC of 0.74 V, a JSC of 14.50 mA/
cm2, and an FF of 68.97%. Impressively, Cao and co-workers
improved the PCE of the P9-based device to 9.2% by applying an
inverted device structure and new interface material.57 In
addition to P9, the combination of BDT and TT units yielded
several high-performance copolymers, such as PBDTTT-C-T,58
PBDT-TS1,59 PTB7-Th,60 etc. For instance, when the alkoxyl
side chains on BDT were replaced by the 2D conjugated thienyl
side chains, the resulting polymer PTB7-Th showed very
impressive photovoltaic performance and became one of the
most studied polymers. The achievements of these polymers are
highlighted by a recent review.61
2,1,3-Benzothiadiazole (BT) is one of the strongest acceptor
units used in D−A copolymers, and several conjugated polymers
have been developed by combining it with different donor units,
such as carbazole,62−64 2,7-silafluorene,65 cyclopenta[2,1-b;3,4-
b′]dithiophene,66 dithdithienosilole,67 and indacenodithio-
phene.68 In addition to the polymers mentioned above,
copolymers based on BDT and BT units were commonly
studied due to their outstanding photovoltaic performances.69
For example, Jones et al. reported the P10 polymer in 2014, and
the influence of the molecular weight on the photovoltaic
performance was studied.70 A UV−vis measurement indicated
that P10 possessed an absorption edge of approximately 710 nm,
thus indicating an optical bandgap of 1.75 eV; furthermore, its
HOMO and LUMO levels were −5.45 and −3.65 eV,
respectively, which were measured using CV measurement.
Inverted PSC device architectures using ZnO as an interface layer
were first fabricated to investigate their photovoltaic perform-
ance, and a high PCE of 8.5% was achieved with a VOC of 0.92 V, a
JSC of 14.5 mA/cm2, and an FF of 64% when the number-average
molecular weight of P10 increased to 112 kDa. Then, the ZnO
layer was modified by fullerene, thus resulting in a higher PCE of
9.4%. Because of its excellent photovoltaic properties, studies on
the PBDT-BT family of copolymers can provide insight into the
rules for designing high-efficiency photovoltaic polymers.
A thienopyrroledione (TPD) unit possesses a simple
symmetric planar structure with an alkyl-substituted imide
fused on thiophene. The imide provides the unit with a relatively
strong electron-withdrawing property, and the solubilities of
polymers based on TPD can be tuned by introducing different
alkyl chains on the pyrrole ring. In 2010, n-alkylthieno[3,4-
c]pyrrole-4,6-dione (TPD) was simultaneously developed and
applied as a building block for organic photovoltaic materials by a
few research groups.71−74 They synthesized the copolymers
using BDT as the donor units, which yielded good PCEs of
approximately 4%−7%. For example, Leclerc and co-workers
synthesized the P11 polymer with branched 2-ethylhexyl on
BDT and linear octyl on TPD, which possessed an absorption
edge of 685 nm (optical bandgap 1.8 eV), and the HOMO and
LUMO were estimated to be −5.56 and −3.75 eV, respectively,
which were measured by the CV.73 The number-average weight
was measured as 13 kDa using high-temperature size-exclusion
chromatography. When a device structure of ITO/PE-
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DOT:PSS/P11:PC71BM/LiF/Al was used to investigate the
photovoltaic performance of P11, a VOC of 0.85 V, a JSC of 9.81
mA/cm2, and a FF of 66% were obtained with an active area of
1.0 cm2, resulting in a PCE of 5.5%. Driven by the further
improvement in the PCE, Beaujuge and co-workers carefully
optimized the alkyl chains on BDT and TPD due to their
considerable effect on photovoltaic properties.75 Lastly, the
PBDT-TPD polymer with a branched 2-ethylhexyl on BDT and
linear heptyl on TPD provided the best PCE of 8.5%, with a VOC
of 0.97 V, a JSC of 12.6 mA/cm2, and an FF of 70%.
The P12 copolymer, which is based on BDT and benzo-[1,2-
c:4,5-c′]dithiophene-4,8-dione (BDD), was developed by Hou
and co-workers in 2012.76 Two clear absorption peaks could be
observed in the P12 film. One of the peaks, located at 622 nm,
could be ascribed to the interchain π−π* transition of the
molecular π−π stacking. Furthermore, the strong π−π stacking
absorption peak was observed in the solution state at ambient
temperature, and the absorption intensity decreased when the
temperature increased, suggesting that strong aggregation
occurred in the solution at low temperatures, which was proven
to have a significant influence on the photovoltaic performance
of the corresponding PSC device. Using PC61BM as an acceptor
material, an optimal PCE of 6.67% with a high FF of 72% was
achieved by manipulating the processing temperature. The
photovoltaic efficiency of the PBDT-BDD was further improved
to 8.75% when a novel cathode interface layer of a-ZrAcac was
used in the device.77
Due to its two strong electronegative nitrogen atoms,
quinoxaline (Qx) is a typical electron-deficient unit, and several
conjugated D−A copolymers based on Qx or its derivatives were
developed and applied in PSC devices.78−80 Because there are
two fused six-member rings in Qx, the Qx-containing D−A
polymers should have less quinoid properties.81 The absorption
edge of P13 was located at 716 nm, and the polymer had a deep
HOMO level of −5.35 eV.82 When this polymer was used to
fabricate the PSC devices, a PCE of 8.55% with a VOC of 0.90 V, a
JSC of 13.52 mA/cm2, and an FF of 70.02% was achieved. Because
PBDT-Qx had good solubility in several common solvents, when
a green solvent known as anisole was used as a processing solvent
to fabricate the cell device, the PSC device yielded an excellent
PCE of 8.37%, thus demonstrating its potential in large-scale
productions.83
Diketopyrrolopyrrole (DPP) was first developed by Farnum
and co-workers with a diphenyl-DPP structure in 1974.84
Afterward, the DPP units were widely used to construct high
mobility organic molecules for OFETs. In recent years, the DPP
units were developed to construct photovoltaic polymers due to
their strong electron-deficient properties. Copolymers based on
BDT and DPP always have narrow optical bandgaps of
approximately 1.45 eV and HOMO levels at −5.29 eV.85 Hou
and co-workers synthesized P14 with different alkyl side chain on
DPP and achieved similar results.85 In Yang’ group, a better PCE
of 6.6% with a VOC of 0.73 V, a JSC of 14.0 mA/cm2, and an FF of
65% was recorded for P14-based PSC device.86 Because of their
broad absorption spectra, the PBDT-DPP polymers were good
candidates for tandem solar cells. Using P3HT/ICBA as the front
cell and PBDT-DPP/PC71BM as the rear cell, an inverted
tandem polymer solar cell was fabricated by Yang and co-
workers, which achieved a high PCE of 8.6% with a VOC of 1.56
V.87
Due to the development of D−A copolymers, the PCE of the
PSCs have been improved to over 10%. The D−A structure has
become a standard model for designing photovoltaic polymers,
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Chemical Reviews Review

Figure 8. Modulation of molecular conformation via fused or linked thiophene units.

Table 3. Optical, Electronic, and Photovoltaic Performances of P15−P23

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P15 1.61 −5.29 0.81 12.27 61.98 5.93 88
P16 1.59 −5.21 0.73 16.63 64.13 7.79 88
P17 1.59 −5.04 0.69 16.35 66.3 7.48 89
P18 1.67 −5.22 0.76 5.32 42.31 1.71 90
P19 1.72 −5.24 0.79 13.56 69.10 7.4 90
P20 1.70 −5.29 0.72 10.12 60.0 4.37 91
P21 1.79 −5.27 0.96 9.10 51.8 4.9 92
P22 1.73 −5.09 0.80 11.83 66.6 6.3 93
P23 1.69 −5.40 0.79 11.9 50 4.7 92

and several novel donor and acceptor units have been developed
as building blocks to construct D−A polymers. Although certain
D−A copolymers already have excellent properties, many of
them need further optimization. Therefore, to enhance the
photovoltaic performance of D−A copolymers, π-bridges,
terpolymers and regioregular structures were developed to
optimize the backbone of the polymers.
3.1.2. π-Bridges. Generally, π-bridges are chromophores
with small sizes, which are widely used to modulate the
backbones of conjugated molecules. Inserting a π-bridge between
the donor and acceptor units will affect the conformation of the
conjugated molecule chain, thus resulting in a change in the
optical absorption, molecular energy levels, hole mobility, as well
as the blend morphology with the acceptor material, which are all
related to the photovoltaic performance of PSC devices.
Therefore, it is important to optimize the polymer conformation
by rationally selecting the π-bridge (e.g., thiophene, furan,
selenophene, benzene, or thieno[3,2-b]thiophene). Besides the
π-bridge units linked by single bonds, a few extended fused π-
systems, such as dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]-
dithiophene (DTBDT), which has two fused thiophene units
in addition to the BDT, were also developed to tune the
backbone of the polymer. Numerous outstanding photovoltaic
polymers were designed via the structural optimization of π-
bridges in different D−A combinations. Figure 8 summarizes
some copolymers based on BDT units and some acceptor units,
7403
and their basic optical and electronic properties as well as
photovoltaic performances are listed in Table 3.
Considering the connecting angle between the conjugated
units, the backbones of conjugated polymers are usually one of
two types, zigzagged or straight; these structures have
considerable influences on the crystalline properties of the
polymers. For instance, Hou et al. synthesized the conjugated
polymer P15, which had a zigzagged backbone with an included
angle of 36°.88 The grazing incident X-ray diffraction (GIXRD)
measurement indicated a weak (010) reflection peak at 1.62 Å−1,
which corresponded to a π−π stacking distance of 3.88 Å. Then,
they modulated the zigzagged-backbone conformation of the
polymer to a straight linear molecular structure via fused
thiophene units near the BDT, and the new P16 polymer
indicated a stronger and closer π−π stacking compared to P15.
The impact of the molecular conformation on the interchain
aggregation could be interpreted by the varied packing modes
existing in different conformations. In the zigzagged-backbone
type, the ordered interchain packing only formed under the
favorable mode, whereas the straight linear molecule had only
one general packing mode. Because of the optimized molecular
conformation, the PSC devices based on P16 resulted in a high
PCE of 7.79% without using any additives whereas the P15 had a
relatively low PCE of 5.93% after the optimization of DIO.
Incorporating π-bridges in the backbone of the conjugated
polymer via a single bond is another simple method used to tune
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Figure 9. Molecular structures of P24−P35 with varied π-bridges.
the molecular conformation. Compared with P15, the new P17
polymer with thiophene bridges also possessed a straight linear
conformation, and the π−π stacking distance of P17 was
measured to be 3.51 Å, which was one of the smallest values for
conjugated polymers.89 The devices based on P17 achieved a
high PCE of 7.81%. Both the interchain packing of the
conjugated polymer as well as the absorption properties and
molecular energy levels will be affected by the change in the
backbone conformation. As observed in the two examples
mentioned above, the P16 and P17 polymers, with closer
molecular stacking distances, had red-shifted absorption spectra
and upshifted HOMO levels. Therefore, a comprehensive
investigation should be performed when designing a novel
photovoltaic polymer by inserting π-bridges.
Furthermore, the conformation of the molecular backbone has
a considerable influence on the hole mobility for conjugated
polymers, which affects the transport of the carriers. For instance,
although P18 and P19 have similar HOMO levels and absorption
ranges, the PSC devices based on them indicated significant
differences in the photovoltaic performance.90 A high PCE of
7.4% was obtained for the P19-based PSC device, whereas a low
PCE of 1.77% was achieved for the P18-based PSC device. The
EQE of the P19-based device was as high as 71%, whereas P18
had an extremely low EQE of 29%, suggesting a large difference
in the generation and transport of the charge carriers. The
introduction of thiophene relieved the direct electron
communication between the BDT and TT units, which caused
a change in the absorption coefficient and hole mobility of the
polymer. As observed by the UV−vis and the using density
functional theory (DFT) calculation, the P19 polymer with the
thiophene π-bridge possessed a higher absorption coefficient
7404
Review
than P18 without the thiophene unit. The hole mobility of the
two polymer blends with PC71BM were measured using the
SCLC method, and the result suggested that the mobility of the
P19 blend was 4 orders of magnitude higher than that of the P18,
which resulted in the fast recombination of the carriers existing in
the P18-based device. Li et al. introduced the thieno[3,2-
b]thiophene as the bridge in the backbone of PBDT-BT, and a
high hole mobility of 0.38 × 10−2 cm2 V−1 s−1 was obtained from
the OFET device fabricated using the new P20 polymer.91 The
different molecular backbone conformations of the polymers
always affect the morphologies of the blends when mixed with
the acceptors. As previously discussed, in comparison with the
P21 polymer with the zigzagged backbone conformation, P23,
which had a straight linear structure, had a different morphology
when blended with PC71BM.92 The AFM and TEM images
indicated that a large and regular molecular aggregation of the
P23 was formed in the blend because the polymer had a straight
linear backbone conformation. Heteroatom replacement is
another effective strategy commonly used in designing highly
efficient photovoltaic polymers, and the subtle modification of
the polymer backbone using this method could often cause
significant changes in the optical and electronic properties for the
resulting material. As a homologue of thiophene, selenophene is
often used to optimize the optical and electronic properties of the
conjugated polymers. The relatively low aromaticity of
selenophene will enhance its ground state quinoid resonance
character; thus, Se-containing polymers generally have broad
absorption spectra. The absorption edge of the P22 polymer
extended to 732 nm compared to 692 nm for P21.93 Hence, the
absorption properties, hole mobility, and morphology of the
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Table 4. Optical, Electronic, and Photovoltaic Performance of P24−P35

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P24 1.46 −5.30 0.73 13.7 65 6.5 96
P25 1.49 − 0.63 13.9 55 4.8 97
P26 1.43 −5.05 0.63 16.25 6.18 6.18 85
P27 1.51 −5.26 0.77 10.9 56 4.7 96
P28 1.38 −5.25 0.69 16.8 62 7.2 96
P29 1.70 −5.47 0.78 3.73 52 1.52 101
P30 1.77 −6.00 0.84 9.18 67 5.30 102
P31 1.71 −5.90 0.82 10.87 59 5.29 102
P32 1.88 −5.56 0.87 7.2 58 3.6 103
P33 1.84 −5.39 0.81 6.11 67 3.30 104
P34 1.82 −5.47 0.88 9.30 68 5.55 104
P35 1.89 −5.42 0.83 10.60 65 5.77 104

Figure 10. Molecular structures of the terpolymers P36−P43.

conjugated photovoltaic polymers could be tuned effectively by
selecting appropriate π-bridges.
In addition to the examples mentioned above, π-bridges such
as thiophene, furan, selenophene, and thieno[3,2-b]thiophene
are widely used to tune the photovoltaic performances of
conjugated polymers with varied D−A structures, such as PBDT-
DPP, PBDT-Qx, and PBDT-TPD (Figure 9 and Table 4).
Thiophene is one of the most common π-bridges used in DPP-
containing polymers, and PDPP3T achieved a PCE of 6.71%
after the optimization of the blend morphology.94 The polymers
based on 2D-BDT and DPP using thiophene as the π-bridge
were developed by several research groups, and PCEs of
approximately 3−7% were achieved.85,86,95,96 Additionally,
bithiophene and thienothiophene were developed as π-bridges
in the backbone of PBDT-DPP copolymers.85,97 In 2010, Frechet
7405
et al. inserted a furan unit into the backbone of the DPP-
containing polymer PDPP2FT, which demonstrated improved
solubility when compared with the PDPP3T polymer containing
the thiophene unit.98 Then, Ma and co-workers developed
conjugated polymers based on a 2D-BDT and furan-DPP unit,
and the new P27 polymer depicted a blueshifted absorption
spectrum and a downshifted HOMO level when compared with
its thiophene equivalent.99 Then they synthesized a series of
furan-bridged polymers to further investigate the influence of
furan bridge on the photovoltaic performance of polymers by
incorporating BT, TPD, and DPP as acceptor units, and PCE
around 5% were obtained in the PSC devices.100 Replacing
thiophene with selenophene in the conjugated backbone always
results in a broad absorption spectra and improved charge
transport properties for conjugated polymers. The P28
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Table 5. Optical, Electronic, and Photovoltaic Performances of P36−P43
polymer x Egopt (eV) HOMO (eV)
P36 0.5 1.60 −5.20
P37 0.25 1.52 −5.47
P38 0.2 1.8 −5.39
P39 0.5 1.34 −5.32
P40 0.25 1.40 −5.35
P41 1 1.61 −5.28
P42 0.25 1.57 −5.08
P43 0.025 1.66 −5.25
copolymer based on selenium-substituted DPP and BDT was
designed and synthesized by Yang and co-workers, and the new
polymer showed an absorption spectrum that is red-shifted by
nearly 50 nm compared with P24.96 Furthermore, the HOMO
level of P28 increased to −5.25 from −5.30 eV for P24. Due to
the P28 copolymer’s advantage of a broad absorption spectrum,
the PSC device resulted in a high JSC of 16.8 mA/cm2, whereas
P24 had a JSC of 13.7 mA/cm2. Benzene-DPP was developed at
an early stage; when the benzene unit was used in the backbone
of the conjugated polymer P29, its absorption spectrum was
blueshifted compared with its thiophene equivalent.101 When
thienothiophene was used as the π-bridge in the backbone of
PBDT-DPP, the P26 polymer had a red-shifted absorption
spectrum compared to P24 for its extended π conjugation.85
Furthermore, thiophene and thienothiophene were used as π-
bridges to optimize the structures of the copolymers based on
BDT and Qx, and the same trends in the absorption spectra and
molecular levels were observed (i.e., the more planar and linear
molecular structure of the thienothiophene-containing polymer
possessed a narrowed optical bandgap but increased HOMO
level compared to the thiophene-containing polymer).102 After
the reported results of the conjugated polymer PBDT-TPD,
Leclerc and co-workers used thiophene as π-bridges to further
optimize the physical-chemical properties of the polymers, and
the influence of alkyl chains on the π-bridge was also studied.103
However, due to the poor morphology of the new polymers, they
did not achieve a good photovoltaic performance. In addition to
the thiophene unit, bithiophene and thienothiophene were also
used as π-bridges in the backbones of the PBDT-TPD polymers.
Yang and co-workers designed and synthesized a series of P33−
P35 copolymers using these different π-bridges, and the PSC
devices based on these polymers achieved varied PCEs of 3%−
8%, suggesting the considerable influence of π-bridges on the
photovoltaic properties for the conjugated polymers.104 Because
π-bridges have a significant effect on the properties of the
photovoltaic polymers, a comprehensive investigation should be
performed when selecting one suitable π-bridge for its unique
characteristics. The optimization of the backbone of the
conjugated polymers through π-bridges will yield more highly
efficient photovoltaic polymers.
3.1.3. Terpolymers. Along with the great success of the D−
A alternating copolymers, a large variety of electron-rich and
electron-deficient building blocks were developed to construct
the conjugated polymers. These building blocks have distinctive
features. For example, certain donors/acceptors possess
chromophores with the absorption of photons in the long
wavelength region, whereas certain units have deep HOMO
levels and the characteristics of these units allow the resulting
copolymers to be unique in different applications. The D−A
alternating copolymers have achieved considerable success in
designing highly efficient photovoltaic polymers by utilizing one
Review
VOC (eV) JSC (mA/cm2) FF (%) PCE (%) ref
0.71 6.41 51.7 2.35 105
0.78 14.13 48 5.29 106
0.78 12.20 68 6.46 107
0.72 14.7 56 6.0 108
0.74 13.99 54 5.61 109
0.79 16.74 63 8.36 110
0.66 13.4 63.5 5.61 111
0.72 16.16 65 7.52 112
donor and one acceptor combination. It is interesting and
promising to construct copolymers with three or more building
blocks. Terpolymers with three units in the backbones of the
conjugated polymers are good examples to further utilize the
properties of the varied donors/acceptors.41 Because the
terpolymers have complicated molecular structures, a compre-
hensive consideration should be performed on the parameters
when designing photovoltaic terpolymers, such as solubility,
absorption spectra, molecular energy levels, charge mobility, and
blend morphology, etc. Figure 10 summarizes the terpolymers
based on BDT units and some acceptor units, and their basic
optical and electronic properties as well as photovoltaic
performances are listed in Table 5.
Ternary copolymerization is an easy and effective method used
to tune the optical and electronic properties of the conjugated
copolymers. In 2010, Wei et al. reported a D−A copolymer based
on pyridopyrazine (PP) and BDT, which exhibited an absorption
band at approximately 550−750 nm.105 When the third
component, thiophene (x = 0.5), was introduced into the
conjugated backbone of PP-BDT, an additional absorption band
at approximately 350−600 nm was observed for P36 and the
absorption edge had a slight redshift. Concurrently, the HOMO
level of the terpolymer was upshifted compared to that of the D−
A copolymer. Similarly, thiophene units were used as the third
component in the molecular backbones of the D−A polymers
PBDT-DPP and PBDT-TPD. P37 was developed by Tan and co-
workers, and the influence of the ratios of the three components
on the properties of the terpolymers was investigated.106 In their
study, the authors used a long conjugated side group,
dithienylbenzodiathiazole, to modify the thiophene unit, which
had a strong absorption at 300−600 nm. When the DPP content
decreased from 75% to 50% or 25%, the absorption band
belonging to DPP decreased gradually, whereas the intensity of
the short wavelength absorption peak increased. Furthermore,
the HOMO levels of the copolymers deceased to −5.47 from
−5.29 eV. The PSC device resulted in a best PCE of 5.29% (VOC
= 0.78 V, JSC = 14.47 mA/cm2, and FF = 0.48) for the balanced
optical and electrical properties (x = 0.25). Furthermore, Tajima
and co-workers reported a terpolymer P38 based on BDT, TPD,
and thiophene, and the thiophene unit had a tris-
(thienylenevinylene) conjugated side chain.107 Compared with
the D−A copolymer PBDT-TPD, the introduction of the third
component leads to a 25% improvement in the PCE for the P38-
based PSC device. By taking advantage of the complementary
absorption properties of the two different components, a full
visible light absorption could be easily realized. For example, the
primary absorption peak of the PBDT-BT polymers were always
located at 400−600 nm, whereas the PBDT-DPP polymers had
absorption bands at 600−900 nm. Due to the complementary
absorption properties of the DPP and DTBO, the terpolymer
P39 exploited in Wei’s group indicated a full visible light
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Table 6. Optical, Electronic, and Photovoltaic Performances of P44−P52

