Small Molecule Semiconductors For High Efficiency Organic Photovoltaics

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Cite this: DOI: 10.1039/c2cs15313k
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Small molecule semiconductors for high-eciency organic photovoltaics

Yuze Lin,ab Yongfang Lia and Xiaowei Zhan*a
Downloaded by FAC DE QUIMICA on 30 March 2012

Published on 28 March 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15313K
Received 18th November 2011

DOI: 10.1039/c2cs15313k
Organic photovoltaic cells (OPVs) are a promising cost-eective alternative to silicon-based solar
cells, and possess light-weight, low-cost, and exibility advantages. Signicant progress has been
achieved in the development of novel photovoltaic materials and device structures in the last
decade. Nowadays small molecular semiconductors for OPVs have attracted considerable
attention, due to their advantages over their polymer counterparts, including well-dened
molecular structure, denite molecular weight, and high purity without batch to batch variations.
The highest power conversion eciencies of OPVs based on small molecular donor/fullerene
acceptors or polymeric donor/fullerene acceptors are up to 6.7% and 8.3%, respectively, and
meanwhile nonfullerene acceptors have also exhibited some promising results. In this review we
summarize the developments in small molecular donors, acceptors (fullerene derivatives and
nonfullerene molecules), and donoracceptor dyad systems for high-performance multilayer,
bulk heterojunction, and single-component OPVs. We focus on correlations of molecular chemical
structures with properties, such as absorption, energy levels, charge mobilities, and photovoltaic
performances. This structureproperty relationship analysis may guide rational structural design
and evaluation of photovoltaic materials (253 references).
Introduction
Nowadays, fossil fuel (such as coal, oil, and gas) production and
use gives rise to a mass of environmental problems, and also their
a
Beijing National Laboratory for Molecular Sciences and Key

Laboratory of Organic Solids, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100190, China.
E-mail: xwzhan@iccas.ac.cn
b
Graduate University of Chinese Academy of Sciences,
Beijing 100049, China
Yuze Lin received a BS degree

in chemistry from Beijing
Institute of Technology in
2009. Now he is a PhD student
at the Institute of Chemistry,
Chinese Academy of Sciences.
His research interests include
synthesis of conjugated small
molecules and polymers and
their application in solar cells.
Yuze Lin
This journal is
The Royal Society of Chemistry 2012
stocks are diminishing. The need to develop renewable energy

sources has become urgent. The development of photovoltaic
cells (PVs), which transform inexhaustible solar energy into
electricity, is therefore one of the most promising long-term
solutions for clean, renewable energy. Currently, the main
barrier that prevents PV technology from providing a large
fraction of energy is the high cost of silicon-based PVs.
Organic photovoltaic cells (OPVs) are a promising cost-eective
alternative to silicon-based solar cells, and possess low-cost, lightweight, and exibility advantages. Contemporary OPVs are based
Xiaowei Zhan obtained a PhD

degree in chemistry from
Zhejiang University in 1998.
He was then a postdoctoral
researcher at the Institute of
Chemistry, Chinese Academy
of Sciences (ICCAS) from
1998 to 2000, and in 2000 he
was promoted to Associate
Professor at ICCAS. Dr Zhan
worked in the University of
Arizona and Georgia Institute
of Technology from 2002 to
2006 as Research Associate
and Research Scientist. He has
Xiaowei Zhan
been a full professor at ICCAS
since 2006. His research interests are in the development of organic
and polymeric materials for organic electronics and photonics.
Chem. Soc. Rev.

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on a heterojunction resulting from the contact of an electron