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P44 1.59 −5.28 0.75 14.39 61.53 6.60 43
P45 1.55 −5.28 0.76 15.68 64.97 7.79 43
P46 1.51 −5.30 0.80 17.72 68.57 9.74 44
P47 1.51 −5.30 0.80 17.99 70.55 10.20 44
P48 − − − − − − 116
P49 1.54 −4.64 0.60 17.77 63.13 6.70 117
P50 1.46 −4.63 0.60 15.21 48.58 4.45 117
P51 1.59 −5.20 0.89 7.25 60.56 3.91 42
P52 1.58 −5.20 0.90 10.82 60.81 5.92 42

Figure 11. Molecular structures of the random and regioregular polymers P44−P52.

absorption.108 When P39 was used to fabricate the PSC device, a
high JSC value of 17 mA/cm2 was achieved. As the number of
copolymerization monomers increased to three, the molecular
structures of the terpolymers became more complex than that of
the D−A copolymers. The ratio of the three monomers plays a
vital role in determining the properties of the final terpolymers. A
series of terpolymers, PBDT-DPP-TPD, with varied ratios (x = 1,
0.9, 0.75, 0.5, 0.25, 0.1, and 0) of monomers were synthesized by
Kim and co-workers, and the influence of the composition of the
random terpolymer on the optical and electronic properties was
studied systematically.109 When the content of the TPD
increased from 0 to 100%, the band gaps in the terpolymers
gradually became larger, and the HOMO levels simultaneously
became deeper. When these terpolymers were used to fabricate
the PSCs, the VOC changed from 0.73 to 0.97 V, whereas the JSC
varied from 6.09 to 13.99 mA/cm2, and an optimal PCE of 5.61%
was achieved for the P40 terpolymer with the optimal
7407
composition (x = 0.75). Except for the optical and electronic
properties of the polymers, the morphology and charge mobility
could be tuned using ternary copolymerization. Cao et al.
reported a series of terpolymers based on BDT and two types of
TT (with or without fluorination) unit, and they determined that
the size of the phase separation decreased as the fluorine content
increased.110 Furthermore, the increasing fluorine content
enhanced the hole mobility of the terpolymers from 9.27 ×
10−6 to 2.75 × 10−5 cm2 V−1 s−1. Additionally, Choi and co-
workers improved the charge mobility of P42 using ternary
copolymerization.111 Pyrene was also used as the third
component of the terpolymers due to its strong π−π
interactions.112,113 For example, Park et al. investigated the
pyrene-driven self-assembly behavior in the conjugated poly-
mers, and the results suggested that the pyrene−pyrene
interactions were beneficial for the formation of fibrous
structures.112 As the pyrene content increased to 2.5%, the
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Table 7. Optical, Electronic, and Photovoltaic Performances of P53−P76

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P53 1.58 −4.90 0.58 12.5 65.4 4.76 54
P54 1.59 −4.94 0.60 12.8 66.3 5.10 54
P55 1.62 −5.01 0.68 10.3 43.1 3.02 54
P56 1.61 −5.01 0.62 7.74 47.0 2.26 54
P57 1.60 −5.29 0.81 17.55 67.2 9.52 122
P58 1.59 −5.29 0.81 16.52 62.3 8.37 122
P59 1.61 −5.29 0.81 16.22 56 7.36 122
P60 − − 0.96 11.1 62 6.6 75
P61 − − 0.97 12.6 70 8.3 75
P62 1.75 −5.48 0.87 8.1 56 3.9 71
P63 1.70 −5.57 0.81 9.7 67 5.4 71
P64 − − 0.92 6.8 51 3.2 75
P65 − − 0.90 9.1 42 3.4 75
P66 − − 0.97 3.6 48 1.7 125
P67 − − 0.94 6.3 65 3.8 125
P68 1.85 −5.61 1.00 9.79 63.0 6.17 126
P69 1.80 −5.47 0.92 8.92 55.0 4.51 126
P70 1.82 −5.56 0.95 8.94 53.2 4.50 126
P71 1.64 −5.09 0.67 9.63 54 3.48 127
P72 1.68 −5.11 0.75 11.82 65 5.76 127
P73 1.75 −5.31 0.90 10.81 53 5.16 127
P74 − −5.06 0.61 14.88 57 5.17 128
P75 1.58 −5.09 0.66 13.53 58.55 5.23 129
P76 1.58 −5.24 0.75 12.42 47.78 4.45 130

PCE of the P43-based PSC device increased to 7.52% from
5.03%.
The optimization of the backbones of the conjugated
photovoltaic polymers by ternary copolymerization has advan-
tages, such as easy preparation and comprehensive modulation of
the properties of the resulting polymers. However, the
fundamental understanding of the structure−property-perform-
ance relationship for the terpolymers is still in its early stages.
Therefore, a rational selection of the three components and the
detailed characterization of the molecular structure with multiple
components should be considered in the near future.
3.1.4. Regioregular Structures. When asymmetric building
blocks exist in the conjugated backbones, the relationship
between the molecular structure and the device performance
becomes more complicated. Early studies on the P3HT
demonstrated that a regioregular structure was beneficial for
improving the absorption and charge transport properties of the
P3HT.114,115 Therefore, a high PCE of 4.4% was recorded for the
PSC devices based on P3HT with a regioregularity of 95.2%,
whereas the PCE was only 1.8% for the P3HT with a low
regioregularity (90.7%). In addition to 3-hexyl-thiophene, several
other asymmetric blocks, such as TT and monofluorinated
benzothiadiazole, were developed to construct photovoltaic
materials, and the influence of the regioregularity on the
photovoltaic performance has been investigated in recent years.
Basic optical and electronic properties as well as photovoltaic
performances for P44-P56 are listed in Table 6.
Although PBDT-TT photovoltaic polymers have been studied
since 2009, there have been few studies addressing the
regioregularity of this type of polymer. Recently, Lee and co-
workers synthesized the regioregular PBDTTT-C-T (P45),
which exhibited a red-shifted absorption spectrum and a higher
degree of crystallinity than its random counterpart P44.43 The
hole mobility of the regioregular polymer was one order
magnitude higher than that of the random P44. A high PCE of
7408
7.79% was obtained for the regioregular P45-based PSC device,
which was 19% higher than that of the random P44-based PSC
device. Similar results were obtained by Hou and co-workers
when they synthesized the regioregular PBDT-TS1 (P47), which
achieved an improved photovoltaic performance of 10.2%.44 Jen
and co-workers used PTB7-Th (P48) as an example to study the
components of the random parts. As depicted in Figure 11, two
major isomers (part A and part B) existed in the random P48, and
the content of the dominant one (part B) accounted for 64% (x =
0.64).116 Because the 4- and 6-positions of the fluorinated TT
unit have different chemical reaction activities, the two isomers
were prepared by controlling the synthesis procedures, and they
indicated distinct absorption properties, packing orders, and
charge mobilities. Zhu et al. reported two copolymers, P49 and
P50, that achieved PCEs of 6.70% and 4.45%, respectively, in the
PSC devices.117 Watkins and co-workers synthesized the
regioregular copolymer P52 based on BDT and monofluorinated
BT.42 Due to its improved intermolecular π-stacking interactions
and enhanced charge carrier mobility, the PCE of the PSC device
based on P52 improved to 5.92% from 3.91% for the random
PBDT-BT (P51). All of these reported results indicate that the
molecular configuration should be carefully considered due to its
significant effects on the photovoltaic properties.
The backbone is one of the parts of conjugated photovoltaic
polymers that determines the fundamental properties of the
photovoltaic materials. Over the past few decades, several
excellent D−A photovoltaic copolymers have been developed,
and each one has its own unique characteristics. Additionally,
different π-bridges, such as thiophene, furan, selenophene,
benzene, and thieno[3,2-b]thiophene, were successfully used to
further optimize the properties of the conjugated polymers.
Terpolymers are an emerging feasible and facile method used to
tune the backbone of the photovoltaic polymers. Furthermore,
recent studies have demonstrated that the fine structure, such as
the regioregularity of the backbone of the conjugated polymer,
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Figure 12. Molecular structures of P53−P76 with different flexible side chains.
played a crucial role in affecting the properties of the resulting
polymers, which should be considered when optimizing the
backbone in the near future.
3.2. Flexible Side Chains Optimization
Selecting a suitable flexible side chain for the conjugated organic
molecule with a definite conjugated backbone is important due to
its role in determining the intermolecular interactions between
the polymer molecules and the polymer−fullerene, thus affecting
their solubility, π-electron transport, and miscibility with
fullerenes. Therefore, alkyl chain engineering parameters, such
as length, shape (linear or branched), positions, and terminal
groups, should be thoroughly determined to obtain a high-
performance organic photovoltaic material. Over the past few
decades, several types of flexible side chains have been used in
designing conjugated polymers for OFET and OPV with the
desired properties.118−120
3.2.1. Alkyl Chain Configuration. Solution processability is
one of the advantages of organic solar cells, which can be
achieved by modulating the flexible side chains of the well-
defined conjugated backbones. Long and branched side chains
will improve the solubility of the polymers in common organic
solvents by reducing the π−π interchain interactions, which have
a negative effect on the carrier transport. Thus, moderate length
and bulkiness are required to balance the solubility and the
intermolecular interactions of the conjugated polymers. Basic
optical and electronic properties as well as photovoltaic
performances are listed in Table 7.
In 2009, after the reported results of P53 (PTB1), Yu and co-
workers synthesized a series of copolymers based on BDT and
TT by changing the side chains on the BDT and TT units.54 As
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Review
depicted in Figure 12, P53−P56 are four copolymers that contain
different alkyl side chains used in their research. These polymers
had similar optical bandgaps of approximately 1.60 eV, and the
HOMO levels changed from −4.90 to −5.01 eV. The PSC
devices based on these polymers achieved a different VOC from
0.58 to 0.68 V. Chen et al. studied the π−π distances of the
conjugated polymers using grazing incident wide-angle X-ray
scattering (GIWAXS) and corrected the results with the
difference in their molecular structures.121 P53 and P55 indicates
the largest π−π stacking distance difference (i.e., 3.65 Å for P53
and 3.89 Å for P55). The large π−π distance of P55 may be
attributed to the branched side chains on BDT because the
branched side chains would occupy a larger space than the linear
side chains. Although P53 and P54 possessed different side
chains on the TT unit, where P53 had a linear alkyl side chain
whereas P54 had a branched side chain, the π−π distances of P53
and P54 were nearly identical. Furthermore, they suggested that
there was a positive correlation between the strength of the π−π
interactions of the PBDT-TT polymers and the fill factor for the
PSC device. Additionally, similar results were determined by
Hou and co-workers when they introduced three types of side
chains (i.e., octyl, 2-ethylhexyl, and 3,7-dimethyloctyl) on
alkylthiothiophene-substituted BDT and synthesized three
copolymers, P57−P59.122 The three alkyl side chains had
minimal influence on the absorption spectra and the molecular
energy levels of the polymers, whereas P57, which had a linear
alkylthio side chain (octyl), demonstrated the strongest and
tightest π−π stacking compared to the other polymers due to its
reduced steric hindrance. The P57-based PSC device demon-
strated the highest JSC value of 17.55 mA/cm2 and an FF of
67.2%, resulting in a high PCE of 9.52%.
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Beaujuge and co-workers performed several studies to
investigate the influence of the alkyl side chains on the
photovoltaic performance of the PBDT-TPD polymers. In
2010, they synthesized a series of copolymers, P11, P62−P63,
and the PSC device results suggested that the varied side chains
on the TPD did not have a significant impact on VOC but had a
noticeable influence on JSC.71 Specifically, the P11-based PSC
device had a JSC of 11.5 mA/cm2, which was significantly higher
than that of the P62-based device when the TPD had a linear
octyl side chain instead of the branched 2-ethylhexyl. The higher
JSC of the P11-based device was attributed to its smaller π−π
distance of 3.6 Å. So et al. determined that the decreased π−π
intermolecular interaction of P62 would cause lower hole
mobility, higher bimolecular recombination, and higher
energetic disorder.123 Furthermore, Beaujuge and co-workers
replaced the branched 2-ethylhexyl side chain of the BDT with
linear dodecyl or myristyl.75 They determined that this would
induce a critical change in the polymer (P64−P65) self-assembly
and preferential backbone orientation in thin films, which would
cause a dramatic drop in the photovoltaic efficiency of the PSC
devices. Using transient optical spectroscopy, Laquai et al.
studied the relationship between the side chain pattern and the
charge carrier dynamics in the PBDT-TPD:PCBM BHJ systems,
and they determined that the varied side chain did not have a
significant influence on the exciton dissociation and ultrafast
charge generation steps; however, the nongeminate recombina-
tion and the subnanosecond geminate recombination would be
suppressed when the branched side chain was used to modify the
BDT unit.124 By fine-tuning the length of the side chain of the
TPD from octyl to heptyl or hexyl, Beaujuge et al. prepared the
P11, P61, and P60 polymers, and a high PCE of 8.5% was
obtained for the P60-based PSC device.75
The side chains not only affected the intermolecular
interactions of the resulting polymers but also had a strong
influence on the intermolecular arrangements at the donor/
acceptor interfaces.125 Beaujuge and co-workers systematically
studied the PBDT-TPD polymer family (P11, P62, and P65−
P67) with varied side chains on the BDT and TPD units and
discussed how the side chains affected the intermolecular
interaction between the conjugated polymers with fullerenes.
They suggested that the electron-accepting moiety (acceptor
unit) of the copolymer should be docked with the fullerene in
highly efficient polymer:fullerene systems, and the preferred
intermolecular arrangement could be realized using side chain
optimization. For example, branched side chains were more
sterically hindered with fullerenes, whereas linear side chains
were more sterically accessible with fullerenes. Therefore, in the
polymer family of PBDT-TPD, the high-performance polymers
should consist of branched side chain-substituted BDT units and
linear side chain-substituted TPD units. Ma et al. synthesized a
series of PBDT-TPD polymers (P68−P70) by incorporating
different alkyl side chains on the thienyl-BDT, and their
experimental results and theoretical calculation suggested the
size and topology of the side chains had impacts on the polymer
solubility, energy levels, and intermolecular packing and thus
influenced the photovoltaic performance.126 Due to its improved
morphology and fine-tuned energy levels of P68 with 2-ethyl-
hexyl as the side chains, a maximum PCE of 6.17% with a high
VOC of 1.00 V was obtained by using PC61BM as acceptor in the
PSC device.
3.2.2. Alkyl Chain Substitution Positions. Additionally,
the substitution positions played an important role in designing
highly efficient photovoltaic polymers due to their influence on
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intermolecular π−π stacking. The optical and electronic
properties of the conjugated polymers are highly dependent on
the π-electron delocalization of the polymer, which can be
affected by the different steric hindrance effects or the rotational
angles caused by the alkyl chains at varied substitution positions.
As depicted in Figure 12, Hou and co-workers designed and
synthesized the P71−P73 copolymers with alkyl side chains at
varied positions.127 The total number of carbon atoms in the side
chains was kept the same to guarantee similar solubility in their
study. A theoretical calculation revealed that when the alkyl
chains occupied different positions of the thiophene unit, the
dihedral angles between the thiophene and the BDT units
changed from 52.7° and 58.2° to 87.8°, and the frontier orbital
electron density distribution was affected. Due to the largest
steric hindrance of the meta-alkyl chains, the resulting P73
polymer had a blueshifted absorption spectrum and a down-
shifted HOMO level compared to the P71 and P72 polymers.
Furthermore, the intermolecular stacking in the P73 film was
disturbed, thus resulting in its low hole mobility. When the three
polymers were used to fabricate the PSC devices, they exhibited
extremely different VOC, ranging from 0.67 V for the P71-based
PSC device to 0.90 V for the P73-based PSC device.
3.2.3. Functional Side Chains. Additionally, unique
functions could be realized by using flexible side chain
optimization. For example, to improve the stability of the PSC
devices, Tan and co-workers introduced the terminal bromine
containing side chains on the TT units and synthesized the
bromine-functionalized low bandgaps in the P74 polymer.128
After the UV light treatment, the bromine-containing group
could be cross-linked without causing a significant impact on the
packing and electronic properties of the conjugated polymers,
thus improving the solvent resistance and the thermal stability of
the corresponding PSC device. By changing the content of the
bromine-containing TT unit, a higher PCE of 5.17% with better
stability compared to its alkyl side chain equivalents was obtained
for the P74-based PSC device.
By changing the flexible alkyl side chains of the polymers, the
conjugated polymers could also be dissolved in nonaromatic and
nonchlorinated solvents. Due to its conjugated backbones,
organic photovoltaic materials are commonly dissolved in
aromatic or chlorinated solvents, such as toluene (TOL),
chloroform (CF), chlorobenzene (CB), and 1,2-dichloroben-
zene (o-DCB). To develop highly efficient conjugated polymers
with environmentally friendly solvents, Hou and co-workers
introduced the triethylene glycol monoether (TEG) side chain
on the BDT unit and synthesized the P75 and P76
copolymers.129,130 Due to the enhanced solubility caused by
the TEG side chain, the P75 copolymer could be dissolved in
tetrahydrofuran (THF), 1,4-dioxane (DIOX), N,N-dimethylfor-
mamide (DMF), and N-methyl-2-pyrrolidone (NMP) et al.129
The PSC device based on the NMP achieved a PCE of 5.23%
(VOC = 0.66 V, JSC = 13.53 mA/cm2, and FF = 58.55%). Using a
novel donor material, P76, and a new synthesized acceptor,
PC71B-DEG, they prepared the PSC device using anisole, and a
PCE of 4.45% was obtained.130
3.3. Functional Substitutions
Introducing functional substitutions (electron-withdrawing or
electron-donating) to the backbone and/or the side chains is a
common and useful strategy to tune the optical and electronic
properties of the conjugated polymers. Over the past few years,
several functional atoms, such as fluorine, oxygen, and sulfur, and
substituted groups, such as ester, carbonyl, sulfonyl, and cyano
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Table 8. Optical, Electronic, and Photovoltaic Performances of P77−P88

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P77 1.63 −5.12 0.74 13.0 61.4 5.90 54
P78 1.58 −5.09 0.68 14.59 62.6 6.21 58
P79 1.58 −5.22 0.80 15.73 74.3 9.35 60
P80 1.75 −5.41 0.68 11.1 42.2 3.2 131
P81 1.73 −5.48 0.75 9.1 39.4 2.7 131
P82 1.60 −4.90 0.56 12.2 66.7 4.5 132
P83 1.65 −4.95 0.60 14.3 65.7 5.6 132
P84 1.64 −5.15 0.74 14.4 67.7 7.2 132
P85 1.64 −5.20 0.78 15.2 72.4 8.6 132
P86 1.98 −5.29 0.70 11.14 55.2 4.30 133
P87 2.00 −5.36 0.79 11.83 72.9 6.81 133
P88 1.84 −5.67 0.97 10.92 71.4 7.52 134

Figure 13. Molecular structures of P77−P88 with different electron-withdrawing substitutions.

groups, were developed to design photovoltaic polymers with the
desired properties.
3.3.1. Electron-Withdrawing Substitutions. The fluorine
atom is the most electronegative atom with a small size in the
periodic table, making it an excellent functional atom to modify
the electronic properties of the conjugated polymers. Due to its
strong electron-withdrawing ability and small size, introducing
fluorine atoms to the conjugated molecules always results in
simultaneously downshifted HOMO and LUMO levels without
causing considerable steric hindrance. Furthermore, fluorination
of the conjugated backbones (donor and/or acceptor segments)
and/or the conjugated side chains have different effects on the
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optical and electronic properties as well as the photovoltaic
performance of the resulting polymers. Basic optical and
electronic properties as well as photovoltaic performances for
P77-P88 are listed in Table 8.
In 2009, Yu and co-workers synthesized a series of copolymers
based on BDT and TT, among which the introduction of the
fluorine atom on the TT unit was an important discovery.54
Compared to its counterpart P54 without fluorination, the P77
copolymer containing a fluorine atom had decreased HOMO
and LUMO levels; however, its optical bandgap remained
unchanged. Due to its downshifted HOMO level, the P77-based
PSC device obtained a high VOC of 0.74 V and a PCE of 5.9%,
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Figure 14. Molecular structures of polymers P89−P100 with different substitutions.
whereas the P54-based PSC device yielded a VOC of 0.66 V and a
PCE of 4.1%. In 2011, Hou and co-workers designed and
synthesized the P78 copolymer based on thienyl-BDT and ester-
substituted TT, which had a HOMO level of −5.09 eV and
demonstrated a PCE of 6.21%.58 When the fluorine atom was
introduced to P79, the HOMO level of P79 was downshifted to
−5.22 eV; Chen and co-workers fabricated an inverted PSC
device, and an impressive PCE of 9.35% was achieved in 2013.60
Huang and co-workers investigated the effects of the fluorine
content on the photovoltaic properties of the resulting polymers
using random copolymerization (P41).110 They synthesized a
series of copolymers with increasing fluorine content, and it was
determined that the crystalline properties of the polymers and
the morphology of the blends with PCBM could also be affected
by the content of the fluorine.
In 2011, Yu and co-workers introduced the fluorine atoms on
the backbones of the conjugated polymers.131 As depicted in
Figure 13, they synthesized the fluorinated BDT unit and
prepared a series of copolymers, P54, P9, and P80−P81, with
varied fluorine atoms (0F−3F). The fluorination of the polymers
lowered their HOMO and LUMO levels and simultaneously
widened the optical bandgaps slightly by 0.1−0.2 eV.
Furthermore, they determined that the perfluorination P81
(3F) introduced fluorophobicity for the PCBM molecules, which
enhanced its crystallinity and increased its phase separation size
to ca. 100 nm. Therefore, the PCE values of the PSC devices
changed from 5.1% to 7.4%, 3.2%, and 2.7% when the number of
fluorine atoms increased from 0 to 1, 2, or 3.
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Hou and co-workers incorporated fluorine atoms on the
conjugated thienyl side chains and synthesized a set of
copolymers, P82−P85, containing different numbers of fluorine
atom from 0 to 3.132 They determined that the introduction of
the fluorine atom on both the donor and acceptor units had a
synergistic modulation effect on the molecular energy levels for
the resulting D−A copolymers. Particularly, when compared
with polymer P82 (0F) without fluorination, the VOC of the PSC
device based on P83 (1F on the TT unit) indicated a 40 mV
increase. Furthermore, the difluorination on the thienyl unit of
BDT resulted in an increase in VOC by 180 mV compared to the
P82-based PSC device. Interestingly, the VOC of the PSC device
based on the trifluorinated polymer P84 was 220 mV higher than
that of the P82-based PSC device. Due to the high VOC of the
device based on P84, a remarkable PCE of 8.6% was achieved
with a VOC of 0.78 V.
As a strong electron-withdrawing substitution, the cyano
group was also developed to modify the photovoltaic polymer
(Figure 13). You and co-workers did a lot work to optimize the
structures of copolymers based on BDT and benzotriazole
(BTz).133,134 To reduce the HOMO levels of the PBDT-TAz
copolymers, they synthesized the P87 copolymer with
fluorinated TAz (triazoles). Although the VOC of the PSC device
based on P87 reached 0.79 V, there was still room for
improvement because the PBDT-BTz possessed a larger optical
bandgap of approximately 2.0 V. Therefore, they introduced the
cyano group on the TAz unit and prepared the P88 copolymer.
The CV measurement indicated that the HOMO level of P88
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Table 9. Optical, Electronic, and Photovoltaic Performances of P89−P100