donor (D) and an electron acceptor (A) material. Absorption
of solar photons creates excitons, which diuse to the D/A
interface, where they are dissociated into free holes and
electrons, and opposite polarity carriers (holes and electrons)
transport through the donor and acceptor channels to anodes
and cathodes respectively, subsequently charges are collected at
the electrodes, resulting in the generation of electrical power.
D/A heterojunctions can be created with two main types of
architectures, bilayer heterojunction1 and bulk heterojunction
(BHJ).2
Before the mid 1980s, in conventional OPVs, a single layer
of single component organic material was sandwiched between
two dierent electrodes with dierent work functions.3 In
these single-layer and single-component cells, the built-in
potential is derived from either a Schottky-type potential
barrier at one of the metal/organic contacts or the dierence in
work function of the electrodes, and the photovoltaic properties
are strongly dependent on the nature of the electrodes. These
early OPVs showed very poor performance.
In 1986, Tang fabricated a bilayer heterojunction solar cell
with an eciency approaching 1%, which was a milestone in
the development of OPVs.1 Bilayer heterojunction architecture
has been intensively investigated and still is an invaluable tool
for the evaluation of new active materials, nevertheless,
performance of OPVs based on this structure is limited by the
short exciton diusion length in organic materials (typically
520 nm).4 Since the exciton dissociation process is conned to
the D/A interfacial zone, only excitons produced at a distance
shorter than their diusion length have a good probability to
reach the interfacial zone and generate free charge carriers. So
the exciton diusion length limits the maximum thickness of the
active layer and thus the maximum fraction of the incident light
that the cell can absorb and covert into electricity.
In 1991, Hiramoto et al. fabricated a novel type of threelayered OPV with a codeposited interlayer of mixed pigments
between the respective pigment layers, and the interlayer acted as
an ecient carrier photogeneration layer.5 Actually, this type
Yongfang Li has been a

professor at the Institute of
Chemistry, Chinese Academy
of Sciences (ICCAS) since
1993. He obtained his PhD
degree in physical chemistry
in 1986 from Fudan University,
then came to ICCAS as a postdoctoral fellow working on
conducting polymers with Prof.
Renyuan Qian (19861988).
He did visiting research in Prof.
Hiroo Inokuchis lab at the
Institute for Molecular Science
in Japan from 1988 to 1991
Yongfang Li
and in Prof. Alan J. Heegers
lab at UCSB from 1997 to 1998. His present research interests
are polymer solar cells and related photovoltaic materials
including conjugated polymer donor, solution-processable organic
molecule donor and fullerene derivative acceptor materials.
Chem. Soc. Rev.
OPV device is the predecessor of hybrid planar-mixed molecular

heterojunction (PMHJ) OPVs.6 And the mixed interlayer was
recognized as the rst bulk heterojunction layer in small
molecule-based OPVs.
In 1992, Sariciftci et al.7 demonstrated that photoexcitation
of a mixture of a conjugated polymer and fullerene (C60)
resulted in an ultrafast, highly ecient photoinduced electron
transfer. And then Yu et al.2 and Halls et al.8 created the bulk
heterojunction (BHJ) concept, which is one of the best OPV
device architectures so far. BHJ is a blend of bicontinuous and
interpenetrating donor and acceptor components in a bulk
volume. Such a nanoscale network exhibits a D/A phase
separation in a 520 nm length scale, which is within a distance
less than the exciton diusion length. Compared to bilayer
heterojunction, BHJ signicantly increases the D/A interfacial
area, leading to enhanced eciency of the OPV devices.9
Two or even more OPV cells can be stacked on top of each
other to form a tandem OPV structure, which enables one to
resolve two limiting factors existing intrinsically among organic
semiconductor molecules: poor charge carrier mobility and a
narrow light absorption range.
The bilayer heterojunction and BHJ OPV device structures
are shown in Fig. 1. In the two devices, the photoactive layers
both sandwiched between a high work function anode, typically
a transparent indium tin oxide (ITO) layer, and a relatively low
work function metal cathode, such as Ca, Al. In the bilayer
heterojunction device, the donor materials stick to the anode
and the acceptor materials stick to the cathode, while the active
layer is blend of donor and acceptor materials in BHJ device.
In principle, there are two processing techniques for the
fabrication of OPV devices, vacuum deposition and solution
processing. Generally, the bilayer heterojunction was fabricated by vacuum deposition since it is dicult to nd suitable
solvents for donor layer and acceptor layer without destroying
the D/A interface. And both of the two processing techniques
are suitable for the BHJ devices. Some of small molecules such
as metal phthalocyanine and C60 can be deposited under high
vacuum conditions by thermal evaporation. By coevaporation
of donor and acceptor materials, BHJ layers can be obtained.
On the other hand, soluble materials can be deposited from
solution, by spin coating, inkjet printing, gravure or exographic
printing.
In OPV devices, principal gures-of-merit include power
conversion eciency (PCE), short-circuit current density
(JSC), open-circuit voltage (VOC), and ll factor (FF), dening,
respectively, the ratio between the output device electrical
energy versus the input solar energy, the device current density
when no reverse bias is applied, and the device voltage when
no current ows through the cell, and the ratio between
maximum power of the device and JSC VOC.
Fig. 1 The architecture structure of bilayer heterojunction (a) and