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P89 1.60 −5.07 0.7 14.7 64.1 6.58 135
P90 1.58 −5.11 0.74 17.48 58.7 7.59 58
P91 1.85 −4.80 0.84 6.28 36.9 1.95 137
P92 1.55 −5.20 0.40 5.27 60.6 1.28 137
P93 2.21 −5.31 0.83 4.18 45 1.56 138
P94 2.03 −5.36 0.91 4.40 43 1.73 138
P95 2.07 −5.41 0.99 7.66 53 4.00 138
P96 1.53 −5.18 0.73 15.17 64.44 7.10 139
P97 1.63 −5.50 0.98 10.15 45 4.48 140
P98 1.66 −5.01 0.64 14.9 70.3 6.70 141
P99 1.64 −5.16 0.81 5.95 37.9 1.85 141
P100 1.70 −5.17 0.78 13.4 71.8 7.50 142

was as low as −5.7 eV, which was 0.28 eV lower than that of P87.
The PSC device based on P88 indicated a very high VOC of 1.0 V,
and a PCE of 5.53% was achieved when the active layer thickness
was approximately 100 nm. When the thickness of the active
layer increased to 300 nm, an impressive PCE of 8.4% was
recorded for the P88-based PSC device.
3.3.2. Electron-Donating Substitutions. The chalcogens
“O” and “S” are widely used to modify the optical and electronic
properties of the photovoltaic materials. Because the alkyloxy has
a much stronger electron-donating effect than the alkyl, previous
studies on thiophene-based polymers have demonstrated that
the alkyl-containing polymers would have deeper HOMO levels
than their alkyloxy substituted counterparts. When the carboxyl
was replaced by carbonyl, the resulting polymer would display a
downshifted HOMO level. Therefore, the carboxyl and carbonyl
substitutions should be carefully selected to modify the
molecular structures of the conjugated photovoltaic materials
(Figure 14).
In 2009, the P55 copolymer, which was based on BDT and
carboxyl-substituted TT and developed by Yu and co-workers,
exhibited promising photovoltaic properties. The P55-based
PSC device yielded high JSC and FF values; however, its VOC was
only 0.6 V.54 Hou and co-workers replaced the carboxyl with
carbonyl to modify the TT unit and synthesized the P89
copolymer, which simultaneously demonstrated downshifted
HOMO and LUMO levels compared to P55.135,136 Benefit for its
higher VOC of 0.7 V, the PSC device based on P89 yielded a PCE
of 6.58%, whereas the P55-based PSC device obtained a PCE of
5.15%. As compared to P78, which was based on the BDT ester-
substituted TT, P90 with carboxyl-substituted TT units had a
similar optical bandgap but a downshifted HOMO level, thus
leading to a higher VOC of 0.74 V for the P90-based PSC device.58
Replacing the alkyl chains with alkoxy chains always had a
significant influence on the photovoltaic properties of the
resulting polymers. For instance, in 2009, Hou et al. synthesized
two polymers, P91 and P92, with an identical conjugated main
chain but different side chains.137 The absorption spectra of the
two polymers in solution and films demonstrated considerable
differences. Specifically, the alkoxy-containing P92 polymer
possessed a narrowed optical bandgap of 1.55 eV, which was 0.27
eV lower than that of P91. Furthermore, from solution to film, a
small redshift (8 vs 51 nm) was observed for P92 and P91,
respectively, suggesting that the alkoxy possessed a lesser steric
hindrance than alkyl. Although the alkoxy-substituted polymer
had a superior absorption property, its HOMO level was 40 mV
higher than that of P91, thus causing its low VOC of 0.4 V in the
corresponding PSC device.
7413
Because sulfur is known to be a poorer electron donor than
oxygen, the S-containing polymers always had lower HOMO and
LUMO levels than the O-containing polymers. Ferraris et al.
introduced the alkylthio substitution on the BDT unit and
synthesized the P95 homopolymer and the P94 copolymer.138
When compared with their alkoxy analogue P93, P94, and P95
showed narrowed optical bandgap from 2.2 to 2.0 eV, and the
HOMO levels of P94 and P95 were lowered to −5.36 and −5.41
from −5.31 eV. Meanwhile, the P95 film possessed a higher
absorption coefficient than the P93 film. The PSC devices
fabricated using P93−P95 exhibited a varied VOC from 0.83, 0.91,
and 0.99 V, respectively.
Li and co-workers conducted a further structural optimization
of P79 (TB7-Th) by replacing the alkyl chain with alkoxy (P96)
and alkylthio (P58) substitutions.139 P58 and P96 indicated a
broad absorption spectra compared to P79, and the HOMO level
of the three polymers were −5.30, − 5.18, and −5.41 eV for P79,
P96, and P58, respectively. Due to its downshifted HOMO level,
the P58-based PSC device yielded a PCE of 8.42% with a high
VOC of 0.84 V, whereas the P96-based PSC device obtained a
PCE of 7.1% with a VOC of 0.73 V. To further improve the VOC of
the PSC device based on the PBDT-TT polymers, Hou and co-
workers introduced the dialkylthio-substituted thiophene on the
BDT unit and prepared the P97 copolymer, which demonstrated
a very high VOC of 0.98 V in the PSC devices.140 However, due to
the P97 copolymer’s blueshifted absorption spectrum and
decreased hole mobility, the PCE of the PSC device fabricated
by P97 was only 4.48%.
Additionally, a sulfonyl substitution was used as an electron-
withdrawing group; by changing the alkyl to alkylthio and then to
sulfonyl, the HOMO levels of the PBDTDTTTs could be
gradually decreased. As presented in Table 9, the VOC of the PSC
devices increased to 0.56, 0.64, and 0.81 V for P82, P98, and P99,
respectively.132,141 In 2014, Hou and co-workers used the meta-
alkoxy-phenyl group to modulate the structure of the thienyl-
substituted copolymer PBDT-DTTT.142 The results suggested
that replacing thienyl with a meta-alkoxy-phenyl substitution had
a minimal effect on their optical absorption, molecular packing,
device morphology, and charge transport properties but
significantly lowered the HOMO level of the polymer. From
P83 to P100, the VOC of the PSC devices changed from 0.6 to
0.78 V, whereas the JSC and FF changed slightly.
3.4. Two-Dimensional Conjugated Benzodithiophene
(2D-BDT)
The 2D conjugated side chain was first used to modify the
structure of polythiophene to obtain broad and strong visible
absorption properties by Li and Hou et al.143,144 After the BDT
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Figure 15. Common conjugated side chains used for 2D-BDT units.

Figure 16. 2D-BDT-based copolymers P101−P115 with different conjugated side chains.

was developed to construct copolymers for the polymer solar
cells, Hou and co-workers used the same concept to further
optimize the structures of the BDT-based conjugated polymers,
obtaining better photovoltaic performance.28 Over the past few
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years, several researchers designed and synthesized many
conjugated units used as side chains in the 2D-BDT polymers
(Figure 15). Thienyl-substituted BDT was the earliest 2D
conjugated BDT unit, and several widely studied highly efficient
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Table 10. Optical, Electronic, and Photovoltaic Performances of P101−P115

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P101 1.55 −5.19 0.69 11.77 64.81 5.28 145
P102 1.58 −5.29 0.81 16.57 65.64 8.78 145
P103 1.39 −5.09 0.44 9.5 55 2.30 147
P104 1.55 −5.31 0.77 14.70 68 7.71 148
P105 1.53 −5.29 0.81 16.00 62.71 8.13 149
P106 1.78 −5.46 0.86 12.8 67 7.4 150
P107 1.78 −5.38 0.81 11.2 60 5.4 150
P108 1.78 −5.40 0.85 11.8 64 6.4 150
P109 1.74 −5.47 0.90 12.93 62.73 7.30 151
P110 1.67 −5.4 0.80 11.94 65.10 6.21 152
P111 1.73 −5.59 0.94 6.17 48.80 2.83 153
P112 1.75 −5.47 0.98 9.62 59.7 5.46 154
P113 1.73 −5.37 0.90 10.6 54.7 5.22 154
P114 1.70 −5.31 0.86 12.3 61.4 6.48 154
P115 1.68 −5.30 0.84 6.35 40.5 2.17 154

conjugated polymers, such as PBDTTT-C-T, PTB7-Th, and
PBDT-TS1, were comprised of thienyl-substituted BDT units.
As a homologous series of thiophene, furan and selenophene
were also frequently used to modify the physicochemical
properties of the thienyl-BDT containing polymers. Additionally,
a benzene ring and thiazole were developed as 2D conjugated
side chains to modify the structure of the BDT-based polymer.
To extend the effects of the 2D conjugated side chain, several
conjugated side chains with larger π-conjugated areas and
increased conjugated lengths were developed, such as
thienothiophene, thianaphthene, oligothiophene, and thiophe-
nevinylthiophene (TVT).
Generally, the introduction of 2D conjugated side chains on
the BDT units had an impact on not only the absorption spectra
of the resulting polymers but also their molecular energy levels,
charge carrier mobilities, and crystalline properties, which
resulted in a comprehensive effect on the photovoltaic
performances of the PSC devices.
Using 2D conjugated side chains with heteroatoms is an easy
and promising method for tuning the optical and electronic
properties of conjugated polymers. Replacing the “S” atom of
thiophene with its homologous series of “O” or “Se” has
frequently been used to tune the photovoltaic performance of the
thienyl-BDT containing polymers. After the results of P79
(PTB7-Th) were reported by Chen’s group,60 Hou and co-
workers introduced furan and selenophene to BDT as
conjugated side chains, and copolymers P101 and P102, which
are based on 2D-BDT and fluorinated TT, respectively, were
prepared as indicated in Figure 16.145 The “O” atom has the
smallest atomic radius of 64 ppm (104 pm for “S” and 118 pm for
“Se”), and the C−O bond has the longest bond length but
smallest C−O−C bond angle, which facilitates planarity between
neighboring heterocycles.146 On the basis of theoretical
calculations using DFT, the dihedral angles between the BDT
and the conjugated side groups increased from 34° to 60° when
the furan group was replaced by thiophene or selenophene,
which had a significant effect on the absorption spectra, HOMO
levels, crystallinities, and aggregation sizes of the resulting
polymers. As listed in Table 10, the furan-substituted P101
copolymer indicated a narrowed optical band gap but a higher
HOMO level than that of the other polymers (P79 and P102),
and the selenophene equivalent P102 possessed the lowest
HOMO level and the same optical bandgap as the thiophene-
based P79 copolymer. The XRD measurement showed that P101
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had a very compact intermolecular packing with a π−π stacking
distance of 3.63 Å, which caused oversized aggregations when
blended with PCBM, and the P101-based PSC device thus
achieved a relatively low PCE of 5.28% (VOC = 0.69 V, JSC = 11.77
mA/cm2, and FF = 64.81%). Under the same conditions, the
PSC based on P79 achieved a PCE of 9% (VOC = 0.78 V, JSC =
16.86 mA/cm2, and FF = 68.16%), whereas the P102-based PSC
device achieved a PCE of 8.78% (VOC = 0.81 V, JSC = 16.57 mA/
cm2, and FF = 65.64%). Furthermore, a thiazolyl-substituted
BDT unit was developed by Wong’s group, and the P103
copolymer with TT as an acceptor unit demonstrated a narrowed
optical bandgap of 1.40 eV but a high HOMO level of −4.96
eV.147 The PSC device based on P103 depicted a relatively low
PCE of 2.3% with a VOC of 0.44 V.
Extending the conjugated surface could enhance the
intermolecular π−π interaction for conjugated polymers. In
2013, Hwang et al. synthesized a thieno[3,2-b]thiophene-
substituted BDT unit and prepared the P104 copolymer using
fluorinated TT unit as an acceptor unit, which indicated a low
optical band gap of 1.55 eV and a low-lying HOMO level of
−5.31 eV.148 The GIWAXS measurement demonstrated that the
P104 film had a preferable face-on orientation with respect to the
substrate. The inverted PSC device yielded a high PCE of 7.71%
(VOC = 0.77 V, JSC = 14.70 mA/cm2, and FF = 68%). Moreover, a
tandem PSC device fabricated using P104:PC71BM as the top cell
and P3HT:IC60BA as the bottom cell indicated a maximum PCE
of 8.66%.
Recently, a rigid long conjugated side chain, thienyleneviny-
lene (TVT), was introduced on the BDT unit by Hou group, and
the copolymer P105 was synthesized.149 As compared to P9,
which had a nonconjugated alkoxyl side chain, P105 with a
prolonged conjugated side chain on BDT displayed a large red-
shifted absorption spectrum with an absorption onset of 810 nm.
Moreover, because the TVT-containing BDT monomer had a
strong absorption character in the range of 300−600 nm, the
absorption spectrum of P105 in the short wavelength region was
significantly enhanced. What’s more, P105 showed closer π−π
stacking and increased hole mobility compared to P9. The PSC
device based on P105 achieved a PCE of 8.13% (VOC = 0.81 V,
JSC = 16 mA/cm2, and FF = 62.71%) when using PC71BM as the
acceptor material. Benefiting from its panchromatic absorption
property, when PC61BM was used as the acceptor material, the
P105-based device also showed an inspiring PCE of 7.67%.
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Figure 17. Highly efficient polymers based on BDT and TT units.
Due to its weak electron-donating properties, large π-
conjugated area and good planarity of the benzene ring, a
phenyl-substituted BDT was also developed by researchers. In
2013, Wei et al. introduced thiophene, furan, and benzene on the
BDT units and synthesized three copolymers, P106−P108.150 A
theoretical calculation using the DFT indicated that P108 had the
largest torsional angle between the conjugated side chain and the
BDT unit, whereas the furan-substituted BDT had the smallest
torsional angle. The three polymers demonstrated similar optical
bandgaps of approximately 1.78 eV; however, their HOMO
levels measured using cyclic voltammograms varied from −5.46
to −5.38 eV. The photovoltaic properties of the three polymers
were evaluated through the PSC devices, and the detailed
parameters are listed in Table 10. The highest PCE of 7.4% was
achieved for the P106-based PSC device.
Yang and co-workers performed several studies to design a
novel conjugated side chain for the BDT unit. To decrease the
electron density of thiophene, which is a six-π-electron five-
membered aromatic compound, they introduced thianaphthene
(thiophene fused with benzene) on the BDT unit.151 When
compared with its thienyl-substituted counterpart, the HOMO
level of the new P109 copolymer decreased from −5.36 to −5.47
eV. Due to the extended π-conjugated system of P109, its
absorption spectrum had a slight redshift compared to that of the
thienyl-based analogues. The deeper HOMO level of P109
resulted in a higher VOC of 0.90 V for the PSC device, and a
maximum PCE of 7.30% was achieved using PC61BM as the
acceptor materials, which was one of the best results for PC61BM-
based PSCs at that time. Then, they attached trialkoxy phenyl on
thiophene to improve the solubility of the P110 polymer, and the
P110-based PSC device showed a PCE of 6.21%. 152
Furthermore, they introduced the terthiophene derivative on
the BDT unit and synthesized the P111 copolymer, which
exhibited a high thermal decomposition temperature of 437 °C,
and the P111-based PSC device achieved a PCE of 3.57%.153
Recently, Cho et al. extended the π-conjugation of 2D-BDT
polymers by introducing oligothienyl side chains on the BDT,
and four copolymers (P112−P115) with alkylated thienyl,
bithienyl, terthienyl, or quaterthienyl side chains were
prepared.154 The polymers exhibited gradually red-shifted
absorption spectra and upshifted HOMO levels as the number
of thienyl units increased. The absorption intensity of the
polymers at a short wavelength range from 350 to 550 nm was
significantly enhanced when the number of thiophene units
increased. GIXRD indicated an amorphous polymeric arrange-
ment in the P112 film, whereas the others had enhanced
crystalline properties, which can be ascribed to their different
intramolecular steric hindrances. Due to the improved optical
absorption property and higher carrier mobility of P114, the
P114-based PSC device showed the highest JSC and PCE values
out of the four polymers (PCE = 6.48% with a JSC = 12.5 mA/
cm2).
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4. BDT-BASED PHOTOVOLTAIC COPOLYMERS
4.1. Copolymers Based On BDT and TT
Thieno[3,4-b]thiophene (TT) was frequently used in low band
gap polymers due to its stable quinoidal structure. In 1997, alkyl-
substituted poly(thieno[3,4-b]thiophene) was first synthesized
as a soluble low band gap conducting polymer.52 Furthermore,
Yang and co-workers prepared a PTT copolymer by copolymer-
izing TT and a thiophene unit in 2006 and used the low band gap
polymer in near-infrared photodetectors.52 In the OPV field, TT
is one of the most well-known building block used in several
highly efficient photovoltaic polymers, such as PTB7,55
PBDTTT-C-T,58 PTB7-Th,60 and PBDT-TS1.59 All of these
polymers achieved record PCEs in the OPV field and were widely
studied by researchers (see Figure 17).
In 2008, Yu et al. initially synthesized the P53 copolymer
(Figure 12) based on BDT and TT.53 The maximum absorption
peak of P53 was located at 690 nm with an absorption onset at
784 nm, and the electrochemical cyclic voltammetry measure-
ment indicated that the HOMO and LUMO levels of the
polymer were −4.90 and −3.20 eV (Table 10), respectively.
When PC61BM was used as the acceptor in the BHJ solar cell
device, a high PCE of 4.76% was achieved (VOC = 0.58 V, JSC =
12.5 mA/cm2, and FF = 65.4%). Due to the better absorption
properties in the visible region of PC71BM, the PSC devices
fabricated by P53 and PC71BM achieved a higher JSC of 15.0 mA/
cm2, and the PCE was boosted up to 5.30% with a VOC of 0.56 V
and an FF of 63.3%. Because of its excellent photovoltaic
performance, P53 was also a good model to further explore the
charge transfer and charge separation steps using atomistic
computer calculation. Lischka and co-workers used P53/
PC61BM as a bulk heterojunction model to conduct a detailed
quantum chemical simulation.155 They determined that the
charger transfer states were located below the bright interchain
excitonic states, and they presented a simple model for the charge
separation process. In addition to the PBDT-TT polymers
discussed above, there are several PBDT-TT polymers that
exhibit excellent photovoltaic properties. For example, when
alkyl-substituted BDT was used as the donor unit, P116 had an
optical bandgap of 1.60 eV and a HOMO level of 5.04 eV and the
P116-based PSC device achieved a PCE of 5.85% (VOC = 0.72 V,
JSC = 13.9 mA/cm2, and FF = 58.5%). By thoroughly
understanding the relationship between the VOC of the PSC
device and the HOMO level of the polymer, Hou and co-workers
systematically tuned the VOC using a molecular design
approach.135 Specifically, the P117 polymer with carbonyl and
a fluorine atom-modified TT unit had a downshifted HOMO
level located at −5.22 eV, which was approximately 200 mV
lower than that of the ester-substituted P55. Therefore, the VOC
of the PSC devices increased from 0.62 to 0.76 V, and an
impressive PCE of 7.73% (certified as 6.77% by NREL in 2010)
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Figure 18. Molecular structures of the copolymers based on BDT and TT units.