BHJ (b) OPV devices.
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The photoactive materials, including polymeric and small

molecular semiconductors, play a key role in inuencing
physical processes involved in energy conversion, which in
turn determine the electrical characteristics of the solar cell,
such as JSC, VOC, and FF, and ultimately PCE. Recently,
OPVs based on a p-type conjugated polymer as a donor and
a fullerene derivative [6,6]-phenyl-C61 (or C71)-butyric acid
methyl ester (PC61BM or PC71BM) as an acceptor have been
rapidly developing, and so far the highest reported PCEs of
this type OPVs are up to 8.3%,10 but still below 10% that is
often regarded as being a prerequisite for large-scale commercial
applications. On the other hand, small molecular semiconductors
for OPVs have attracted considerable attention, due to their
advantages over their polymer counterparts, which include
well-dened molecular structure, denite molecular weight,
and high purity without batch to batch variations.11 An
increasing number of publications on OPVs based on small
molecules have appeared, the PCEs of devices based on small
molecule donors and fullerene acceptors fabricated by vacuum
deposition or solution processing are both in excess of
6%.1215 As for small molecule acceptors, compared to the
fullerene derivatives such as PC61BM and PC71BM, the development of nonfullerene small molecular acceptors has been lagged
with relatively low performance. Recently, research on nonfullerene acceptors has become more active due to their
interesting potentials, such as convenient synthesis, low cost,
easy tunability of energy levels, and perhaps most importantly,
better absorption in the visible spectrum.
A number of reviews have summarized the synthesis and
application of conjugated polymeric active materials,1631
small molecular donors,3238 fullerene acceptors,3941 small
molecular nonfullerene acceptors42,43 in OPVs as well as
device physics.4452 In the present review, we focus on the
representative small molecular donors, acceptors and donor
acceptor dyads in single OPVs. Progress in the past decade has
been substantial, but continued development of OPV materials
will require a better understanding of the relationships between
molecular structure, electronic structure, materials microstructure,
charge transport and photovoltaic properties than is currently
available. For these reasons, we will survey and analyze what
is currently known concerning structure/property relationships
of photovoltaic small molecules.
Small molecular donors

Small molecular semiconductors can be generally classied as
hole or electron transporting (p-type or n-type) materials
according to the type of orderly transferring charge carriers,
under a given set of conditions, stemming from removal of
electrons from the lled molecular orbitals or from the addition of
electrons to empty orbitals, respectively. Many small molecular
p-type semiconductors have been studied for decades.53
Among these molecules, only a small fraction has been applied
successfully as electron donors in OPV devices due to the
various optical, electrical, and stability requirements demanded
of the chosen materials. The properties of materials, such as
hole mobility (i.e., the distance over which holes are transported
per second under the unit electric eld), exciton diusion
length, thin lm morphology, frontier energy level alignment,
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band gap, and absorption coecient, all greatly aect the