Table 11. Optical, Electronic, and Photovoltaic Performances of P116−P123

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P116 1.60 −5.04 0.72 13.9 58.5 5.85 54
P117 − −5.22 0.76 15.2 66.9 7.73 135
P118 1.69 −5.60 0.82 12.75 55 5.76 162
P119 1.71 −5.60 0.79 9.47 55 4.11 162
P120 1.67 −5.61 0.78 8.38 48 3.16 162
P121 1.65 −5.12 0.76 14.1 58 6.22 163
P122 1.44 −4.95 0.63 6.37 51.0 2.04 164
P123 1.91 −5.44 0.86 4.97 55 2.72 165

was achieved for the P117-based PSC device, which was the
highest value at that time.
At almost the same time, Yu and co-workers developed the
well-known P9 (PTB7)55,56 after an extensive structural
optimization of PBDT-TT, and a PCE of 7.40% was achieved
for the P9-based PSC device, which was one of the few PCE
values over 7% reported in 2010. After the reported results of
PTB7, its excellent properties attracted several researchers to
further improve its photovoltaic performance and explore the
working mechanism of the OPV. By increasing its molecular
weight to 128 kDa with a low polydispersity (PDI) of 1.21, Cao
and co-workers pushed the PCE of the P9-based device to
8.5%.156 Additionally, a theoretical calculation using DFT was
used to explore the nanostructures and electronic properties of
P9. The results suggested that P9 possessed a nonplanar
conformation with an inter-ring torsional angle of approximately
25°, and the effective conjugation length of P9 was calculated as
147 Å.157 Different device structures and several interface
materials were applied in the P9-based PSC devices to improve
its PCE, and a PCE over 9% was reported by several
groups.57,158,159 Among them, Cao and co-workers improved
the PCE of the P9-based PSC device to 9.2% using an inverted
cell device structure with MoO3 and PFN as the interlayer
materials.57 Ge et al. further improved the PCE of the P9-based
PSC device to 10.02% using a nonconjugated small molecule
electrolyte.160 Furthermore, studies on the BHJ morphology of
the PSC device, dissociation of the exciton, and transfer of the
charges were all performed using P9/PCBM as a model.161
Lee et al. synthesized a triisopropylsilylethynyl-substituted
BDT unit, and they used TT with different substitutions as the
acceptor units to prepare the copolymers P118−P120.162 The
PCEs of the PSC devices based on these polymers ranged from
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3.16% to 5.76%. In 2011, Hou and co-workers used the strong
electron-withdrawing sulfonyl to modify the TT unit and
synthesized the P121 copolymer, which showed a PCE of
6.22% with a VOC of 0.76 V.163
Because the PBDT-TT polymer family has excellent photo-
voltaic properties, many building blocks derived from BDT or
TT were designed and synthesized by researchers. For example,
Yu et al. synthesized the bi-TT unit and prepared the P122
copolymer,164 which possessed a broad absorption in the near-IR
region with an absorption onset of 863 nm corresponding to an
optical band gap of 1.44 eV, and the HOMO energy level of P122
was located at −5.19 eV. Furthermore, the effects of the dipole
moment of the conjugated polymers on the charge separation
process were studied. The theoretical calculation results
suggested that P122 possessed a large electron−hole pair
binding energy due to its minimized dipole moment, which
resulted in its difficult charge separation. In 2012, Ding and co-
workers synthesized an interesting electron-accepting unit,
cyclopenta[2,1-b:3,4-c′]dithiophene-4-one, and the copolymer
P123 copolymerized with BDT exhibited a PCE a 2.72% with a
VOC of 0.86 V for the PSC device.165 Figure 18 summarizes the
copolymers based on BDT units and TT units, and their basic
optical and electronic properties as well as photovoltaic
performances for P53-P76 are listed in Table 11.
Generally, copolymers based on 2D-BDT and TT have
superior photovoltaic properties compared to those of their
counterparts with alkoxy side groups. In 2011, Hou and co-
workers initially designed and synthesized copolymers based on
2D-BDT and TT by replacing the alkoxy group with an
alkylthienyl group of the BDT unit.58 When compared to their
alkoxy-substituted counterparts, copolymers with 2D side groups
(P78 and P90) indicated an enhanced thermal stability,
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Figure 19. Molecular structures of P124−P148.
improved absorption properties, downshifted molecular energy
levels, and thus improved photovoltaic performances. For
instance, P90 had an optical band gap of 1.58 eV and a
HOMO of −5.11 eV. Due to its extended π-conjugated area, the
hole mobility of the P90/PC71BM film blend reached 0.27 cm2
V−1 s−1, which was a 3 orders of magnitude enhancement over its
alkoxyl substitution counterpart. These advantages of the 2D-
BDT polymers contributed to the improvement in their
photovoltaic properties. The P90-based PSC device achieved
the best PCE of 7.59% with a VOC of 0.74 V. P79 (PTB7-Th) was
another successful application of 2D-BDT. When thienyl group
was used to replace the alkoxyl of P9 (PTB7) by Chen and co-
workers, the absorption spectrum was extended by 25 nm to a
longer wavelength due to the improved coplanarity of P79.60 A
CV measurement indicated that the HOMO level of P79 was 80
mV lower than that of P9. Furthermore, the GIWAXS showed
that the intermolecular π−π stacking of the P79/PC71BM blend
film was stronger than that of P9/PC71BM. Using a novel
fullerene derivative-doped zinc oxide (ZnO-C60) nanofilm as
the cathode interlayer, the P79-based inverted PSC device
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Review
achieved a high PCE of 9.35%, which was one of the best results
at that time. Li et al. determined that a polymer based on an
alkylthio-substituted BDT exhibited an improved VOC in the
corresponding PSC device.139 Hou et al. designed and prepared
the P57 copolymer with a linear alkylthio side chain, which had
an optical band gap of 1.51 eV and a HOMO level of −5.33 eV.59
An impressive PCE of 9.48% was recorded for the P57-based
PSC device, and a PCE over 10% was also obtained by further
optimization of the PSC devices.166 Very recently, an impressive
PCE of 9.67% was obtained for the P57-based PSC device using a
novel environmentally friendly single-solvent (i.e., 2-methyl-
anisole).167
4.2. Copolymers Based On BDT and BT
Benzothiadiazole (BT) units were widely applied for construct-
ing conjugated D−A copolymers due to their strong electron-
withdrawing properties, many of which had good applications in
solar cell devices.69 From the view of the chemical structure of
the BT unit, it could be modified by several methods. First, the
“S” atom could be replaced by its congeners “O” or “Se”, and TAz
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Table 12. Optical, Electronic, and Photovoltaic Performances of P124−P148

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P124 1.7 −5.40 0.87 10.03 57.3 5.0 168
P125 1.7 −5.54 0.91 12.91 6.12 7.2 168
P126 1.67 −5.48 0.85 11.4 50.6 5.28 170
P127 1.70 −5.31 0.78 15.38 69.2 8.30 171
P128 1.73 −5.37 0.81 8.00 55 3.65 91
P129 1.95 −5.17 0.76 8.96 59 4.02 172
P130 1.96 −5.44 0.94 6.5 46 2.81 172
P131 1.78 −5.21 0.76 13.87 66.6 7.05 173
P132 2.03 −5.56 0.84 10.59 49 4.32 174
P133 1.92 −5.44 0.83 10.16 50.2 4.23 175
P134 1.93 −5.38 0.86 9.40 39 3.17 176
P135 1.82 −5.42 0.87 7.61 49.8 3.27 177
P136 1.74 −5.27 0.86 10.4 64.4 5.7 178
P137 1.91 −5.34 0.83 10.6 64.7 5.6 197
P138 1.77 −5.31 0.69 11.34 63.0 4.93 179
P139 1.55 −5.81 0.60 13.58 64 5.18 180
P140 2.0 −5.04 0.61 4.8 47 1.4 181
P141 1.95 −5.06 0.61 4.5 62 1.7 181
P142 1.83 −5.38 0.91 11.81 58.2 6.25 182
P143 1.81 −5.32 0.88 12.36 71.2 7.74 182
P144 2.02 − 0.78 13.3 70.5 7.3 184
P145 1.51 −5.47 0.85 12.78 58.2 6.32 185
P146 2.00 −5.59 0.89 6.81 48 2.92 186
P147 1.95 −5.40 0.80 12.69 55 5.53 187
P148 1.97 −5.26 0.77 7.87 48 2.88 187

was also developed by researchers. Moreover, the BT unit could
be modified by the alkoxy groups or fluorine atoms. Additionally,
different π spacers were used to tune the properties of the BT-
containing conjugated materials. Copolymers based on BDT and
BT are a type of “weak donor” and “strong acceptor” D−A
combination, which would result in a deep HOMO level, thus
leading to a high VOC for the BHJ PSC devices. Figure 19
summarizes the molecular structures of P124-P148.
You and co-workers performed several studies on copolymers
based on fluorinated BT units. In 2011, they prepared P124 and
P125 and applied them in PSC devices.168 The spectra of the
polymers indicated an 80 nm blueshift when the solution
temperature increased from 25 to 100 °C. In comparison, the
fluorinated polymer P125 indicated an enhanced absorption
coefficient and a downshifted HOMO level compared to P124
without fluorine. In the PSC devices, P125 exhibited a high PCE
of 7.2% (VOC = 0.91 V, JSC = 12.9 mA/cm2, and FF = 61%) using
PC61BM as the acceptor material. At almost the same time, Ding
et al. also reported similar results.169 To further investigate the
influence of the number of fluorine atom on the properties of the
conjugated polymers, You and co-workers synthesized the P126
polymer using monofluorination BT and compared it with P124
(0F) and P125 (2F). From 0F to 2F, the VOC of the PSC devices
increased from 0.81 to 0.91 V.170 Furthermore, the JSC and FF of
the devices improved as the number of fluorine atom increased,
which could be ascribed to the suppressed charge recombination.
On the other hand, a quantum mechanical calculation indicated
that the polymer with 2F had a larger change in the dipole
moment between the ground and excited states (Δμge)
compared to polymers with 0F and 1F, which may contribute
to the suppressed geminate recombination. Furthermore, P125
displayed an enhanced face-on crystalline orientation and
improved π−π stacking along with a higher domain purity
compared to its counterparts. The PCE of the device fabricated
7419
by P125 increased to 7.16% from 4.53% in the case of P124.
When the alkoxy-modified benzodithiophene replaced the alkyl-
substituted benzodithiophene to construct the P127 copolymer,
the PSC devices achieved a high PCE of 8.30% in Jiang’s
group.171 Recently, P20 and P128 with thienothiophene as the π
spacer was developed by Wang et al., and their results suggested
that the fluorination of the polymer could enhance the intra- and
intermolecular interactions.91
In 2011, Wang et al. developed the P129 and P130 polymers
with different π spacers and investigated their influence on the
photovoltaic properties.172 As compared to P129, P130 with a
furan spacer had a deeper HOMO level, and thus, a higher VOC of
0.94 V was achieved in the PSC device. Then, they compared the
different π-bridges of furan, thiophene, and thienothiophene
(P131).173 The theoretical calculations indicated that the
polymer structures gradually changed from z-shaped to an
almost straight line when the π-bridges varied from furan to
thiophene and then to thienothiophene, and the absorption
bandgaps of the polymers ranged from 1.96 to 1.78 eV when the
HOMO levels changed from −5.44 to −5.21 eV.
Additionally, the dithienybenzothiadiazole (DTBT) unit was
developed as a side group to optimize the properties of the
photovoltaic materials. Tan et al. attached the DTBT to the main
chain of P132 using a vinylene group, which improved the
coplanarity of the polymer backbone.174 The P132-based PSC
device achieved a maximum PCE of 4.32%. Li and co-workers
further investigated the photovoltaic properties of this type of
polymer by selecting the fluorination BT unit.175 Zhu et al.
synthesized two interesting copolymers, P134 and P135, with
pending benzothiadiazole as a side group.176,177
Replacing “S” with “O”, “Se”, or “N” was proven to be an
effective strategy for optimizing the properties of BT-containing
polymers. By replacing the “S” with more electronegative “O”,
D−A copolymers containing benzooxadiazole (BO) units would
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Figure 20. Molecular structures of P149−P173.

possess lower HOMO levels than their BT equivalents. For Wei et al. achieved a maximum PCE of 5.7% with a VOC of 0.86 V
example, the P136 polymer-based BDT and BO synthesized by by blending PC61BM as the acceptor in the PSC device.178 Then,
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Table 13. Optical, Electronic, and Photovoltaic Performances of P149−P173

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P149 1.75 −5.31 0.92 10.70 57.5 5.66 188
P150 1.73 −5.26 1.00 5.80 34.6 2.11 205
P151 1.63 −5.14 0.82 5.78 49.5 2.34 189
P152 1.65 −5.11 0.78 12.46 62.0 6.03 189
P153 1.70 −5.35 0.88 12.94 70.9 8.07 190
P154 1.73 −5.39 0.82 13.11 65.28 7.02 191
P155 1.72 −5.33 0.85 13.3 68.0 7.7 192
P156 1.78 −5.28 0.86 8.7 59.0 4.4 192
P157 1.69 −5.29 1.03 7.05 48 3.52 193
P158 1.65 −5.40 0.86 7.72 43 2.92 193
P159 1.75 −5.04 0.98 10.60 57.8 6.37 194
P160 1.53 −5.48 0.79 7.23 47.08 2.70 196
P161 1.63 −5.41 0.86 12.05 59.9 6.21 197
P162 1.67 −5.32 0.82 12.53 54.9 5.64 197
P163 1.78 −4.92 0.54 9.47 60.6 3.1 199
P164 1.91 −5.26 0.75 11.90 67.2 6.00 202
P165 1.93 −5.32 0.89 17.43 61.48 9.53 203
P166 1.56 −5.29 0.66 8.3 44.0 2.4 93
P167 1.60 −5.19 0.78 11.80 54 5.0 200
P168 1.85 −5.44 0.86 9.1 58.6 4.5 198
P169 1.79 −5.40 0.83 12.7 62.0 6.5 198
P170 1.62 −5.46 0.78 9.3 47.0 3.4 204
P171 1.58 −5.19 0.80 11.71 61.0 6.00 205
P172 1.93 −5.23 0.92 11.71 65.0 7.11 206
P173 1.53 −5.44 0.75 12.56 54.2 5.11 207

thienothiophene was used as a spacer to prepare the P138
polymer in Li’s group, which indicated an enhanced hole
mobility of 0.023 cm2 V−1 s−1.179 In comparison with its BT
counterpart P131, P138 had a broader absorption spectrum and a
lower HOMO level by 0.1 eV. The inverted PSC device with a
structure of ITO/PFN/polymer:PC61BM/MoO3/Al was used to
investigate the performance of P138, and a maximum PCE of
7.05% was obtained with a VOC of 0.76 V. When the “S” atom
changed to the “Se” atom, the benzoselenadiazole (BSe)-
containing polymer P139 was developed by Tajima and co-
workers.180 Compared to its BT analogue, P139 had a red-shifted
absorption spectrum along with a higher HOMO level. The PSC
devices fabricated using P139 exhibited a PCE of 5.18% with a
VOC of 0.60 V.
Benzotriazole (BTz) is another BT derivative, which can be
easily modified by an alkyl chain to improve the solubility of the
resulting polymer. The more electron-rich “N” atom made BTz a
slighter weaker acceptor unit, which resulted in a higher HOMO
level compared to its BT-based counterpart. In 2010, Zou et al.
designed and synthesized the P140 and P141 polymers based on
the BTz unit; however, they achieved a relatively low PCE of
approximately 1%−2% and a low VOC approximately 0.61 V.181
As a useful method to improve the HOMO level, alkylthiol-
substituted BDT and fluorinated BT were used to improve the
properties of this type of polymer by Peng’s group.182 After the
optimization of the π spacer, the VOC of the device fabricated by
P143 increased to 0.88 V and a PCE of 7.74% was achieved.
Furthermore, Ade et al. conducted a series of studies on
copolymers based on BDT and BTz units. They determined that
the morphology of the P144/PC61BM blend was insensitive to
the processing conditions. It was believed that the low
equilibrium miscibility of PC61BM in P144 played a crucial role
in the morphological development of varied solvents.183 Then,
they investigated the influence of molecular weight on the
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photovoltaic performance using P144, and a maximum PCE of
7.3% was obtained from the PSC devices.184 Pyridine is a more
electron deficient unit than the benzene ring. When pyridine
replaced the benzene ring in the BT unit, the thiadiazolopyridine
(PyT) acted as a stronger acceptor than BT.185 As compared to
the BT-containing polymer, P145, which was based on BDT and
PyT, indicated a smaller bandgap and a decreased HOMO level,
and a maximum PCE of 6.32% was achieved in the PSC devices.
Additionally, the unsubstituted BDT and triisopropylsilyl-
ethynyl (TIPS)-substituted BDT were used in designing BTz-
containing conjugated polymers, and the photovoltaic parame-
ters of the PSC devices are listed in Table 12.186,187
Two-dimensional side chain groups, such as furan, thiophene,
selenophene, or benzene, were frequently introduced on BDT to
modify the properties of the PBDT-BT polymers (Figure 20 and
Table 13), and some very impressive photovoltaic results were
obtained. For example, P10 could yield PCE of 9.4% in the PSC
device. In 2010, Huo and co-workers synthesized the P149
copolymer-based thienyl-substituted BDT and BT, and the
polymer had an optical bandgap of 1.75 eV and a deep HOMO
level of −5.31 V.188 A PCE of 5.66% with a high VOC of 0.92 V
was obtained for the PSC device. When thienothiophene was
used as the π-bridge in P152, P151 and P152 depicted little
differences in the absorption spectra and molecular energy levels.
However, the hole mobility of P152 (1.97 × 10−3 cm2 V−1 s−1)
was considerably higher than that of P151 (1.58 × 10−5 cm2 V−1
s−1).189 The photovoltaic properties of the two polymers were
evaluated by blending PC61BM as the acceptor in the PSC
devices. Due to the enhancement of the hole mobility of P152,
the JSC of the device reached 12.46 mA/cm2, which was
significantly higher than that of P151 (5.78 mA/cm2). The
alkylphenyl-substituted BDT had a wide application in
constituting conjugated photovoltaic polymers for its large π-
conjugated area and good planarity. The polymer P153
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Figure 21. Molecular structures of P174−P186 based on BDT and TPD.
developed in Hou’s group possessed an absorption edge of
approximately 730 nm and a HOMO level of −5.35 eV.190 The
authors determined that 0.5% of DIO would result in a significant
improvement in the PCE from 5.09% to 8.07%; thus, they used a
series of characterization techniques, including AFM, TEM,
GIXD, and resonant soft X-ray scattering (RSoxS), to study the
change in the blend morphology. The results revealed that the
additive increased the crystallinity of the polymer, and a
multilength scale morphology was formed after the addition of
DIO, which was beneficial for exciton dissociation and charge
carrier transport. A maximum PCE of 8.07% was achieved with a
VOC of 0.88 V for the PSC device. Yang et al. synthesized the
polymer P154 based on alkoxyphenyl BDT and DTBT, and the
fluorine atom was used to decrease its HOMO level.191 The PSC
device based on P154 exhibited a PCE of 7.02% with a VOC of
0.82 V.
The fluorinated BT and alkoxy-substituted BT units were
widely used to optimize the PBDT-BT polymers with 2D side
chains. Janssen and co-workers prepared the P155 and P156
copolymers with thiophene or furan as the π spacer, and a
maximum PCE of 7.7% was obtained for the P156-based PSC
devices.192 Furthermore, the photovoltaic performance of the
device was insensitive to a wide range of active layer thicknesses
(i.e., from 100 to 250 nm). Stefan and co-workers synthesized the
polymers P157 and P158 by extending the thienyl side chains,
which showed moderated PCE around 3%−4% in the PSC
devices.193 Jiang and Cho et al. developed the P159 polymer with
a similar molecular structure and achieved a PCE of
approximately 6% for the PSC device processed without any
additives or post-treatments.171,194 Recently, Jo et al. synthesized
a medium bandgap copolymer based on thienylthio-substituted
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BDT and fluorinated BT, and the PSC device achieved a PCE
exceeding 9%.195 Li and co-workers synthesized P160 based on
alkoxyphenyl-substituted BDT and fluorinated BT, which
exhibited a broad absorption at 300−800 nm.196 Dai and co-
workers prepared P161 and P162 based on alkoxyl-substituted
BT and fluorinated BT.197 The HOMO level of P161 was lower
than that of P162 by 90 mV. A PCE of 6.21% with a VOC of 0.86 V
was obtained from the PSC device fabricated using P161,
whereas the P162-based PSC device yielded a PCE of 5.64% with
a VOC of 0.82 V.
Additionally, heteroatom substitution was widely studied by
researchers when designing copolymers based on BDT and BT
units.92,93,198−201 For example, Zou et al. synthesized the P163
polymer using BTz as the acceptor unit.199 Compared to its
counterpart with BT or BO as the acceptor, P163 indicated a
larger optical bandgap of approximately 1.82 eV and a high-lying
HOMO level of −4.92 eV; thus, the VOC of the PSC device was
only 0.54 V. Li and co-workers designed and synthesized the
polymer P164 composed of thienyl-substituted BDT and
fluorinated BTz, which showed a maximum PCE of 6.0% in
the PSC device.202 PCE of 4.74% was also recorded when the
thickness of active layer increased to 400 nm. Recently, they
incorporated alkylthio-substituted BDT into the polymer and
synthesized P165, and a very impressive PCE of 9.53% was
recorded by using a nonfullerene acceptor.203 “Se”, which is
another chalcogen, has a larger size and is less electronegative
than “S”. Due to their enhanced ground-state quinoid resonance
and improved planarity, the Se-containing polymers always had
narrow optical bandgaps.146 Wei and co-workers synthesized a
series of Se-substituted copolymers with Se substitution on the
side chain and/or a π spacer and/or an acceptor building block.93
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Table 14. Optical, Electronic, and Photovoltaic Performances of P174−P186

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P174 1.93 −5.67 1.0 2.0 39 0.8 211
P175 − − − − − − 103
P176 1.88 −5.56 0.89 7.6 57 3.9 103
P177 1.86 −5.66 0.66 1.2 26 0.2 103
P178 1.78 −4.85 0.9 7.8 42 3.0 214
P179 1.85 −4.98 0.98 8.7 48 4.7 214
P180 1.79 −5.41 1.05 10.6 60.0 6.7 216
P181 1.86 −5.30 0.92 10.94 60.4 6.08 217
P182 1.88 −5.48 0.87 9.20 62.8 5.03 217
P183 −− −5.62 1.00 14.32 52 7.59 218
P184 1.70 −5.52 0.91 3.22 45 1.33 219
P185 1.76 −5.42 0.96 13.20 55.88 7.14 220
P186 1.87 −5.40 0.87 10.90 63.0 6.04 221