performance of OPV device. In this section, some representative
small molecular donors such as dyes, fused acenes, oligothiophenes,
and triphenylamine-based molecules used in the active layer of
OPVs are described and discussed.
Dyes
Of a variety of small molecular donors that have been reported
in the literature, dye-based molecules are rst and common.
Several famous classes of dyes are believed to be potential
materials in OPVs, such as phthalocyanine (Pc), subphthalocyanine (SubPc), merocyanine (MC), squaraine (SQ), diketopyrrolopyrroles (DPP), borondipyrromethene (BODIPY),
isoindigo (ID), perylene diimides (PDI), and quinacridone
(QD). As several groups have demonstrated, functionalizing
a dye molecule has been conrmed to be a successful approach
to donor design. Table 1 provides a summary of electronic
properties as well as OPV data for representative dye-based
donors (Fig. 2).
Pc, comprising four isoindole units connected by 1,3-aza
linkages, is a planar and highly aromatic 18-p-electron macrocycle. Pc derivatives typically exhibit excellent thermal and
chemical stability,54 and they also oer exibility in their
optical and electronic properties through synthetic modications, such as attaching functional groups to the molecule
perimeter. The optoelectronic properties and stacking in the
solid state of Pc derivatives can be turned by replacing of the
two protons in the molecular cavity with a metal ion.
Although many metal Pc complexes have been used in OPVs,
CuPc (a1) and ZnPc (a2) have been the most common choices
to date for application in Pc-based OPV devices, due to longer
exciton diusion length of CuPc and ZnPc as compared to the
other Pcs.55
In 1986, CuPc was rst used as a donor material in bilayer
heterojunction OPV by Tang, and the device showed a PCE
value of 1%.1 Inspired by this pioneering contribution, Pc has
been commonly applied in vacuum-deposited OPV devices, due to
high absorption coecient and long exciton diusion length.5660
And Pcs are frequently paired with fullerenes in the OPV active
layer. The CuPc/C60 combination is among the most common for
small molecule OPV active layers at present, and devices
deriving from this system exhibited high performance.6 In
2001, Forrest and Peumans demonstrated that bilayer heterojunction OPVs based on CuPc and C60 with PCE of 3.6% can be
achieved under 150 mW cm2 simulated AM1.5G illumination,57
while the BHJ OPVs based on a mixture of vacuum codeposited
CuPc and C60 were fabricated and the best PCE was up to 3.5%
at 100 mW cm2 simulated AM1.5G illumination.59 Later,
Forrest et al. fabricated an OPV structure with a planar-mixed
heterojunction (PMHJ), i.e., a mixed layer consisting of CuPc
and C60 sandwiched between homogeneous CuPc and C60
layers, and the device aorded a maximum PCE of 5.0%, at
120 mW cm2 under simulated AM1.5 solar illumination.6
Additionally, stacking two of these cells together in a tandem
cell resulted in a ca. 15% increase in device performance and
a PCE of 5.7% at 100 mW cm2 AM1.5 simulated solar
illumination.60
Planar Pcs have relatively narrow absorption band and cannot
eectively absorb low-energy photons, while ca. 50% of photons
Chem. Soc. Rev.
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Table 1
Optical and electronic properties, mobilities, and OPV performance of dye-based donors
lmaxa/nm
Egopt/eV mhb/cm2 V1 s1
HOMOc/LUMO/eV Active layerd
a1
a3
a4
a6
a7
755
850
590
688
2 105 (S, N)
1.7

a8 607
a9 649
a10 616
a11
a12
a13
a14
a15
a19
a20
a21
a22
a23
a24
a25
a26
a27
a28
5 105 (O, N)
7 106 (O, N)
105104 (O)
1.2 104 (O, N)
1.3 103 (O, N)
595
760
770
820
700
a16 710
a17 588
a18 675
1 105 (O, N)
1.95
1.70
672
742
720
660
695
1.70
2.01
676
660
1.72
1.67
550
1.94
1.7
1.73
5.1 105 (S, N)