The effects of the Se atom number on their absorption spectra,
molecular energy levels, hole mobilities, and photovoltaic
properties were studied. In comparison with their thiophene
equivalents, the absorption onsets of the Se-containing polymers
were red-shifted by 40−100 nm. The absorption onset of the all-
Se polymer P166 located at 792 nm and its HOMO was as high as
−4.64 eV. A relatively low PCE of 2.4% with a VOC of 0.66 was
obtained for the P166-based PSC device, thus suggesting that a
careful selection of heteroatoms should be considered when
designing highly efficient photovoltaic polymers. Chen and co-
workers developed P167 based on monofluorine-substituted
benzoselenadiazole and BDT, which indicated an optical band
gap of 1.60 eV. A PCE of 5.0% with a VOC of 0.78 V was obtained
for the corresponding PSC device.201 Several reports showed the
replacement of thiophene with furan would improve the
solubility of the polymer and result in a deeper HOMO level.98
Ge and co-workers developed three copolymers based on BDT
and benzooxadiazole with furan as the π-bridge. They used
alkoxy, thiophene, and furan-substituted BDT units as the
electron-donor unit to construct copolymers P130, P168, and
P169, respectively.198 Copolymers with 2D conjugated side
groups (P168 and P169) had a broader absorption range
compared to those with the alkoxy-substituted counterpart
(P130). Specifically, the optical bandgaps of the three polymers
were 1.91, 1.85, and 1.79 eV for P130, P168, and P169,
respectively. The authors determined that the treatment of the
polar solvent (such as methanol and ethanol) helped improve the
PCE of the PSC devices. For the P169-based devices, the VOC,
JSC, and FF values improved after the polar solvent treatment,
and the PCE thus increased to 7.0% from 3.0%, which resulted
from the increased hole mobility, more-balanced charge
transport, and better interpenetrating morphology. A copolymer
P170 with alkoxyphenyl-substituted BDT and benzooxadiazole
was synthesized in Zou’s group.204 In comparison with its BO-
containing counterpart, P170 possessed a similar optical band
gap but a deeper HOMO level. The P170-based PSC device
achieved a PCE of 6.2% with a VOC of 0.89 V.
Cao and co-workers applied naphtho[1,2-c:5,6-c]bis[1,2,5]-
thiadiazole (NT) when designing highly efficient copolymers in
2011.205 Compared with its BT counterpart P150, the NT-
containing P171 polymer demonstrated a pronounced red-
shifted absorption spectrum and higher hole mobility while
maintaining a suitable energy level. P171 exhibited a promising
photovoltaic performance with a PCE of 6%. Furthermore, they
developed naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole)
(TZNT) to enlarge the π-conjugated area of the BT-containing
7423
polymers.206 After optimization of the alkyl side chains, P172
exhibited a PCE of 7.11% with a high VOC of 0.92 V. Ma et al.
synthesized P173 by combining thienyl-substituted BDT as
donor unit and PyT as an acceptor unit, which showed a PCE of
5.11% with a VOC of 0.75 V, a JSC of 12.56 mA/cm2, and a FF of
54.2%.207
4.3. Copolymers Based On BDT and TPD/BDD
In 2010, a few groups designed and synthesized PBDT-TPD
polymers.71−74 Due to the low-lying HOMO levels of the PBDT-
TPD polymers, the PSC devices based on this type of polymer
always resulted in a relatively high VOC. In addition to the
copolymers based on BDT building blocks, TPD units were also
widely used as acceptors to construct other highly efficient
polymer systems.208,209 Figure 21 summarizes the copolymers
based on BDT units, and their basic optical and electronic
properties as well as photovoltaic performances are listed in
Table 14.
PBDT-TPD polymers based on alkoxy-substituted BDT and
alkyl-modified TPD were first synthesized and investigated, and
the P11-based PSC device achieved an initial PCE of 5.5%. A
further improvement in the PCE to over 8% was achieved by side
chain engineering of the polymer and fine-tuning the blend
morphology.75,210 Additionally, researchers synthesized the
P174 copolymer with alky-substituted BDT and TPD and
explored its photovoltaic properties.211 The P174 film possessed
an optical bandgap of 1.93 eV, which was slightly larger than its
alkoxy-substituted analogues (1.83 eV). The PSC device based
on P174 and PC61BM showed a high VOC of 1.0 V. Studies
incorporated thiophene spacers on both sides of the TPD unit
(DTTPD) to tune the physicochemical properties of PBDT-
TPD. Leclerc et al. and Zhang et al. synthesized a series of PBDT-
DTTPD copolymers, and the impact of the alkyl side chains on
the properties of the resulting copolymers was studied.103,212
Compared with PBDT-TPD without spacers, the nonsubstituted
thiophene spacer-containing P175 polymer demonstrated
similar absorption spectra, whereas the introduction of flexible
alkyl side chains on thiophene would result in a blueshift of the
absorption spectra. Furthermore, the effects of the π spacers on
the molecular energy levels and blend morphology were
observed.
As discussed above, polymers P68 composed of thienyl-BDT
and TPD developed by Ma’s group showed a maximum PCE of
6.17% with an impressive VOC of 1 V, which was the highest result
with a VOC over 1 V at that moment.126 The high VOC can be
attributed to its low-lying HOMO level of −5.61 eV, and this
result demonstrated its potential application in a tandem solar
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Table 15. Optical, Electronic, and Photovoltaic Performances of P187−P204

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P187 1.83 −5.39 0.89 8.0 67 4.8 211
P188 1.60 −5.59 0.88 6.70 47 2.74 222
P189 1.51 −5.79 0.41 1.53 44 0.28 222
P190 1.31 −5.37 0.72 13.5 54 5.3 223
P191 1.53 −5.40 0.80 6.50 60 3.12 224
P192 1.93 −5.63 0.92 9.62 62 5.50 226
P193 − −5.44 0.85 7.06 54.7 3.28 227
P194 − −5.25 0.62 3.39 53 1.13 228
P195 − −5.40 0.72 8.76 62 3.90 228
P196 − −5.42 0.73 10.68 62 4.84 228
P197 − −5.45 0.79 1.2 45 0.27 228
P198 − −5.36 0.88 12.37 62 6.78 228
P199 1.78 −5.59 0.96 11.00 58.5 6.18 229
P200 1.79 −5.60 0.97 8.28 41.7 3.35 230
P201 1.92 −5.41 0.87 2.64 33 0.73 231
P202 1.86 −5.40 0.83 1.81 30 0.45 231
P203 1.78 −5.49 0.87 4.75 45 2.18 232
P204 1.81 −5.32 0.86 13.13 71.8 8.12 233

Figure 22. Molecular structures of P187−P204.

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cell. Similar results were obtained by Wei and co-workers.213
Additionally, furan and selenophene were incorporated on BDT
as 2D side chains, and the effects of the ring substituents on the
morphology of the blends with PCBM were studied by
researchers.214,215 The DFT calculations indicated that the
optimal torsion angles between the BDT unit and the adjoining
ring substituents had considerable differences. The BDT with a
furan substituent had a more planar structure than the BDT with
thiophene and selenophene. The photovoltaic properties of the
polymers were investigated using standard solar cell devices, and
they showed very poor performance when the additive was not
used. After the optimization of the DIO, the short-circuit current
had a significant increase, and the PCE of the P68-based device
reached 6.5%. Then, the authors examined the morphology of
the polymers/PC71BM blends using a bright-field TEM, and the
results suggest that the use of the DIO prevented the formation
of large fullerene clusters, thus increasing the JSC. Beaujuge et al.
modified the TPD with a carbonyl substitution to further
decrease the HOMO and LUMO levels of the resulting P180
polymer.216 By fine-tuning the flexible side chains, the PSC
device based on P180 achieved a PCE of 6.7% with a high VOC of
1.05 V. Wei and co-workers introduced the thiophene unit as the
π spacer to tune the properties of the 2D PBDT-TPD
polymers.217 When the unsubstituted thiophene was used, the
resulting polymer had a poor solubility in most common
solvents, so a hexyl-substituted thiophene spacer was used and
P181 was synthesized. Although the DFT calculation results
suggested that the coplanar structure of the BDT and TPD unit
was distorted, the solubility and absorption coefficient improved.
Compared to P68, P181 maintained a similar optical absorption
but higher HOMO level. The PSC device based on P181
demonstrated a lower VOC but a higher JSC than that of P68, and a
PCE of 6.08% was achieved for the P181-based PSC device.
Recently, to increase the density of the acceptor units, Wei et al.
introduced two TPD units in one repeating unit and synthesized
the P183 copolymer.218 P183 possessed a low-lying HOMO level
of −5.62 eV, and the PSC device fabricated by P183 achieved a
PCE of 7.59% with a high VOC of 1 V. By extending the 2D
conjugated side chain on BDT, Stefan and co-workers
synthesized the polymer P184, which showed a PCE of 1.33%
in the PSC device by using PC61BM as an acceptor.219 Jin and co-
workers synthesized the alkoxyphenylthiophene-substituted
BDT unit and prepared the P185 copolymer. 220 They
determined that the PCE of the PSC devices had a significant
improvement from 4.19% to 7.14% when the active layer was
treated with methanol. Kang et al. introduced alkylthienylene-
vinylene thiophene (TVT) on BDT as a highly conjugated side
group and synthesized the P186 polymer, which had an
enhanced absorption intensity at short wavelengths (∼400
nm).221 The PSC devices based on P186 achieved a higher PCE
of 6.04% compared to its thienyl-substituted equivalent (4.82%)
due to its increased JSC value (from 8.05 to 10.9 mA/cm2). Basic
optical and electronic properties as well as photovoltaic
performances are listed in Table 15.
As shown in Figure 22, several novel TPD-like building blocks
were developed and applied when designing photovoltaic
polymers. Olson and co-workers designed and synthesized the
P187 copolymer based on thienoisoindoledione (TID) and
BDT.211 When the benzene ring was inserted into the middle of
the TPD, the quinoid structure of the copolymer was stabilized
by the aromatic resonance and intramolecular charge transfer,
which resulted in a red-shifted absorption spectrum as compared
to its analogue based on TPD and BDT (P11). Although P187
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Review
had an optimized absorption spectrum, the P187 film exhibited a
disordered molecular arrangement, which resulted in a negative
impact on its photovoltaic performance. Fréchet et al. replaced
the imide of TPD with either the ester group or nitrile group to
investigate the effects of electron-withdrawing substituents on
the optical and electronic properties of the copolymers.222 In the
PSC devices, when mixed with PC61BM, the authors determined
that copolymers based on imide and ester (P188) acted as donor
materials. However, when mixed with poly(3-(4-n-octyl)-
phenylthiophene), the nitrile-containing polymer P189 per-
formed as an n-type material in the bilayer device. By
incorporating a thiophene into the TPD, an unique unit
known as n-octyl-2,7-dithia-5-azacyclopenta[a]pentalene-4,6-
dione (DTPD) was synthesized in Kwon’s group.223 P190 had
a wide absorption range from 300 to 900 nm. The photovoltaic
performance of the polymer was investigated using a BHJ solar
cell with a device structure of ITO/PEDOT:PSS/poly-
mer:PC71BM/TiO2/Al, and a PCE of 5.3% was obtained. Hou
and co-workers incorporated a thiophene spacer between the
BDT and the TID to further improve the photovoltaic
performance of this type of copolymer.224 Compared to its
counterpart, which was based on BDT and TPD, the new P191
polymer possessed a broad absorption spectrum and a higher
HOMO level due to its strong quinoid structure, and the PSC
device fabricated by P191 and PC61BM obtained a PCE of 3.12%
with a VOC of 0.80 V. The bithiophene imide (BTI) unit had a
structure consisting of an imide group in the middle of two
thiophene spacers, which possessed a smaller steric hindrance
than that of the TPD unit. When the polymers based on BTI and
BDT were designed and applied to organic thin-film transistors,
they exhibited a good carrier mobility over 0.1 cm2 V−1 s−1.225
Marks et al. synthesized the P192 copolymer based on BTI and
BDT and applied it in the PSC device.226 P192 had an absorption
onset of 740 nm and an electrochemical HOMO level of −5.60
eV. With the use of an inverted architecture with an ITO/ZnO/
polymer:PC71BM/MoOx/Ag structure, the P192-based device
achieved a PCE of 5.50% with a VOC of 0.92 V. Yu and co-workers
and You et al. conducted a series of studies on the relationship
between the dipole moment and the photovoltaic performance
for conjugated polymers, and they concluded that the increased
dipole change (Δμge) was beneficial for improving the PCE of
the devices.164,170 Therefore, they replaced one of the carbonyls
with a sulfonyl group on the TPD unit to increase the local dipole
moment change between the ground and excited states.227
However, the resulting P193 polymer exhibited a diminished
photovoltaic performance. The authors believed the strong
electron-withdrawing sulfonyl group was detrimental to charge
separation, and the results demonstrated that the positive linear
correlation between the PCE value and Δμge were suitable only
in a certain range. A series of copolymers (P194−P197) based on
BDT and the acceptors with varied electron-withdrawing
capabilities were synthesized in Kim’s group.228 The theoretical
calculation and experiment results suggested that a stronger
electron-withdrawing acceptor unit would result in lower
HOMO and LUMO levels of the resulting polymers, and the
LUMO decreased more rapidly than the HOMO, which caused a
narrowed bandgap. According to their findings, they synthesized
P198 polymer, and the PSC device achieved a PCE of 6.78%. Ma
and co-workers introduced the 2D conjugated thienyl side chain
on BDT and synthesized polymer P199, and PCE about 6% was
obtained in the PSC device with a D/A ratio of 1:0.5.229 Then
they synthesized P200 by modifying the molecular structure of
P199, and a PCE of 3.35% was recorded in the PSC device.230
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Figure 23. Molecular structures of P205−P227.

Additionally, benzo-[1,2-c:4,5-c′]dithiophene-4,8-dione conjugated polymers. In 2012, Aso and co-workers synthesized

(BDD) units were widely used when designing photovoltaic the copolymers P201 and P202.231 P201 demonstrated a larger
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Table 16. Optical, Electronic, and Photovoltaic Performances of P205−P227

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P205 1.78 −5.41 0.77 5.0 50.3 1.9 235
P206 1.68 −5.43 0.65 6.3 55.2 2.3 235
P207 1.81 −5.48 0.81 4.74 42 1.55 236
P208 1.85 −5.62 0.91 10.61 62 6.08 236
P209 1.62 −5.11 0.65 12.5 54 4.39 237
P210 1.38 −5.16 0.72 11.47 62 5.12 238
P211 1.67 −5.52 0.76 17.9 57.6 7.8 239
P212 1.74 −5.12 0.71 7.00 61.5 3.06 81
P213 1.73 −5.12 0.76 10.13 64.3 5.0 81
P214 1.72 −5.35 0.83 11.71 40 3.90 241
P215 1.82 −5.41 0.95 10.82 61.4 6.3 242
P216 1.78 −5.51 0.94 11.28 64.7 6.9 243
P217 1.80 −4.98 0.83 6.37 54 2.9 244
P218 1.80 −5.07 0.87 6.52 55 3.1 244
P219 1.81 −5.08 0.91 6.84 59 3.7 244
P220 1.72 −5.20 0.86 12.77 69.93 7.68 245
P221 1.77 −5.87 0.96 6.5 54 3.4 246
P222 1.72 −5.31 0.85 11.3 75.7 7.25 247
P223 1.64 −5.05 0.64 12.56 70.05 5.63 82
P224 1.66 −5.19 0.76 13.05 63.34 6.25 82
P225 1.68 −5.19 0.80 13.60 67.68 7.39 82
P226 1.59 −5.34 0.70 11.10 62.5 4.86 248
P227 1.64 −5.97 0.98 10.4 48 4.9 249

optical bandgap (1.92 eV) than P202 (1.86 eV), and they had
similar HOMO levels around −5.40 eV. However, both of the
polymers showed very low PCEs for the PSC devices. Ding et al.
prepared the P203 copolymer, and the PSC device showed a
PCE of 4.33%.232 Very recently, Sun and co-workers developed
the P204 copolymer based on alkylphenyl-BDT and BDD, which
indicated an optical bandgap of 1.82 eV and a HOMO level of
5.32 eV.233 The P204-based PSC device achieved a high PCE of
8.12%.
4.4. Copolymers Based On BDT and Qx
Due to its strong electronegativity, Qx and its derivatives were
widely used as electron moieties to build novel photovoltaic
polymers by copolymerizing with thiophene, fluorene, and IDT
electron-rich units.234 In comparison with BT, Qx has more
substitution positions, which could be used to improve the
solubility of the resulting polymers. For example, alkyl,
alkylphenyl, and alkylthienyl substitutions were frequently used
as side chains to modify the Qx units. Additionally, the fluorine
atom and alkoxyl groups were commonly seen in the Qx-
containing polymers. Among the numerous Qx-based D−A
polymers, polymers based on BDT and Qx demonstrated
excellent photovoltaic performance. Figure 23 summarizes the
molecular structures and electronic properties as well as
photovoltaic performances for P205-P227 are listed in Table 16.
In 2008, the first BDT-Qx polymer P5 reported by Hou and
co-workers only achieve a very low PCE of 0.23%.26 In 2012,
Park et al. synthesized P205 and P206 based on phenyl-
substituted Qx and BDT.235 Due to its enhanced intermolecular
interaction of P206 with the thiophene spacer, the P206-based
PSC device showed improved JSC and FF values, and a maximum
PCE of 2.3% was thus obtained. Hwang et al. reported the P207
and P208 polymers based on triisopropylsilylethynyl (TIPS)-
substituted BDT and Qx with or without fluorination.236 P208
indicated downshifted HOMO and LUMO levels compared to
P207 without causing a considerable influence on their
absorption properties. Due its improved VOC from 0.79 to
7427
0.91 V for the P208-based PSC device, a high PCE of 6.08% was
obtained. Cao et al. synthesized a series of copolymers based on
alkylthienyl-substituted Qx.237 After optimization of the side
chains, P209 achieved the best PCE of 4.39% with a relatively low
VOC of 0.65 V. Sharma and co-workers introduced thiadiazolo-
quioxaline to prepare the P210 copolymer, which possessed a
low bandgap of 1.38 eV.238 Because P210 exhibited superior
solubility in THF, the authors fabricated the PSC device using
THF/DIO as a processing solvent, and a notable PCE of 5.12%
was recorded. Chou et al. synthesized the P211 copolymer based
on BDT and meta-phenoxyl-substituted Qx.239,240 They
determined that by increasing the molecular weight form 37 to
71 kDa, the PCEs of the P211-based PSC devices increased to 8%
from 7%.
In 2012, Hou and co-workers incorporated the thienyl-BDT
when constructing the P213 polymer.81 As compared to its
alkoxyl-substituted counterpart P212, P213 showed a broader
absorption spectrum and a higher hole mobility. The PSC device
based on P213 obtained a PCE of 5%, which was 60% higher than
that of the P212-based PSC device, suggesting that the
application of the 2D conjugated side chains would be a feasible
approach to improve the photovoltaic performance of the Qx-
based polymers. Furthermore, Li et al. prepared P214 without
the thiophene spacer, which achieved a PCE of 3.9%.241
Additionally, alkoxy groups were introduced to modify the Qx
unit, and the P215 and P216 polymers were designed and
synthesized by Zhu’s group.242,243 P215 exhibited very low-lying
HOMO level of −5.51 eV, which resulted in a VOC over 0.9 V for
the PSC device and a PCE of 6.31% was obtained. P216 showed
broad absorption spectrum and higher carrier mobility than
P215; hence, the PCE was raised to 6.9% due to the enhanced JSC
and FF values.
To further investigate the effects of the fluorine substituents on
the device performance, Luscombe and co-workers synthesized
three polymers, P217−P219, with different numbers of fluorine
atoms.244 The HOMO levels of the three polymers were located
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Chemical Reviews
Figure 24. Molecular structures of P228−P253.
at −4.98, − 5.07, and −5.08 eV for P217, P218, and P219,
respectively. Due to its improved VOC for the P219-based PSC
device, a maximum PCE of 3.7% with a high VOC of 0.91 V was
achieved. Wang et al. systematically studied the effects of the 2D
conjugated side chains on the photovoltaic performance of the
PBDT-Qx polymer and synthesized a series of PBDT-Qx
polymers with alkoxyphenyl or alkylthienyl on the BDT and/or
Qx units.245 Among which, P220 achieved the best PCE of 7.68%
7428
Review
due to its broad absorption spectrum and close molecular
packing. Andersson et al. introduced two alkyl side chains on the
BDT unit and synthesized the P221 polymer.246 Even though
P221 demonstrated a blueshifted absorption spectrum compared
to its one alkyl side-substituted analogue, the P221-based PSC
device achieved a very high VOC of 0.96 V. Recently, Cao et al.
synthesized a series of polymers based on monofluorinated Qx
and BDT.247 By fine-tuning the side chains on the thienyl
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Table 17. Optical, Electronic, and Photovoltaic Performances of P228−P253