9.7 105 (S, N)
5 107 (S, B)
1.0 104 (S, N)
3 105 (S, B)
4 105 (O, N)
2.5 103 (S, N)
7.18 103 (O, N)
5
3.64 10
5.25 105
5.4(U)/
5.2(U)/
5.6/3.6
5.4/3.6
5.80/3.76
5.59/3.68
5.75/3.59
5.69/3.54
5.0/3.3
5.0/3.3
5.14/3.37
5.3/3.4
5.3/3.7
5.69/3.66
5.56/3.75
5.03/3.0
5.2(U)/3.7
5.2(U)/3.4
5.46/3.46
5.40/3.68
5.5/3.9
(S, B) 5.27/3.54
(S, N) 5.55/3.42
a1/f1
a1/C60
a1:C60 (1 : 1 vac)
a1/a1:C60 (1 : 1 vac)/C60
a3/C60
a4/C60
a6/C60
a7(sol)/C60
a7(vac)/C60
a8:PC61BM (1 : 3)
a9:PC61BM (3 : 7)
a10:PC61BM (9 : 11)
a10:C60 (1 : 1 vac)
a10:C60 (9 : 11 vac)
a11:PC71BM (9 : 11)
a12:PC61BM (1 : 3)
a13:PC71BM (1 : 3)
a14:PC71BM (3 : 2)
a15/C60
a15(sol)/C60
a15:PC71BM (1 : 6)
a16(sol)/C60
a17:PC61BM (1 : 2)
a18:PC61BM (1 : 2)
a17:a18:PC61BM (1 : 1 : 2)
a19:PC61BM (1 : 2)
a20:PC61BM (7 : 3)
a21:PC71BM (1 : 1)
a22:PC71BM (3 : 2)
a23:PC61BM (1 : 1)
a24:PC71BM (2 : 1)
a25:PC61BM (3 : 2)
a26:PC61BM (1 : 1)
a27:PC61BM (1 : 2)
a28:PC71BM (1 : 2)
JSC /mA cm2 VOC/V FF
PCEe (%) Ref.
2.3
18.8
15.4
15.0
15.1
3.36
5.6
6.1
5.3
6.3
8.24
11.5
12.6
10.2
5.70
9.32
12.6
6.89
9.71
12.0
10.0
4.43
4.14
4.70
7.00
8.42
9.2
10
4.9
8.3
11.27
6.3
5.94
8.87
0.95f
3.6g
3.5
5.0h
2.1i
4.2
2.1
1.5
2.5
1.54
1.74
2.59
4.9j
6.1
4.5
1.24
1.99
1.79
3.2
4.1
5.5
5.7
1.17
1.34
1.70
2.17k
2.33
3.0
4.4
1.53
3.7
4.06
1.76
1.42
2.22
0.45
0.58
0.50
0.54
0.68
0.57
0.97
0.55
0.79
0.90
0.76
0.94
0.80
0.96
1.0
0.62
0.57
0.31
0.83
0.78
0.92
0.90
0.80
0.75
0.87
0.75
0.67
0.75
0.92
0.77
0.76
0.84
0.76
0.78
0.72
0.65
0.52
0.46
0.61
0.50
0.53
0.57
0.49
0.49
0.32
0.36
0.34
0.48
0.47
0.44
0.35
0.37
0.47
0.55
0.54
0.5
0.64
0.34
0.44
0.42
0.45
0.44
0.48
0.41
0.58
0.42
0.38
0.31
0.35
1
57
59
6
61
63
67
69
70
72
72
73
74
12
75
79
80
81
82
83
84
86
88
88
89
90
91
92
93
94
95
96
97
99
100
a
In lm. b O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. c From electrochemistry unless stated otherwise,
U: from UPS. d Donor/acceptor: bilayer by vacuum deposition unless stated otherwise; donor:acceptor: blend by solution process unless stated
otherwise; vac: vacuum deposition; sol: solution process. e AM1.5, 100 mW cm2 unless stated otherwise. f AM2, 75 mW cm2. g 150 mW cm2.
h
120 mW cm2. i 119 mW cm2. j 88 mW cm2. k 90 mW cm2.
in the solar spectrum have energies corresponding to wavelength of 6001000 nm. Nonplanar Pc molecules, such as
chloroaluminum phthalocyanine (AlClPc, a3), exhibited an
absorption peak in the near-infrared around 755 nm and
harvested a greater percentage of infrared photons.61 The
out-of-plane Cl atom bonded to the central Al atom with
square-pyramidal geometry strongly inuences the molecular
packing, inducing an interleaved slip-stack arrangement and
signicant red shift in absorption compared to CuPc (maximum
absorption wavelength of ca. 630 nm). Additionally, ultraviolet
photoelectron spectroscopy (UPS) measurements indicate that
the highest occupied molecular orbital (HOMO) energy of a3 is
shifted to 5.4 eV, ca. 0.1 eV farther from vacuum than that of
a1, which is benecial for an increased VOC. The optimized
a3/C60 bilayer devices exhibit an overall improvement in PCE
from 1.8% of a1/C60 bilayer devices to 2.1%.61
Oxo-titanium phthalocyanine (a4) has also been applied in
the OPV devices as donor materials leading to both a higher
absorbance at long wavelengths and an increased VOC in
a4/C60 bilayer OPV devices as compared to a1.62,63 The studies
of a4 lms have determined that vapor deposition results in
the formation of at least two distinct phases with dierent
absorption spectrum. In 2009, Armstrong et al. reported that
Chem. Soc. Rev.
polymorph a4 lm has changed to crystalline form that

absorbs light at the longest wavelengths by exposure of the
as-deposited thin lm to concentrated solvent vapors (solvent
annealing). The optimized OPVs based on a4 showed a
relatively high PCE of 4.2%, with JSC of 15.1 mA cm2,
VOC of 0.57 V, and FF of 0.53.63
A metal-free Pc (a5) with aliphatic side chains was one of
the earliest small molecule donors in solution-processed BHJ
OPVs.64 The reported a5-based devices were prepared by spincasting a mixed solution of a5 and PDI derivative (f3, Fig. 7)
in chloroform. These very rst reported devices exhibited poor
device performance, but recent work has shown that Pc derivatives
are viable donors for application in solution-processed BHJ OPVs.
Signicantly improved performance was realized by using
a combination of three ZnPc-based donors and a fullerene
acceptor to give PCE of 0.12%, with a JSC of 1.24 mA cm2,
VOC of 0.41 V, and FF of 0.24.65
The OPVs based on Pcs showed relatively low VOC (generally
less than 0.6 V), which was one of factors limiting the PCEs of
OPVs. The VOC value generally depends on the energy dierence
between the lowest unoccupied molecular orbital energy
(LUMO) of the acceptor and HOMO energy of the donor.66
Thus, one way to increase the VOC is to lower the HOMO level
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Fig. 2 Chemical structure of dye-based donors.
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Chem. Soc. Rev.

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of donor materials. In 2006, Thompson and coworkers

reported a subphthalocyanine (a6)/C60-based bilayer heterojunction OPV.67 Due to the deep HOMO level of a6, the
devices exhibited much higher VOC (0.97 V) as compared to
conventional devices based on CuPc/C60 bilayer heterojunction
(0.42 V), without a concomitant reduction in JSC, resulting in
enhancement in PCE from 0.9% to 2.1%. Gommans et al.
reported a higher JSC (5.4 mA cm2) and higher PCE (3.0%)
from this device architecture.68
In 2009, solution processing of subnaphthalocyanine (SubNc, a7)
was carried out for the rst time to form a donor layer in
ecient bilayer heterojunction OPVs.69 Due to its unique
properties, such as good solubility, low tendency to aggregate,
and strong light absorption in the visible region, amorphous
a7 lms with good charge transporting and light-harvesting
properties can be prepared via simple solution casting. The
a7/C60 bilayer device based on solution processed a7 donor
layer demonstrated a PCE of 1.5%, with a JSC of 5.6 mA cm2,
VOC of 0.55 V, and FF of 0.49 after thermal annealing at 120 1C
for 40 min. At the same time, Verreet et al. reported that the
a7/C60 bilayer OPVs based on vacuum deposited a7 donor layer
produced a higher PCE of 2.5%, with JSC of 6.1 mA cm2, VOC
of 0.79 V, and FF of 0.49.70 The decreased VOC as compared
to that of a6-based devices results from greater conjugation
imparted by the additional benzene rings in a7, which raises
the HOMO energy level.71 However, the benzene rings are also
responsible for the shift in absorption to longer wavelengths and
a resultant improvement of JSC, compared to a6-based OPVs.
Merocyanine (MC) dye-based molecules oer high absorption
coecients (usually over 1 105 M1 cm1) and suciently large
variability in the position of the HOMO and LUMO levels.72,73
In 2008, Wurthner, Meerholz and coworkers have successfully
applied MC dyes in solution-processed BHJ OPVs for the rst
time. The optimized PCEs were up to 1.54% or 1.74% for blends
of MC dyes (a8 or a9):PC61BM.72 Later, they modied the push
pull dye a8 with a exible alkyl chain to achieve more ecient
photovoltaic molecules by bridging the electron donating unit
with a propylene group in a10 to diminish the exibility of the
structure and to ensure a more planar geometry.73 a10 exhibited
relatively high hole mobility of 5 105 cm2 V1 s1, ve times
of that for a8. Solution-processed devices based on a a10:PC61BM
blend showed a JSC of 8.24 mA cm2, larger than that of
a8:PC61BM (5.30 mA cm2), resulting in a remarkably improved
PCE of 2.59%. Moreover, vacuum processed BHJ OPVs based
on a10 and C60 were also fabricated, and the best vacuum
processed device showed a promising PCE of 4.9%.74 More
recently, a PCE of 6.1% was achieved by introducing MoO3
instead of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)
(PEDOT:PSS) as hole-collecting contact sandwiched between
the active layer and anode after solvent annealing in CH2Cl2
for 10 min.12 They developed a new dye a11 for application in
solution-processed OPVs, the optimized device showed a PCE
of 4.5% with a VOC of 1.0 V.75 They reported a parallel-BHJ
cell that forms in situ driven by dipolar intermolecular forces
when mixing two merocyanine dyes with complementary
absorption as double-donors with C60 acceptor. By optimizing
the ratio of the two donor components and the thickness of the
active layer, the PCE (3.2%) of the blend donor cells was
higher than either (2.62.7%) of the reference devices based on
Chem. Soc. Rev.
the individual dyes only. This synergetic eect is attributed to