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P228 1.45 −5.15 0.71 9.4 61 4.1 259
P229 1.36 −5.10 0.62 5.2 43 1.4 259
P230 1.50 −5.30 0.66 15.9 48.9 5.12 261
P231 1.44 − 0.76 16.21 65 8.00 262
P232 1.46 −5.35 0.76 13.6 60 6.2 86
P233 1.52 −5.33 0.77 7.42 59 3.3 86
P234 1.44 −5.16 0.69 10.46 48.9 3.5 263
P235 1.47 −5.24 0.72 12.64 56.5 5.1 263
P236 1.37 −5.26 0.78 5.69 58.09 2.60 264
P237 1.29 −5.31 0.78 2.67 52.36 1.09 153
P238 1.46 −5.47 0.88 6.59 54.1 3.14 140
P239 1.39 −5.25 0.74 13.17 57.28 5.58 265
P240 1.29 −5.20 0.68 9.89 50 4.04 265
P241 1.82 −5.39 0.68 4.11 44.8 1.2 266
P242 1.53 −5.51 0.98 6.2 53 3.2 267
P243 1.54 −5.11 0.71 7.93 34 1.91 275
P244 1.71 −5.24 0.77 11.71 71 6.41 277
P245 1.66 −5.38 0.80 10.20 65 5.36 278
P246 − −5.81 0.85 6.40 52 2.80 279
P247 − −5.75 0.79 9.38 66 4.85 279
P248 − −5.62 0.72 14.96 68 7.31 279
P249 − −5.62 0.66 11.82 52 3.98 279
P250 1.59 −5.38 0.85 10.48 65.8 5.86 280
P251 1.60 −5.52 0.88 8.95 60 4.76 281
P252 1.58 −5.64 0.92 11.30 68 7.04 281
P253 1.05 −4.96 0.38 11.74 57.2 2.55 280

substitution, the P222-based PSC device achieved the best PCE
of 7.25%. Furthermore, Hou and co-workers designed four
polymers, P13 and P223−P225, with increasing fluorine atoms
from 0 to 4.82 The results suggested that the introduction of
fluorine atoms did not have a significant impact on their optical
bandgaps (less than 0.1 eV) but had a distinct influence on the
molecular energy levels, ranging from −5.05 to −5.35 eV. The
PSC devices fabricated using these four polymers demonstrated
similar JSC and FF values with VOC increasing from 0.64 to 0.90 V,
and a maximum PCE of 8.55% was obtained for the P13-based
(4F) PSC device.
In addition to the Qx units discussed above, there were several
other Qx derivatives developed by researchers. For example,
pyrene-fused Qx was synthesized by Zhu and co-workers, and the
P226-based PSC device achieved a PCE of 4.86%.248 Wang et al.
synthesized the P227-based pyrrole-fused Qx and BDT. Due its
low-lying HOMO level, the P227-based PSC device showed a
maximum PCE of 4.9% with a high VOC of 0.98 V.249
4.5. Copolymers Based On BDT and DPP/IID
Early in 1974, the DPP unit was synthesized by researchers,
which possessed a strong electron-deficient amide group and a
planar conjugated backbone.84 In OFET devices, the DPP-based
molecules showed excellent transport properties for both the
electron and the hole.250−252 Over the past few years,
photovoltaic materials based on DPP have emerged and
demonstrated good applications for its broad absorption
properties and high carrier mobility.95,253 PCEs over 8% have
been achieved by PSC devices fabricated by DPP-based
polymers.254−257 Furthermore, polymers containing BDT as
the donor unit and DPP as the acceptor unit gained considerable
attention, especially due to their successful application in
multiple junction solar cells.86,96,258 Here, a few representative
BDT-DPP-based polymers have been summarized.
7429
Ding et al. synthesized a series of copolymers based on alkyl-
substituted BDT and DPP, and the influence of the alkyl side
chains on the charge transport and the photovoltaic properties of
the conjugated polymers were studied, as indicated in Figure
24.259 P229 demonstrated a broader absorption spectrum and a
higher-lying HOMO level than P228. In the OFET devices, P229
demonstrated a considerably higher hole mobility than P228 (1.6
× 10−3 vs 3.6 × 10−4 cm2 V−1 s−1) due to its improved interchain
interactions. However, in the PSC devices, P228 achieved a PCE
of 4.1%, whereas P229 achieved a PCE of 1.4%, suggesting that
the effects of the alkyl side chains on the performances of the
OFETs and PSCs were quite different. Furthermore, copolymers
based on alkoxyl-substituted BDT and DPP were frequently seen
in the PSCs, which showed PCEs of approximately 2%−
3%.101,260 Recently, Morse et al. further optimized the side chain
length on the BDT and DPP, and the PCE was improved to
4.35% for the P230-based PSC device.261 A further improvement
in the PCE to 5.12% was obtained for the optimized inverted
device structure. In 2014, Hwang et al. synthesized P231 by
incorporating TIPS-substituted BDT and DPP, which achieved a
low bandgap of 1.44 eV.262 As a result, P231 showed an OFET
hole mobility of up to 0.12 cm2 V−1 s−1, and an extraordinary
PCE of 8.0% with a VOC of 0.76 V was recorded for the PSC
device.
The 2D-conjugated side chains were widely used to improve
the photovoltaic performance of PBDT-DPP polymers. Except
for the thiophene unit (see P14, P24), the benzene ring, furan,
and other conjugated side chains were developed when
constructing PBDT-DPP polymers. For instance, Yang and co-
workers prepared the P232 and P233 copolymers using phenyl-
substituted BDT as the donor unit and thiophene or furan as the
π-bridges.86 Compared with their thienyl-BDT counterparts,
phenyl-containing polymers indicated deeper HOMO levels.
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After optimization of the PSC devices, P232 exhibited the best
PCE of 6.2% with a VOC of 0.76 V. Ge et al. introduced furanyl-
BDT to construct the PBDT-DPP polymers and synthesized
P234 and P235 with different π-bridges.263 As compared to their
alkoxyl-substituted analogues, P234 and P235 showed narrowed
optical bandgaps and downshifted HOMO levels. P235 using
furan as the π-bridge achieved a maximum PCE of 5.1% with a
VOC of 0.72 V.
To extend the conjugated side chain, Lee et al. introduced
benzothiophene on BDT and synthesized the P236 polymer.264
P236 showed a lower HOMO level of −5.26 eV and a broader
absorption spectrum with a bandgap of 1.37 eV, and a PCE of
2.6% was recorded for the P236-based PSC device. Polymer
P237, which was developed by Yang and co-workers, possessed a
terthiophene group as the side chain on BDT, which showed a
HOMO level of −5.31 eV and an optical bandgap of 1.29 eV.153
However, the P237-based PSC device showed a relatively low
PCE of approximately 1%. To improve the VOC of the PSC
devices based on the DPP-containing polymer, Hou et al.
introduced a dialkylthio-substituted BDT to construct the P238
polymer, which showed a low-lying HOMO level of −5.47 eV
(130 mV lower than its thienyl-BDT counterpart).140 A high VOC
of 0.88 V was obtained for the P238-based PSC device.
In addition to the PBDT-DPP polymers mentioned above,
several interesting molecules (P239−P242) have been devel-
oped by researchers. For example, modifications on the BDT or
DPP units using thiazole as the bridge were all studied, and the
photovoltaic parameters of the PSC devices are summarized in
Table 17.265−267
Isoindigo (IID) was another strong electron-withdrawing unit
widely used for the construction of low bandgap D−A
polymers.268,269 After molecules based on IID were first reported
by Reynolds et al. in 2010, it was soon recognized as a superior
building block due to its planar conjugated backbone, electron-
deficient character, and outstanding absorption property.270−272
The IID-based polymers always exhibited low bandgaps from 1.3
to 1.8 eV as well as low-lying HOMO levels. A high PCE over 8%
and a high mobility over 3 cm2 V−1 s−1 were successfully achieved
for IID-based polymers.273,274 Here, we summarized some
representative PBDT-IID polymers and discussed their
applications in PSCs.
In 2011, Zhang et al.275 and Pan et al.276 independently
reported the P243 polymer based on BDT and IID. They both
selected the alkoxyl-substituted BDT to be used as the donor unit
to construct the P243 copolymer, which indicated an optical
bandgap of 1.54 eV and a HOMO level of −5.20 eV. Due to the
low JSC and FF values, P243-based PSC devices showed PCEs
approximately 1%−2%. Polymer P244 developed by Sun and co-
workers exhibited a PCE of 6.41% by applying PCBM as donor in
the PSC device.277 In 2013, Andersson’s group reported the
P245 polymer based on alkyl-substituted BDT and IID.278 The
P245-based PSC device achieved an impressive PCE of 5.4% with
a VOC of 0.80 V.
In 2014, Wang and co-workers conducted a systematic study
on the photovoltaic properties of IID-based polymers using
different numbers of thiophene spacers.279 They prepared four
polymers, P246−P249, containing different thiophene spacers
from 0 to 3. P248 and P249 showed red-shifted spectra in the
solid state, and the HOMO levels of P246−P249 were located at
−5.81, − 5.75, − 5.62, and −5.62 eV, respectively. For the planar
polymer structure of P248 using bithiophene as the π spacer, the
PSC device based on P248 achieved the best PCE of 7.4%.
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Recently, 2D-BDT was used to improve the photovoltaic
performance of PBDT-IID polymers. Chou et al. synthesized the
P250 polymer based on thienyl-BDT, which exhibited a high
hole mobility of 0.1 cm2 V−1 s−1 in the OFET device.280 When it
was applied in the PSC device, a promising PCE of 5.86% with a
VOC of 0.85 V was obtained.
Peng et al. introduced the fluorine atom on the IID unit and
synthesized the P252 copolymer.281 As compared to its
counterpart P251 without fluorination, P252 showed a more
planar configuration. P252 possessed a smaller optical bandgap
and a deeper HOMO level as well as a higher carrier mobility
compared to P251. The P252-based PSC device achieved a
notable PCE of 7.04% with a high VOC of 0.92 V.
Chou and co-workers prepared the P253 copolymer based on
thienoisoindigo and BDT, which showed a very low optical
bandgap of 1.05 eV.280 Furthermore, P253 demonstrated
excellent ambipolar mobility in the OFET devices. However,
the P253-based PSC device achieved a poor photovoltaic
performance.
4.6. Copolymers Based On BDF or DTBDT
Because BDT-based polymers have achieved considerable
success in designing highly efficient photovoltaic materials,
several block units derived from BDT were developed and
applied to construct photovoltaic polymers and small molecules,
such as benzodifuran (BDF), BDSe, dithienobenzodithiophene
(DTBDT), naphthodithiophenes, anthradithiophene, tetrathie-
noanthracene, and BDT isomers (Figure 25).282−291 Polymer
Figure 25. Building blocks derived from BDT units.
solar cells fabricated using copolymers based on both BDF and
DTBDT all achieved PCEs over 9%; in this section, we used BDF
and DTBDT as examples and summarized their application in
constructing highly efficient photovoltaic materials.
Furan is a common renewable product, which can be prepared
using vegetable residues in the food and agricultural industries.
When compared to thiophene, the more electronegative oxygen
of furan affects the electronic and optoelectronic properties.
Moreover, because the atomic radius of the oxygen atom is
smaller than that of the sulfur atom, the furan-containing
polymers have increased planarity and conjugation due to its
reduced steric hindrance. Figure 26 summarizes the copolymers
based on BDF.
As shown in Figure 27, Biewer et al. synthesized the
phenylethynyl-substituted BDF unit and prepared three
polymers, P254−P256.292,293 The three polymers exhibited
similar optical bandgaps of approximately 2.0 eV, whereas their
HOMO levels increased from −5.39 to −5.30 or −5.10 eV for
P256 to P255 or P254. Due to the relatively low JSC and FF
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Figure 26. Molecular structures of P254−P262 based on BDF.

Figure 27. Molecular structures of P263−P271 based on BDF.

Table 18. Optical, Electronic, and Photovoltaic Performances of P254−P262

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P254 2.05 −5.10 0.75 4.0 34 1.05 293
P255 2.04 −5.30 0.81 2.24 44 0.79 292
P256 2.07 −5.39 0.83 3.71 39 1.19 292
P257 1.73 −5.63 0.85 2.89 59 1.44 294
P258 1.64 −5.49 0.75 1.74 48 0.65 294
P259 1.6 −5.7 0.74 1.66 48.6 0.59 295
P260 1.7 −5.7 0.64 1.31 36 0.30 295
P261 1.4 −5.5 0.69 7.0 60 2.89 296
P262 1.3 −5.6 0.66 7.4 47 2.28 296

values, PSC devices fabricated using these polymers only
achieved a PCE of approximately 1%.
Nonsubstituted BDF units were developed when synthesizing
conjugated polymers. Zhang and co-workers designed the
synthesized benzo[1,2-b:5,4-b′]difuran (syn-BDF) and benzo-
7431
[1,2-b:5,4-b′]difuran (anti-BDF) units and prepared the two
copolymers by copolymerizing with the isoindigo unit.294 As
summarized in Table 18, P257 had a considerably larger optical
bandgap of 1.73 eV compared to P258 (1.64 eV), whereas P257
possessed a deeper HOMO level compared to P258, suggesting
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Table 19. Optical, Electronic, and Photovoltaic Performances of P263−P271

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P263 1.6 −5.10 0.78 11.77 54.6 5.01 297
P264 1.73 −5.11 0.69 9.87 65.3 4.45 298
P265 1.93 −4.99 0.44 4.92 57.5 1.24 298
P266 1.70 −5.19 0.82 5.04 70.0 2.88 298
P267 1.60 −5.33 0.62 9.17 58.4 3.3 299
P268 1.68 −5.08 0.73 9.94 60.9 4.42 300
P269 1.61 −5.11 0.80 5.84 55.6 2.60 300
P270 1.63 −5.20 0.78 13.51 61.0 6.42 301
P271 1.56 −5.11 0.68 14.4 62 6.1 302

Figure 28. Molecular structures of P272−P280.

Table 20. Optical, Electronic, and Photovoltaic Performances of P272−P280

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P272 1.53 −5.03 0.54 13.13 60.03 4.26 303
P273 1.52 −5.11 0.63 13.88 59.81 5.23 303
P274 1.53 −5.07 0.61 15.75 53.82 5.17 303
P275 1.60 −5.44 0.87 5.88 44.59 2.28 303
P276 1.61 −5.25 0.59 14.21 60.70 5.08 303
P277 − −5.05 0.64 14.6 66 6.13 283
P278 − −5.04 0.64 16.8 64 6.87 283
P279 1.51 −4.98 0.78 13.04 61.55 6.26 305
P280 1.50 −5.12 0.65 12.11 64 5.01 306

that the syn and anti structures of BDF had significant influences
on the optical and electronic properties of the conjugated
polymers.
Jeffries-El and co-workers synthesized the alkyl-substituted
BDF unit and prepared the P259 and P260 copolymers. When
the alkyl side chains were introduced into the different positions
of the thiophene spacer, the two resulting polymers demon-
strated a distinct absorption spectra and photovoltaic perform-
ance. Specifically, the optical bandgap of P259 was 1.6 eV, while
that of P260 was 1.7 eV.295 Both polymers showed photovoltaic
responses in the PSC devices; however, the PCEs were lower
than 1%. Then, they prepared a series of copolymers using
thiophene or furan as π-bridges, and these polymers depicted
similar optoelectronic properties.296 The furan-containing
polymer P261 achieved the best PCE of 2.89%. Basic optical
and electronic properties as well as photovoltaic performances
are listed in Table 19.
7432
In 2012, Hou and co-workers initially synthesized the alkoxy-
substituted BDF unit and used it to synthesize photovoltaic
polymers.297 By copolymerizing with the DTBT unit, they
prepared the low bandgap P263 polymer, which had an optical
bandgap of 1.6 eV and a HOMO level of −5.1 eV. A promising
PCE of 5.01% was achieved for the PSC device, demonstrating its
potential in designing highly efficient polymers for PSCs.
Li and co-workers selected three different electron-deficient
groups, BT, BO, and BTz, as acceptor units and synthesized the
copolymers P264−P266.298 The optical bandgaps of the three
copolymers ranged from 1.70 to 1.93 eV, whereas their HOMO
levels changed from −4.99 to −5.11 eV. The PSC device based
on P264 achieved the highest PCE of 4.45%. Zou and co-workers
prepared the P267 copolymer based on BDF and monomer-
fluorinated BT, and a PCE of 3.3% was achieved for the PSC
device.299
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Figure 29. Molecular structures of P281−P286 based on BDF.
Table 21. Optical, Electronic, and Photovoltaic Performances of P281−P286
polymer Egopt (eV) HOMO (eV) VOC (V)
P281 1.97 −5.41 0.97
P282 1.65 −5.33 0.87
P283 1.70 −5.31 0.80
P284 1.67 −5.25 0.83
P285 1.68 −5.30 0.83
P286 1.83 −5.43 0.92
Li and co-workers used thiophene and furan rings as side
chains to replace the alkoxy side chains, and they synthesized the
P268 and P269 copolymers.300 P268 using thiophene as a side
chain showed larger optical bandgap and higher HOMO level
than P269. However, the hole mobility of P268 reached 9.0 ×
10−3 cm2 V−1 s−1, which was much higher than that of P269. The
PSC device based on P268 achieved a PCE of 4.42%, whereas the
P269-based device achieved a PCE of 2.6%.
Zou et al. designed an interesting thieno[2,3-f ]benzofuran
unit and prepared the P270 copolymer by copolymerizing with
the DTBT unit, which achieved a PCE of 6.42%.301 Furthermore,
Li and co-workers prepared a P271 copolymer by adopting the
monofluorinated BT as the acceptor unit, and the PSC device
achieved a PCE of 6.1%.302
Hou and co-workers synthesized a series of copolymers
constructed using BDF and TT, and varied functional groups,
such as carbonyl, ester, fluorine, sulfuryl, and cyano, were
introduced on the TT units to finely tune the molecular energy
levels of the P272−P276 polymers (Figure 28 and Table 20).303
The P275 and P276 copolymers with sulfuryl and cyano groups
had blueshifted absorption spectra compared to other polymers.
On the basis of the electrochemical measurements, they arranged
the electron-deficient abilities of these functional groups in
order: carbonyl < fluorine + ester < fluorine + carbonyl < sulfuryl
< cyano + ester. The VOC of the PSC devices based on these
polymers ranged from 0.54 to 0.87 V, and the PCEs ranged from
2.28% to 5.23%. Additionally, Li et al. prepared a copolymer
based on BDF and carbonyl-substituted TT with different alkyl
side chains, which demonstrated an improved VOC from 0.54 to
0.66 V for the PSC device.304 Yu et al. designed the
benzodiselenophene unit and synthesized the P277 and P278
copolymers by copolymerizing with the selenopheno[3,4-
b]selenophene and thieno[3,4-b]thiophene units.283 The
selenium-containing polymers showed narrowed bandgaps and
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Review
JSC (mA/cm2) FF (%) PCE (%) ref
11.2 68 7.4 307
9.14 59.2 4.71 308
9.81 58.7 4.61 309
5.28 51.0 2.22 310
8.74 61.2 4.44 310
13.28 77.4 9.43 233
improved hole mobilities. A best PCE of 6.87% with a VOC of 0.64
V was recorded for the all-Se polymer P278; however, due to the
relatively high-lying HOMO levels, the PSC devices based on
these polymers were lower than 0.7 V, thus limiting the PCEs.
The 2D conjugated substitutions, such as thiophene and furan,
were introduced to BDF as side chains by researchers. Hou and
co-workers synthesized the P279 copolymer based on thienyl-
BDF and carbonyl substituted TT.305 Compared with its alkoxy-
substituted counterpart, P279 showed narrowed optical bandgap
and downshifted HOMO level. Furthermore, the hole mobility
of the P279/PC71BM blend reached 0.128 cm2 V−1 s−1. The VOC
of the PSC device based on P279 was improved to 0.78 V, and a
PCE of 6.26% was obtained, suggesting that the 2D conjugated
side chains had a universal role in designing the BDT and BDF
containing polymers. Biewer et al. introduced furan on the BDF
and synthesized the P280 copolymer, which exhibited a
narrowed optical bandgap but higher HOMO level. A maximum
PCE of 5.23% with a VOC of 0.65 V was achieved for the P280-
based PSC device.306 Figure 29 summarizes the molecular
structues, and their energy levels, band gaps, as well as
photovoltaic performances are listed in Table 21.
In addition to the BT and TT units, there were many other
units, such as TPD, BDD, DPP, and Qx, that were used to
construct the BDF-containing photovoltaic polymers. For
instance, following their work of PBDT-TPD, Beaujuge and
co-workers synthesized a series of copolymers based on BDF and
TPD.307 As compared to PBDT-TPD, P281 showed a slightly
larger optical bandgap of approximately 1.97 eV and the HOMO
level of P281 was lower than that of PBDT-TPD by 0.12 eV. In
their study, varied flexible side chains were used to investigate
their influence on photovoltaic performance. By selecting 2-
ethylhexyl on BDF and n-octyl on TPD, the P281 obtained a
maximum PCE of 7.4% for the PSC device.
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Figure 30. Molecular structures of P287−P301.