a more ecient photon harvesting eciency of the mixed
donor cells compared to either of the single donor devices.76
MC dyes show a great potential for the application in highly
ecient tandem solar cells. Very recently, a dye a8 and C60-based
novel tandem-cell device architecture, combining bilayer and
bulk heterojunctions, was fabricated by fully vacuum depositing,
consisting of only four organic layers.77 The optimized PCE was
up to 4.8%, with a strikingly high VOC of 2.1 V, which is the
highest VOC value reported for small molecule tandem solar
cells. Wurthner et al. also investigated the charge dissociation at
the D/A heterointerface of thermally evaporated bilayer heterojunction MC dye (an analog with propyl replacing butyl in a8)/C60
OPVs, where they found that the FF value can be improved by
evaporating the dye lm on a heated substrate or postannealing the completed devices above the glass transition
temperature (Tg) of this MC donor. The optimized bilayer
device showed PCE up to 3.9% with very high FF of 0.70.78
Squaraine (SQ) has been eectively applied to small molecule OPV devices.7986 The SQ dye-based molecules showed
broad absorption from 500 to 900 nm in the lm, high
absorption coecients (over 1 105 M1 cm1), good photochemical and thermal stability.87 In 2008, Marks and coworkers
reported that a series of SQ-based molecules exhibited promising
performance in solution processed BHJ OPV, and the optimized
a12-based device processed in air exhibited a PCE of 1.24%.79
Subsequently, the structure modication by using hexenyl
groups (a13) instead of 2-ethylhexyl side chains improved
the device PCE up to 1.99% after thermal annealing at 50 1C
for 30 min.80 Wurthner, Meerholz and coworkers replaced the
ketone on the SQ moiety with dicyanovinyl group (a14), leading
to increased crystallinity and relatively high hole mobility
(1.3 103 cm2 V1 s1 after annealing).81 The BHJ device
based on a14 and PC61BM (annealing at 110 1C for 5 min)
showed a PCE of 1.79%, with an unusually high JSC of up to
12.6 mA cm2, a high FF of 0.47, but a rather low VOC of
0.31 V. Thompson, Forrest and coworkers also recently
reported a SQ-based molecule (a15) as donor in OPVs.8284
Initially, a15 was used to fabricate bilayer heterojunction OPVs by
vacuum deposition, which exhibited a PCE of 3.2% under 1 sun,
AM1.5G simulated solar irradiation.82 Later, bilayer devices
using solution processed a15 layers with evaporated C60 layers
were found to have a higher PCE of 4.1%, while the BHJ
device achieved a PCE of 2.9%.83 Recently, they found that
post-annealing through additional extended exposure of the
blend to dichloromethane can lead to control of the nanoscale
phase separation of a15:PC71BM (1 : 6) blend lms and an
optimized morphology reduces series resistance.84 By optimizing
morphology and molecular ordering of the a15:PC71BM BHJ
OPVs, a peak PCE of 5.5% has been achieved, with a maximum
cell performance achieved when the exciton diusion length is
approximately equal to the mean a15 crystallite size. This
result suggests that the high BHJ OPV performance could be
achieved by the precise structural control of phase separation.
Furthermore, they developed a series of new SQ-based dyes;85,86
the optimized a16/C60 bilayer device with using solution processed
a16 layer with evaporated C60 layer showed the best OPV
performance after thermal annealing at 90 1C: PCE of 5.7%,
JSC of 10.0 mA cm2, VOC of 0.90 V, and FF of 0.64.86
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Crystallographic data suggest that the intermolecular stacking