Table 22. Optical, Electronic, and Photovoltaic Performances of P287−P301

polymer Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
P287 1.59 −5.15 0.68 9.85 54 3.64 284
P288 1.67 −5.24 0.89 13.0 65.3 7.6 311
P289 1.66 −5.18 0.65 12.2 63.0 5.0 312
P290 1.77 −5.20 0.30 0.96 28.8 0.083 312
P291 1.84 −5.23 0.71 7.23 54.6 2.8 312
P292 1.63 −5.29 0.72 15.77 59.4 6.74 313
P293 1.66 −5.53 0.79 6.64 53.9 2.83 313
P294 1.48 −5.13 0.62 6.41 60.9 2.42 314
P295 1.47 −5.19 0.65 12.61 63.4 5.19 314
P296 1.45 −5.25 0.75 13.9 61.3 6.39 314
P297 1.50 −5.35 0.75 9.80 65 4.75 316
P298 1.58 −5.38 0.70 12.58 50.28 4.43 317
P299 1.58 −5.51 0.70 14.98 60.0 6.28 318
P300 1.85 −4.82 0.83 15.1 54.3 6.81 319
P301 1.85 −5.36 0.92 14.1 75 9.74 320

Li et al. synthesized the naphtho[2,3-c]thiophene-4,9-dione
unit and prepared the P282 copolymer.308 When compared to its
BDT-based counterpart, the absorption spectrum of P282 was
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slightly red-shifted, and its HOMO level was downshifted. The
PSC device fabricated by P282 yielded a PCE of 4.71%.
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Figure 31. Molecular structures of S1−S27.
Tang et al. optimized the synthesis route of 4,8-functionalized
BDF units with different substitutions and prepared a series of
copolymers, which showed varied optical and electronic
properties.309 They used P283 as an example to investigate
their photovoltaic properties, and a PCE of 4.61% was obtained
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Review
with a VOC of 0.8 V. P284 and P285 were prepared by An and co-
workers by selecting fluorinated Qx as the acceptor units.310
P285 showed a similar absorption spectrum but downshifted
HOMO level by 50 mV compared to P284. The P285-based PSC
device yielded a PCE of 4.44% with a VOC of 0.83 V.
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Table 23. Optical, Electronic, and Photovoltaic Performances of S1−S27

molecules Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
S1 1.83 −5.11 0.93 9.77 59.9 5.44 330
S2 1.74 −5.02 0.93 12.21 65.0 7.38 331
S3 1.79 −5.08 0.94 12.56 70.0 8.26 332
S4 1.74 −5.07 0.91 14.45 73.0 9.95 327
S5 1.60 −5.16 0.92 8.58 64.8 5.11 333
S6 1.60 −5.16 0.92 11.05 66.4 6.75 333
S7 1.59 −5.18 0.91 9.47 48.2 4.15 333
S8 1.61 −5.19 1.03 10.07 54.7 5.67 333
S9 1.72 −5.02 0.93 13.17 66.3 8.12 334
S10 1.76 −5.06 0.96 11.92 59.4 6.79 334
S11 1.76 −5.07 0.92 12.09 72.1 8.02 335
S12 1.78 −5.13 0.91 12.93 71.0 8.70 336
S13 1.80 −5.15 0.90 12.20 70.0 8.01 336
S14 1.77 −5.51 0.94 12.5 69.0 8.1 326
S15 1.73 −5.18 0.97 13.45 70.5 9.2 337
S16 1.97 −5.36 0.97 9.1 52.0 4.62 338
S17 1.86 −5.34 0.90 10.5 46.3 4.37 339
S18 1.82 −5.25 0.90 7.88 63.7 4.51 340
S19 1.79 −5.13 0.908 9.65 60.1 5.27 341
S20 1.75 −5.18 0.968 8.80 63.6 5.42 341
S21 1.88 −5.15 0.96 10.32 59.0 5.84 342
S22 1.82 −5.15 0.97 8.67 60.0 5.03 342
S23 1.83 −5.33 0.92 6.89 63.0 4.0 343
S24 1.76 −5.19 0.94 8.0 70.0 5.26 344
S25 1.77 −5.11 0.87 9.94 65.0 5.64 344
S26 1.82 −5.34 0.90 13.90 74.0 9.3 345
S27 1.80 −5.37 0.95 11.86 70.0 7.93 346
S28 1.87 −5.20 0.88 6.30 75.0 4.16 347

Sun et al. introduced the benzene ring on the BDF unit and
synthesized the P286 copolymer.233 P286 had a large optical
bandgap of 1.83 eV and a HOMO level of −5.43 eV.
Furthermore, its hole mobility reached 0.014 cm2 V−1 s−1. The
P286-based PSC device achieved an impressive PCE of 9.43%
with a VOC of 0.92 V, a JSC of 13.28 mA/cm2, and an FF of 77.4%,
which was the highest PCE value obtained in BDF-containing
polymers. Figure 30 summarizes the molecular structures, and
their basic optical and electronic properties as well as
photovoltaic performances are listed in Table 22.
To extend the π-conjugated system of BDT, DTBDT was
designed and applied by researchers when preparing photo-
voltaic polymers. In 2012, Hou and co-workers first synthesized
the P287 copolymer based on alkoxy-substituted DTBDT and
TT.284 P287 had an optical bandgap of 1.59 eV and a HOMO
level of −5.15 eV, which was similar to its BDT-based
counterpart. The P287-based PSC device achieved a PCE of
3.64% (VOC = 0.68 V, JSC = 9.85 mA/cm2, and FF = 54%). Yu et
al. synthesized the alkyl-substituted DTBDT and prepared three
P288 copolymers by copolymerizing with the fluorinated TT
unit.311 The P288-based PSC device exhibited a PCE of 7.6%
(VOC = 0.89 V, JSC = 13 mA/cm2, and FF = 65.3%). Afterward,
they further extended the π-conjugated system and prepared the
P290 and P291 copolymers using a ladder-type structure.312 As
the conjugated area increased, the optical bandgaps increased to
1.66, 1.78, and 1.84 eV for P289, P290, and P291, respectively.
Furthermore, the HOMO levels of these copolymers were
located at −5.03, − 5.14, and −5.12 eV for P289, P290, and P291,
respectively. The P289-based PSC device achieved a PCE of
5.0%, whereas the P291-based PSC device achieved a PCE of
5.5%. Unexpectedly, the PSC device fabricated P290 achieving
7436
an extremely low efficiency of nearly 0%, which may be caused by
its low mobility.
Recently, Kim et al. synthesized the P292 and P293 copolymer
using thienyl-substituted DTBDT as the donor unit.313 Due to
P292’s flat structure, highly crystalline properties were observed
in its film. Conversely, the twisted structure of P293 resulted in
its amorphous character. Photovoltaic devices fabricated by P292
and P293 achieved a PCE of 6.74% and 4.44%, respectively. It
should be noted that the PSC device based on P292 exhibited
good stability in air (i.e., retaining 95% of the initial PCE after
being stored for over 1000 h without encapsulation).
Chu and co-workers prepared a series of copolymers, P294−
P296, based on DPP and DTBDT, and different substitutions,
alkoxy, thienyl, and TIPS, were introduced on the DTBDT to
tune the optical absorption, molecular energy levels, and charge
transporting properties of the polymers.314 The optical bandgaps
of P294−P296 ranged from 1.45 to 1.48 eV, and their HOMO
levels changed from −5.13 to −5.25 eV. A best PCE of 6.39%
with a VOC of 0.75 V, a JSC of 13.9 mA/cm2, and an FF of 61.3%
was obtained for the P296-based PSC device. Additionally, Son
and co-workers prepared the P297 copolymer based on alky-
substituted DTBDT and DPP, demonstrating a hole mobility as
high as 2.7 cm2 V−1 s−1.315 Then, they fabricated the PSC device
based on P297, which achieved a PCE of 4.75%.316
In addition to the copolymers discussed above, researchers
also designed several other DTBDT-based polymers by applying
different acceptor units. For example, Yang and co-workers
prepared the P298 copolymer, which achieved a maximum PCE
of 4.43% in the PSC device.317 P299, which was developed by
Cao et al., achieved a PCE of 7.52% for an inverted PSC
device.318 Park et al. used the highly polarized group,
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dithieno[3,2-b:2′,3′-d]phosphole oxide, as the acceptor unit to
construct the P300 copolymer, which achieved a PCE of 6.81% in
the PSC device.319
Recently, Sun et al. prepared the P301 copolymer, which
possessed a wide optical bandgap of 1.85 eV and a low-lying
HOMO level of −5.36 eV.320 The PSC device achieved a high
PCE of 9.74% with an impressive FF of 75%, which was the
highest PCE value for the PSC devices constructed with
DTBDT-based polymers, thus suggesting that DTBDT had
significant potential in designing highly efficient conjugated
molecules for solar cells.
5. BDT-BASED PHOTOVOLTAIC SMALL MOLECULES
In recent years, small molecule solar cells (SMSCs) emerged as
challenging rivals to PSCs due to their advantages of defined
structure and thus less batch-to-batch variation.321−325 The gap
between the PCEs of SMSCs and PSCs is further diminished in
the wake of state-of-the-art SMSCs achieving PCEs over
10%.326−328 In the early stages, several triphenylamine (TPA)-
based molecules and hyperbranched molecules were used as the
photovoltaic active layer in the SMSC device and achieved great
progress. Over the past few years, following the considerable
success of the BDT unit in designing highly efficient photovoltaic
polymers, researchers incorporated the BDT units in small
molecules and the SMSC devices achieved good photovoltaic
performance.
Before BDT, thiophene core-based small molecules achieved
the highest PCE of approximately 5% for solar cell devices.329
Compared to the thiophene unit, BDT possesses a large and rigid
conjugated structure, which is in favor of electron delocalization
and coplanar π−π stacking, thus benefiting the charge transport
and resulting in a higher FF value. Additionally, as a relative weak
electron donor, BDT would lower the HOMO level of the
resulting molecule, thus, the corresponding device possessed a
high VOC value.
In this section, we summarize the BDT-containing small
molecules and discuss their application in SMSCs. For the
structures of the BDT-containing molecules, various alkyl side
chains, π-bridges, and electron-withdrawing units have been
widely used to modify the optical, electronical properties of the
materials and thus the photovoltaic performance of the SMSCs.
Furthermore, a few other small molecules based on the building
blocks derived from BDT will be presented.
5.1. Side Chain Engineering of BDT-Based Photovoltaic
Small Molecules
In 2011, Chen et al. first introduced BDT units as the core
building block in SMSCs to improve the film quality and the
charge mobility of small molecules.330 They designed and
synthesized S1 using the unsubstituted BDT unit as the central
unit and the electron-withdrawing alkyl cyanoacetate group as
the end-capped group (Figure 31 and Table 23). S1 had an
optical bandgap of 1.83 eV and a HOMO level of −5.11 eV.
Furthermore, its absorption spectrum showed a shoulder peak at
a long wavelength, suggesting that a rigid coplanarization of the
conjugated systems existed in the S1 film. Additionally, the XRD
measurement suggested that S1 possessed a highly crystallized
character, which was beneficial for the charge transport. The
optimized device based on the S1/PC61BM blend achieved a
PCE of 5.44% (VOC = 0.93 V, JSC = 9.77 mA/cm2, and FF =
59.9%) without being subjected to any special treatments.
Afterward, side chain engineering was performed by
researchers to modulate the properties of the molecules, such
7437
Review
as solubility, molecular stacking, energy levels, absorption
spectrum, and morphology. To investigate the effects of the
alkyl side chains on the photovoltaic performance of small
molecule donors, a series of BDT-based small molecules, S2,331
S3,332 and S4,327 were synthesized by Chen et al. These three
small molecular donors shared the same backbone structure and
end-capped groups but different substitutions on the BDT. By
replacing the branched alkoxy with octyl on the BDT, a deeper
HOMO level and a higher VOC value were obtained for S3 due to
the weaker electron donating ability of alkyl.332 After a two-step
annealing (TSA) approach involving thermal annealing and
solvent vapor annealing to optimize the film morphology, a best
PCE of 8.26% was acquired for the S3-based SMSC device. The
alkylthiol side chain was used to modify the BDT unit to further
optimize the optoelectronic properties and molecular packing for
S4.327 A remarkable PCE as high as 9.95% was achieved using a
TSA-processed S4-based device (a VOC = 0.92 V, JSC = 14.61
mA/cm2, and FF = 74%), which was one of the highest PCE for
single junction OPVs.
2D-BDT units were frequently used to further improve the
photovoltaic performance of BDT-based SMSCs. Li et al.
introduced thiophene substitution on BDT and synthesized S6
and S8. As compared to the alkoxy substituted counterparts S5
and S7, S6, and S8 showed enhanced and extended absorption
properties.333 Benefiting from their improved absorption
properties, the JSC of the SMSC devices based on S6 and S8
increased to 11.05 and 11.07 mA/cm2 from 8.58 and 9.47 mA/
cm2 for S5 and S7, respectively. Chen et al. constructed a range of
2D conjugated small molecules, S9−S11, using varied 2D
conjugated side chains.334,335 Compared with S2, which used the
alkoxy-substituted BDT, the introduction of conjugated side
chains on BDT resulted in a red-shifted absorption spectrum. An
initial PCE of 8.12% was obtained for the S9-based SMSC
device.334 After solvent annealing the S9/PC71BM blend using
carbon disulfide, a high PCE of 9.58% was achieved for the S9-
based SMSC device.335 When a longer alkyl side chain 2-
hexyldocyl (HD) was attached to the thienyl-BDT, the resulting
S10 showed an improved VOC of 0.96 V, which may be caused by
the larger steric hindrance of HD. However, the JSC and FF values
of the S10-based SMSC device were all lower than that of the S9-
based device, thus limiting its PCE. The insertion of bithiophene
increased the electron-donating ability and the delocalization of
the π electron, thus slightly lifting the HOMO level of S11.
Recently, Chen et al. introduced an alkyl- and alkylthio-
substituted thieno[3,2-b]thiophene (TT) unit on BDT and
synthesized the S12 and S13.336 The alkylthio-containing
molecule S13 demonstrated an increased dihedral angle between
the thiophene and the BDT, thus slightly decreasing its
intermolecular interactions. The SMSC device based on S12
achieved a PCE of 8.70% with a notable FF of 72%.
Yang et al. synthesized S14 and fabricated the SMSC device,
and they determined that using polydimethylsiloxane (PDMS)
as an additive in the blend solution could improve the PCE from
7.2% to 8.1%.326 With the use of a homotandem device structure,
a record PCE of 10.1% (VOC = 1.82 V, JSC = 7.70 mA/cm2, and FF
= 72%) was achieved. Li et al. introduced alkylthio-substituted
thiophene on the BDT and synthesized the S15 molecule.337 The
introduction of alkylthio-thienyl downshifted the HOMO level,
slightly red-shifted the absorption spectrum, and enhanced the
hole mobility of S15, thus leading to an overall improvement in
the photovoltaic properties for the S15-based device. Surpris-
ingly, a maximum PCE value of 9.20% was obtained for the S15-
based SMSC device processed without any additives and
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Figure 32. Different building blocks in the backbone of S29−S61.

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Table 24. HOMO Energy Levels, Optical Bandgap, and Photovoltaic Parameters of S29−S61
molecules Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
S29 1.84 −5.04 0.95 8.00 60.0 4.56 331
S30 1.72 −5.45 0.91 5.17 46.0 2.13 348
S31 1.75 −5.40 0.90 9.08 66.0 5.42 348
S32 1.84 −5.08 0.89 9.98 72.0 6.4 349
S33 1.76 −5.18 0.92 10.2 68.0 6.4 349
S34 1.85 −5.11 0.93 6.1 53.0 3.0 349
S35 1.93 −5.27 0.92 4.7 54.4 2.40 350
S36 1.96 −5.33 0.89 2.7 55.2 1.33 350
S37 1.90 −5.44 0.89 7.94 40.0 2.83 351
S38 1.80 −5.13 0.89 2.07 29.0 0.54 352
S39 1.77 −5.17 0.89 9.33 54.5 4.53 353
S40 1.77 −5.11 0.82 4.74 40.5 1.58 353
S41 1.78 −5.20 0.85 10.48 66.0 5.88 354
S42 1.85 −5.37 0.97 11.48 70.0 8.10 355
S43 1.75 −5.5 0.85 8.7 51.0 3.8 356
S44 1.71 −5.30 0.76 5.22 55.0 2.19 358
S45 1.55 −5.14 0.67 4.12 58.3 1.62 357
S46 1.60 −5.20 0.80 3.49 52.5 1.46 357
S47 1.65 −5.23 0.84 11.97 57.6 5.79 359
S48 1.59 −5.36 0.76 12.2 62.0 5.9 362
S49 1.51 −5.08 0.62 15.64 59.4 5.77 363
S50 1.51 −5.13 0.67 8.35 57.0 3.20 363
S51 − − 0.82 7.6 60.0 3.74 372
S52 1.66 −5.15 0.74 9.32 54.6 3.76 364
S53 1.69 −5.15 0.73 4.62 54.9 1.83 364
S54 1.69 −5.15 0.64 0.45 42.4 0.12 364
S55 1.58 −5.16 0.78 4.22 27.0 0.91 365
S56 1.53 −5.17 0.78 3.44 57.0 1.52 365
S57 1.55 −5.13 0.64 9.66 46.0 2.85 365
S58 1.85 −5.10 0.89 8.83 66.2 5.20 366
S59 − −5.20 0.83 4.60 43.0 1.62 361
S60 1.82 −5.20 0.975 10.08 51.3 5.05 368
S61 1.68 −5.38 0.92 11.68 62.0 6.66 369

annealing treatments. Except for the thiophene unit, several
other 2D conjugated side chains were developed by researchers
to modify the BDT. For example, Kim et al. designed and
synthesized S16338 and S17339 using alkylthienyl and alkylsele-
nophenyl-substituted BDT units, respectively. From S16 to S17,
the optical bandgaps shrank substantially from 1.97 to 1.86 eV,
which played a key role in improving the JSC of the SMSC
devices. Lastly, a PCE of 4.37% with a JSC of 10.5 mA/cm2 was
achieved for the S17-based SMSC device.
Yang et al. attached the alkoxyphenyl substituent on the BDT
unit as a weak electron-donating conjugated side chain and
synthesized the S18 molecule, which achieved a PCE of 4.51%.340
Li et al. designed and synthesized S19 and S20 using
alkoxyphenyl-substituted BDT and meta-fluorinated-alkoxy-
phenyl-substituted BDT as the core, respectively.341 They
determined that the introduction of F atoms on BDT
significantly lowered the HOMO level of S20, thus resulting in
an increase of ca. 60 mV in VOC for the corresponding SMSC
device. Using the triisopropylsilylethynyl (TIPS) substitution,
Ko et al. synthesized S21 and S22.342 The best PCEs of 5.84%
and 5.03% were obtained for devices fabricated from the S21 and
S22/PC61BM blend with a small amount of a high boiling point
additive, respectively. Wong et al. used TVT as a side chain to
synthesize S23, which achieved a PCE of 4.0%.343
To investigate the effects of the alkyl side chains on the
photovoltaic performances of small molecules, Wei et al.
7439
designed molecules S24 and S25 with different lengths of their
alkyl side chains attached to the π-bridge and end-capped
group.344 S25, which had a shortened alkyl side chain, exhibited
more dense packing and a higher degree of crystallinity than S24,
which was also consistent with the DSC and GIXRD
measurements. The SMSC device based on S25 achieved a
PCE of 5.64% with an enhanced JSC of 9.94 mA/cm2, which was
due to the purer crystalline domains of the donor material.
S26, which was synthesized by Jones and co-workers and based
on dialkyl-substituted thienyl-BDT, exhibited a nematic liquid
crystalline behavior, which was seldom observed in previous
reports.345 The GIWAXS pattern indicated that S26 possessed
two different molecular arrangements (including both edge-on
and face-on) in the pristine film. Benefiting from its high hole
mobility, S26 exhibited excellent photovoltaic performance. A
best PCE of 9.3% with a remarkable FF of 77% was obtained for
the SMSC device. Additionally, when the thickness of the active
layer increased to 400 nm, an FF exceeding 70% with ca. 8% PCE
was achieved for the SMSC device. These inspiring results
proved the application potential of S26 in the large-area printing
technology field. Furthermore, S27 and S28 were developed by
researchers and depicted similar results.346,347
5.2. Electron-Withdrawing Units used in the Backbone of
BDT-Based Photovoltaic Small Molecules
The electron-withdrawing moiety plays an important role in
tuning the absorption spectra molecular energy level and charge
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carriers mobility of small molecules. In addition to the end-
capped groups, such as rhodamine and indenedione, several
other electron-withdrawing units, such as BT, DPP, and BT, were
developed by researchers to construct small molecules for solar
cells. The rational selection of end-capped groups is of great
significance in improving the photovoltaic performances of the
SMSCs.
Additionally, during the preparation of S2, Chen et al.
synthesized S29 end-capped with octyl cyanoacetate, which
showed a red-shifted absorption spectrum of approximately 40
nm compared to S2.331 The SMSCs based on S29 achieved a
moderate PCE of 4.56% with a high VOC of 0.95 V. Chu et al. also
designed two molecules, S30 and S31, that were end-capped with
dicyanovinyl (CN) or cyanoacetate (CNR) units, respec-
tively.348 The XRD pattern indicated that S31, using the CNR
terminal group, showed enhanced crystalline property. The
SMSC device based on S31 exhibited a PCE of 5.42%, whereas its
counterpart fabricated from S30 only obtained a PCE of 2.13%
due to the dramatically reduced JSC value.
Wei et al. synthesized S32−S34 with three different end-
capped groups [i.e., octyl-2-cyanoacetate, 3-oxoundecanenitrile,
and 2-(octylsulfonyl) acetonitrile].349 The authors determined
that S32 depicted the strongest molecular interaction, whereas
S34 demonstrated the weakest. As the electron-withdrawing
capability of acceptors increased, the molecular HOMO levels
were downshifted while their absorption spectra were red-shifted
to a certain extent. Lastly, the best PCE of 6.4% was achieved
from the SMSC device based on S33. Figure 32 summarizes the
different building blocks in the backbones, and their energy
levels, band gaps, as well as photovoltaic performances are listed
in Table 24.
Park et al. incorporated TPD as the electron-withdrawing unit
to synthesize the S35 and S36 molecules, which achieved a
relatively low PCE of approximately 1%−2%.350 Lee and co-
workers synthesized S37 using BT and TPA as the terminal
groups.351 Benefiting from a highly ordered π-stacked structure
upon thermal annealing, the corresponding device obtained a
PCE of 2.83%. Yang et al. synthesized the S38 molecule using the
BT unit as the electron-withdrawing unit.352 The OFET device
based on S38 showed a remarkable hole mobility as high as 0.016
cm2 V−1 s−1 due to its uniform film morphology, which was one
of the highest values for solution processing small-molecule
donors in organic solar cells at that time. However, the SMSC
device based on S38 achieved a PCE of 0.54% with a low FF of
0.29. Furthermore, Li and co-workers synthesized two BT-based
small molecules, S39 and S40, to investigate the impact of the
moiety sequence in the backbone structure.353 S40 showed a red-
shifted absorption spectrum than S39 in the solution state. Due
to the low-lying HOMO level of S39 and its enhanced crystalline
property, the device based on S39 achieved a considerably higher
PCE of 4.53% whereas the PCE of the device fabricated by S40
was only 1.58%. Li et al. introduced monofluorinated BT to
synthesize S41, which exhibited a PCE of 5.88% at a relative low
fullerene acceptor content of 25%.354 Generally, small molecules
have a better crystallinity than their polymer counterparts, thus
forming purer domains. Wei et al. reported a novel D−A−D−A−
D-structured small molecule S42 with thiophene-substituted
BDT as donor and BT as acceptor.355 Compared to its polymeric
counterpart (i.e., the copolymer based on BDT and BT), S42 had
a shorter conjugated length and a larger optical band gap (1.83
eV). However, the HOMO energy levels of the two compounds
were similar, thus resulting in close VOC values in the
photovoltaic devices. Benefiting from the better crystalline
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behavior and film morphology, the SMSC device based on S42
exhibited a PCE of 8.10%. This result offered a new strategy in
the structural design of small molecule donors.
Marks et al.356 and Nguyen et al.357 independently synthesized
molecule S43 based on BDT and DPP. S43 possessed a relatively
low optical bandgap of approximately 1.7 eV. The S34-based
SMSC device achieved a PCE of 3.8% with a VOC of 0.85 V.
Furthermore, Tu and co-workers reported similar results using
S44.358 Nguyen et al. focused on the effect of end-capped groups
on the molecular energy levels and absorption spectra and
reported the molecules S45 and S46 end-capped with thiophene
and benzofuran, respectively.357 Zhan et al.359 and Yao et al.360
independently used thienyl-substituted BDT and DPP to
synthesize a 2D-counjugated S47, which showed a low optical
bandgap of 1.64 eV. The SMSC device based on S47 gave a PCE
of 5.29% by optimizing the blend film morphology. Sub-
sequently, Yao et al. also utilized S43 and S47 to fabricate
nonfullerene solar cell devices by blending them with a perylene
diimide dimer as the acceptor, and a PCE of 2.01% was
obtained.361 By changing the end-capped groups of S47, a series
of molecules S48−S50 were synthesized by researchers, and the
corresponding SMSC devices achieved PCEs of approximately
3%−6%.362,363 Yao et al. synthesized S52−S54 to explore the
effects of anchoring terminals on the photovoltaic perform-
ance.364 They determined that S53 with a COOCH3 side chain
demonstrated a stronger molecular interaction and smaller π−π
stacking distance than the others. The SMSC device based on
S53 achieved a maximum PCE of 3.76% with an increased JSC of
9.32 mA/cm2. They also synthesized S55−S57 to investigate the
influence of end-capped groups on the photovoltaic perform-
ance.365 Among them, S56 with the CNR terminal demonstrated
a low bandgap of 1.53 eV. The morphological characterization
suggested that the end-capped groups had a significant influence
on the phase separation of the blend film.
In addition to the end-capped groups, the π-bridges also
played critical roles in tuning the photovoltaic performance for
small molecules. Yang et al. synthesized S58 using thieno[3,2-
b]thiophene as the π-bridge.366 The introduction of thieno[3,2-
b]thiophene prolonged the conjugation length of the main chain
and enhanced the π−π stacking, which facilitated the charge
carrier transport. The S58-based SMSC device achieved a PCE of
5.20%. Yao designed a new small molecule S59 by increasing the
number of thiophene π-bridges.361 A theoretical calculation
demonstrated that the introduction of the extra thiophene in the
main chain caused a more twisted backbone structure. Due to its
poor blend morphology, the S59-based SMSC device achieved a
relatively low PCE of 1.62%. Then, they synthesized a series of
small molecules based on the BDT core and methyl-dioxocyano-
pyridine (MDP) terminal to systemically investigate the effects of
the oligothiophene π-bridges on the photovoltaic perform-
ance.367 Chen and co-workers used dithieno[3,2-b:2′,3′-d]silole
(DTS) as the π-bridge to synthesize the S60 molecule.368
Compared with S9, which used thiophene as the π-bridge, S60
showed a narrowed absorption spectrum with a band gap of 1.82
eV. Meanwhile, the deeper HOMO level resulted in a high VOC of
0.98 V for the S60-based SMSC device. However, only a
moderate PCE of ca. 5% was attained due to the lower JSC and FF
values. Palomares et al. used a cyclopentadithiophene moiety as
the π-bridge to synthesize the S61 molecule.369 After performing
a TSA approach, the devices achieved a PCE of 6.66%.
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Figure 33. Small molecules based on building blocks derived from BDT.

Table 25. HOMO Energy Levels, Optical Bandgap, and Photovoltaic Parameters of S62−S78
molecules Egopt (eV) HOMO (eV) VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
S62 1.75 −5.48 0.88 6.32 53.6 2.98 370
S63 1.72 −5.41 0.86 9.94 59.1 5.05 370
S64 1.88 −5.61 0.85 10.6 56.0 4.98 371
S65 1.72 −5.40 0.84 11.2 42.7 4.0 374
S66 1.70 −5.11 0.755 11.7 50.1 4.4 374
S67 2.16 −5.16 0.93 3.79 28.0 0.98 375
S68 1.96 −5.34 0.95 6.18 37.0 2.20 375
S69 1.71 −5.19 0.766 11.4 63.2 5.53 376

5.3. Photovoltaic Small Molecules Based On BDT Derivatives
In addition to the BDT-based small molecules, there were several
photovoltaic small molecules constructed by building blocks
derived from BDT, such as naphtho[1,2-b:5,6-b′]-dithiophene
(NDT) and DTBDT. For example, Chu et al. synthesized S62
and S63 using benzotrithiophene as the core to investigate the
effects of the length of the π-bridge in the backbone.370 S63 with
more thiophene units achieved a better PCE of 5.05%. Kim et al.
synthesized S64 based on DTBDT and TPD, which achieved a
PCE of 4.98% for the S63-based SMSC device.371 Inganäs et al.
replaced one of the thiophene with furan on the BDT unit and
synthesized the thieno[2,3-f ]benzofuran unit, and the S51-based
SMSC device achieved a PCE of 3.74%.372 Figure 33 summarizes
the small molecules based on different building blocks derived
from BDT, and their energy levels, band gaps, as well as
photovoltaic performances are listed in Table 25.
In 2011, Marks and co-workers synthesized S65 by
incorporating NDT as the core.373 Due to its broad absorption
and ordered molecular packing, the SMSC device based on S65/
PC61BM achieved a PCE of 4.0% with a VOC of 0.84 V.
Furthermore, they synthesized the NDT analogue, naphtho[1,2-
b:5,6-b′]dithiophene.374 As compared to S65, S66 exhibited a
7441
similar absorption spectrum but a higher HOMO level and
enhanced hole mobility. The SMSC device based on S66
achieved a PCE of 4.4%. Additionally, Lee et al. synthesized S67
and S68 using an unsubstituted NDT unit, and the SMSC device
based on S68 achieved a PCE of 2.2%.375 Marks et al. introduced
benzo[1,2-b:6,5-b′] dithiophene when designing photovoltaic
small molecule and synthesized S69, which achieved a PCE of
5.53% in the SMSC device.376
In conclusion, various excellent small molecule donors based
on BDT units have been synthesized and applied to SMSCs in
recent years, and a PCE over 10% was achieved. BDT units have
been approved as successful building blocks for constructing
photovoltaic small molecules, and the absorption spectra,
molecular energy levels, molecular stacking, and blend film
morphologies can be finely tuned through comprehensive side
chain engineering and rational selection of other electron-
withdrawing building blocks in the backbone.
6. APPLICATION OF BDT-BASED POLYMER DONORS
IN FULLERENE-FREE PSCS
Fullerene derivatives (PC61BM and PC71BM) are the most
common and successful acceptor materials used in highly
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Figure 34. Highly efficient BDT-containing polymer donors used in fullerene-free PSC device.
efficient BHJ PSCs. However, the fullerene-based PSCs suffer
relatively large energy loss (generally over 0.6 eV) and thus limit
its further improvement.267,377 What is more, fullerene-based
materials have some other drawbacks such as poor absorption
properties and costly preparation.378,379 To address these
problems, more and more efforts have been devoted to designing
and synthesizing nonfullerene acceptor materials, and the PCE of
fullerene-free PSCs has been improved to over 11%, almost
approaching the best results of its fullerene counter-
parts.203,380−383 Over the past several years, many types of
polymers and small molecules acceptors (as shown in Figure 35)
containing perylene diimides (PDIs),384−391 naphthalene
diimides (NDIs), 3 8 0 , 3 9 2 − 3 9 7 or indacenodithiophenes
(IDTs)398−402 units as core structures379,403 were developed
and applied in PSCs, and some of them achieved very impressive
results. The rapid development of fullerene-free PSCs has
opened a new avenue for the fundamental study of organic
photovoltaics.
Even though a lot of polymer donors exhibited superior
photovoltaic properties in fullerene-based PSC systems, selecting
proper donors with suitable energy levels, complementary
absorption spectra, as well as favorable blend morphology for
nonfullerene acceptors is of sigificance to obtain highly efficient
fullerene-free PSCs. As continued research focuses on the
fullerene-free PSCs, BDT-based polymers donors, especially the
2D-BDT-based polymers, have come to the fore in fabricating
PSC devices due to their superior properties. BDT-based
polymers like PBDT-TT, PBDT-BT, and PBDT-BDD families
(Figure 34) were widely used as donor materials in the highly
efficient fullerene-free PSC devices. In this section, we present a
short review and have a discussion about the application of BDT-
based polymers donors in fullerene-free PSCs.
PDI-based molecules (polymers and small molecules, as
shown in Figure 35 and Table 26) are promising nonfullerene
acceptors due to their high electron mobility, strong absorption
ability, and high environmental/thermal stability.386 Traditional
PDIs often have overstrong aggregation in the active layer, which
limits the exciton diffusion and separation process, leading to
poor photovoltaic performance of the devices.404 For example, in
2013, the PSC device fabricated from monomeric PDI molecule,
7442
Review
NF1, as acceptor and P90 as donor only gave a PCE of 0.13%.
Therefore, twisted PDIs were designed to avoid the large
aggregation domains, by means of PDI dimers linked at the imide
positions or bay positions. When blended with the same polymer
donor P90, a thiophene-linked bis-PDI molecule, NF2, showed
significant reduction of aggregation size in the blend film, and
thus leading to an outstanding PCE of 4.03% for the PSC device.
Similarly, PDI dimers were linked together through different
methods. For instance, Wang et al. synthesized NF3 by directly
linking the bay positions of two PDI units and introduced
branched alkyl chains on the imide positions.405 By using P90 as
polymer donor material, PCE of 3.63% was obtained in the
fullerene-free PSC device. Jen and co-workers replaced P90 by
P79 as donor material in the NF3-based cell device, and PCE was
boosted to 5.9% after the optimization of device engineering.384
Recently, Jen et al. synthesized a series of fused PDI derivatives
(NF5−NF7) bridged by furan, thiophene, and selenophene to
alleviate the overstrong aggregation problem.388 In comparison
with the unfused PDI molecule (NF4), the reduced reorganiza-
tion energy and extended effective π-conjugation of NF5-NF7
facilitated the exciton diffusion and charge transport, which
might contribute to the improved photovoltaic performance. By
selecting P79 as the donor material, PCE of 6.48% was recorded
in the NF6-based PSC device. Wang et al. introduced sulfur and
selenium atoms into the cores of PDIs and synthesized NF8386
and NF9,383 respectively. By incorporating a wide bandgap
polymer PDBT-T1 as donor material, the NF8- and NF9-based
fullerene-free PSC devices yielded very impressive PCE of 6.90%
and 8.23%, respectively.
In addition to the bay-linked PDIs discussed above, linking
two PDI units via the imide positions is another effective method
to disrupt the planarity of PDIs, and thereby PDI dimers and PDI
trimers were designed and synthesized. In 2013, Narayan and co-
workers fabricated the PSC device by employing the NF10 as
acceptor and P90 as donor, and PCE of 3.2% was obtained.406 By
changing the alkyl chain of NF10 and selecting P57 as donor in
the device, Hou et al. improved the PCE of the NF11:P57-based
PSC device to 5.4%.407 Jen and co-workers systematically
investigated the impact of the molecular geometry of the polymer
donors (P9 and P79) and the PDI dimer acceptors (NF3 and
DOI: 10.1021/acs.chemrev.6b00176
Chem. Rev. 2016, 116, 7397−7457
Chemical Reviews
Figure 35. Molecular structures of some representative nonfullerene acceptors.
NF11) on the BHJ morphology of the blend films.387 Their
results suggested polymer with 2D conjugated side chains could
enhance the miscibility with PDIs and thus lead to better
photovoltaic performance. Furthermore, the N−N linked PDI
trimer, NF12, exhibited impressive PCE of 7.25% when blended
with P57 as donor material.408
Helical PDIs were also developed as acceptors for PSC devices
and achieved some very impressive results. For example, NF13−
NF15 were synthesized by Nuckolls and co-workers and showed
PCE ranging from 5.94% to 8.3%, when blended with P79 as
donor material in the PSC devices.381,385 From their results, we
7443
Review
also could find that polymer with 2D conjugated side chains
always showed better photovoltaic performance than their 1D
counterparts. Jenekhe et al. synthesized NF16409 and NF17,382
which showed PCE of 3% and 6.7%, respectively, in the PSC
devices blended with P79 as donor material.
Over the past two years, small acceptor molecules based on
IDT units have been explored and showed great potential in
achieving outstanding photovoltaic performance. In 2015, Zhan
et al. reported the synthesis of NF18, which showed a low
bandgap of 1.57 eV and appropriated LUMO level of −3.82
eV.400 PSC device based on NF18:P79 showed high PCE of
DOI: 10.1021/acs.chemrev.6b00176
Chem. Rev. 2016, 116, 7397−7457
Chemical Reviews Review

Table 26. Photovoltica Paremeters of Fullerene-Free PSC Polymer acceptors containing PDIs 389,411−413 and
Devices NDIs380,392−394,414,415 were also developed and applied in
fullerene-free PSC devices, and some of them achieved very
acceptor donor VOC (V) JSC (mA/cm2) FF (%) PCE (%) ref
good photovoltaic performance. For instances, polymer NF22
NF1 P90 0.97 0.33 41.8 0.13 404 composed of NDI and thiophene was synthesized by Kim and
NF2 P90 0.85 8.86 54.1 4.03 404 co-workers, which exhibited a PCE of 5.96% by incorporating
NF3 P90 0.73 10.58 46.80 3.63 405 P79 as donor material in the PSC device.394 Jenekhe et al.
NF3 P9 0.78 10.51 58 4.77 387 replaced the thiophene of NF22 with selenophene and
NF3 P79 0.79 12.86 54 5.45 387 synthesized NF23, and a high PCE of 7.73% was recorded in
NF3 P79 0.80 11.98 59 5.90 384 the PSC device by using the same donor.415 N24 was also a
NF4 P79 0.88 9.74 41 3.54 388 widely studied polymer acceptor, and some impressive results
NF5 P79 0.92 8.71 40 3.20 388 were obtained by N24 and BDT-based polymer donors. In 2014,
NF6 P79 0.93 11.95 58 6.48 388 via incorporating P79 as donor, a PCE of 5.73% was obtained by
NF7 P79 0.92 11.19 55 5.59 388 Ito et al. in the N24-based PSC device.396 Li and co-workers
NF8 P301 0.90 11.65 65.5 6.90 386 further improved the PCE of N24-based PSC device by using
NF9 P301 0.947 12.48 69.7 8.23 383 P164 as donor material.380 Hou et al. conducted a deep research
NF10 P90 0.77 9.0 46 3.20 406 about the influence of the donor/acceptor molecular interactions
NF11 P9 0.79 3.66 51 1.47 387 and orientation on the PSC device performance, and their results
NF11 P79 0.79 13.12 60 6.19 387 suggested that BDT-containing polymer donors with 2D
NF11 P57 0.82 12.51 53 5.40 407 conjugated side chains were more likely to obtain better
NF12 P57 0.732 16.52 60.03 7.25 408 photovoltaic performance than their 1D counterparts.393 Jen et
NF13 P9 0.789 11.0 59 5.14 385 al. synthesized a fluorinated nonfullerene acceptor, N25, and
NF13 P79 0.796 13.5 55 5.94 385 showed a maximum PCE of 6.71% when blended with P79 as
NF14 P9 0.77 13.2 63 6.4 381 donor in the PSC device.392 In addition, PDI-based polymers like
NF14 P79 0.81 14.5 67 7.9 381 NF26389 and NF27411 were also developed and applied in
NF15 P9 0.79 12.9 64 6.5 381 fabricating PSC devices, and moderate PCE were recorded in the
NF15 P79 0.80 15.2 68 8.3 381 PSC devices.
NF16 P79 0.96 9.02 35 3.00 409
As discussed above, the best PCE of fullerene-free PSC device
NF17 P79 0.95 13.99 51 6.70 382
have reached 11.21%, approaching the fullerene-based PSCs. As
NF18 P79 0.97 13.55 48 6.31 400
more efforts continue to develop highly efficient nonfullerene
NF19 P79 0.81 14.21 59.1 6.80 399
acceptors and suitable donors, further improvement of PCE is
NF19 P165 0.89 17.43 61.48 9.53 203
expected in the near future, and we believe BDT-containing
NF19 P12 0.899 16.81 74.2 11.21 410
polymers will still be the most promising donors for the fullerene-
NF20 P301 0.88 16.24 67.1 9.6 402
free PSCs.
NF21 P301 0.89 15.05 65 8.71 401
NF22 P79 0.79 13.46 56 5.96 394
7. SUMMARY AND OUTLOOK
NF23 P79 0.81 18.80 51 7.73 415
NF24 P79 0.794 13.0 55.6 5.73 396 Organic semiconductors based on BDT units are promising
NF24 P164 0.83 14.18 70.24 8.27 380 photovoltaic materials for flexible and low-cost solar cells. There
NF24 P12 0.87 11.7 57.5 5.8 393 have been rapid advances in the PCEs of these materials over the
NF25 P79 0.81 13.53 62 6.71 392 past several years. In this article, we offered an overview of the
NF26 P57 0.77 13.74 53.22 5.63 389 organic photovoltaic materials based on BDT and its equivalents
NF27 P90 0.752 8.55 51.5 3.31 411 from the aspects of backbones, functional groups, alkyl chains,
and device performance. The impressive results indicate that
BDT and its analogs are versatile and useful building blocks for
the design of high-performance photovoltaic materials. Although
6.31%. Then they designed and synthesized a series of the current record efficiency of OPVs based on BDT-polymers is
nonfullerene acceptors containing indacenodithieno[3,2-b]- ∼11%, which is approaching the requirement for industrializa-
thiophene with different side chains to further optimize their tion, certain fundamental challenges and interesting research
photovoltaic performance.399,401,402 NF19 with phenyl side- topics still need to be addressed.
chains was developed in 2015 and exhibited initial PCE of 6.8% For example, devices based on BDT materials still have
when P79 was used as donor material.399 By applying novel comparatively low VOC values and thus cause considerable energy
polymer donor materials based on benzodithiophene and loss (>0.6 eV) during the photoelectric conversion process.
fluorobenzotriazole, further improvement of PCE was obtained Minimizing the energy loss will be a key to realize high VOC. The
for NF19-based PSCs by Li and co-workers.203 For instance, a geminate and bimolecular recombination in OPV devices still
high PCE of 9.53% was obtained when P165 was used as donor in needs to be reduced, thus improving the JSC and FF values.
the PSC device. Recently, a breakthrough PCE of 11.21% with Recent studies revealed that BDT-based polymer materials could
excellent thermal stability was recorded by Hou and co-workers also be used as good electron acceptors,413,416 and systematic
by using P12 as donor and NF19 as acceptor in the PSC studies on this topic still need to be performed. Furthermore,
device.410 Furthermore, they also certified a high PCE of 10.78% BDT-based polymers can be used as donors in fullerene-free
for the PSC device with an area of 1 cm2. When the phenyl of OPV devices,380−383,386,388,389,393,399,400,407 and our team
NF19 was replaced by alkyl401 or thienyl402 as side chains, PCEs recently demonstrated that a single junction OPV device using
of 8.71% and 9.6% were obtained, respectively, in the PSC a BDT-polymer donor and nonfullerene acceptor could achieve a
devices by selecting P12 as donor material. PCE of 11.2%.410 We believe that BDT-polymers will be good
7444 DOI: 10.1021/acs.chemrev.6b00176
Chem. Rev. 2016, 116, 7397−7457
Chemical Reviews
candidates to fully explore the potential of fullerene-free OPVs.
The stability of OPVs based on BDT materials has seldom been
studied. Therefore, testing the water and oxygen/air stability and
long-term lifetime of high-performance materials as well as
screening good candidate materials for practical applications is
required.
We anticipate that more exciting BDT-based photovoltaic
materials and devices will be developed in the near future
through synergistic efforts in material synthesis/design, device
processing/optimization, and interface/architecture design.
AUTHOR INFORMATION
Corresponding Author
*E-mail: hjhzlz@iccas.ac.cn.
Notes
The authors declare no competing financial interest.
Biographies
Huifeng Yao has been a Ph.D. candidate at Institute of Chemistry,
Chinese Academy of Sciences (ICCAS) under the supervision of Prof.
Jianhui Hou since 2012. His research interests focus on designing and
synthesizing high-performance organic photovoltaic materials.
Long Ye completed his Ph.D. research (Adviser: Prof. Jianhui Hou) in
Polymer Physics and Chemistry at Institute of Chemistry, Chinese
Academy of Sciences (ICCAS) in July 2015. Currently, he is a
postdoctoral research associate at Prof. Harald Ade’s group in North
Carolina State University. His research interests are understanding the
thermodynamics of polymer photovoltaics and revealing the critical
factors related to the morphology/performance of organic electronic
devices using soft X-ray scattering/microscopy.
Hao Zhang has been pursuing a Ph.D. degree in polymer physics and
chemistry at Institute of Chemistry, Chinese Academy of Sciences
(ICCAS) under the mentorship of Prof. Jianhui Hou since 2013. His
research interests are centered on the molecule design and application of
photovoltaic polymers for solar cells.
Sunsun Li obtained her B.S. degree in chemistry from University of
Science and Technology Beijing, in 2013. She is currently a Ph.D.
candidate majoring in material sciences, under the direction of Professor
Jianhui Hou. Her current research focuses on the design and synthesis of
novel organic semiconducting materials for nonfullerene solar cells.
Shaoqing Zhang has been a joint Ph.D. student at Institute of Chemistry,
Chinese Academy of Sciences (ICCAS) and University of Science and
Technology Beijing (USTB) under the supervision of Prof. Jianhui Hou
since 2012. Her research interests are the molecular design and
preparation of high-efficiency photovoltaic polymers.
Jianhui Hou received his Ph.D. degree in physical chemistry from
ICCAS in 2006. During 2006−2008, he worked as a postdoctoral
researcher at the University of California, Los Angeles (UCLA). Before
he joined ICCAS as a full professor in 2010, he worked as a team leader
of research department of Solarmer Energy Inc. His recent research
focuses on the design, synthesis, and application of the organic/polymer
photovoltaic materials.
ACKNOWLEDGMENTS
This work was supported by the National Basic Research
Program 973 (2014CB643501), NSFC (Grants 21325419,
91333204 and 51261160496), and the Chinese Academy of
Science (Grant XDB12030200).
7445
Review
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