of a16 molecules is closer than that of a15, thereby reducing
the device series resistance and increasing its ll factor.
Roncali and coworkers rstly reported borondipyrromethene
(BODIPY) derivatives as photovoltaic materials.8890 This type
of dyes can be used as a platform for the design of donor
materials owing to a unique combination of facile synthesis,
good stability, and high absorption coecients. Additionally,
based on the presence of a tetrahedral boron atom in the
structure, BODIPY appears as an interesting potential of
isotropic active materials for OPVs. In a rst exploration of
BODIPY-based donors, the dyes a17 and a18 were synthesized
and applied in BHJ OPVs blending with PC61BM acceptor. The
absorption spectra of a17 and a18 show a maximum at 572 and
646 nm, respectively, with high molecular extinction coecients
(1.01.3 105 M1 cm1). The OPV cells based on a17 or
a18:PC61BM (1 : 2) delivered PCE of 1.17% or 1.34%.88
Combining these two dyes with complementary absorption
characteristics and blending with PC61BM, the devices were
fabricated showing broad IPCE (the incident photon-to-current
conversion eciency, i.e., the current obtained outside the
photovoltaic device per incoming photon) spectrum from 350
to 700 nm, yielding a PCE of 1.7%, with a JSC of 4.7 mA cm2,
VOC of 0.87 V, and FF of 0.42.89 Bithiophene was incorporated
into a18 to build the new molecule a19, leading to improved hole
mobility of 9.7 105 cm2 V1 s1 from 5 105 cm2 V1 s1
for a18, while retaining the broad and strong absorption of
BODIPY. The BHJ OPV based on a19 and PC61BM showed an
improved JSC of 7.0 mA cm2 and PCE of 2.2%.90
Due to several attractive properties of diketopyrrolopyrrole
(DPP) dyes for photovoltaic applications, such as strong light
absorption, good photochemical stability, and facile synthetic
modication, Nguyen et al. have applied a series of DPP-based
materials in solution processable BHJ OPVs.9193 In 2008, they
explored the rst soluble DPP-based molecule (a20) with
terthiophene arms as a donor blending with PC61BM; the
BHJ device exhibited a JSC of 8.42 mA cm2, VOC of 0.67 V,
FF of 0.45, and an overall PCE of 2.3%.91 However, inherent
aspects of this material limit the device performance, including
high HOMO energy level, potential morphological instability
from the thermally labile alkyl group, and imbalance of carrier
mobilities (hole mobility of 5 107 cm2 V1 s1 and electron
mobility (i.e., the distance over which electrons are transported
per second under the unit electric eld) of 3 104 cm2 V1 s1
as measured using single-carrier diodes). By using 2-ethylhexyl
group instead of t-Boc substituent in a20, the new DPPbased molecule (a21) showed deeper HOMO level (5.2 eV),
improved morphological and thermal stability, and balanced
carrier mobilities when blending with PC71BM (hole mobility
of 1.0 104 cm2 V1 s1 and electron mobility of 4.8
104 cm2 V1 s1). Owing to these improvements, the OPVs
based on a21:PC71BM (1 : 1) exhibited a PCE of 3.0%, with
JSC of 9.2 mA cm2, VOC of 0.75 V, and FF of 0.44.92
The OPV performance of DPP-based materials was further
improved by replacing hexylbithiophene end groups with
benzofuran (a22). Blending a22 with PC71BM, very little phase
separation was apparent in the as-cast lm. However, thermal
annealing leads to suitable phase separation so that eective
BHJ morphologies are obtained. The degree of phase separation
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can be controlled by adjusting annealing temperature; 110 1C

yielded optimum device properties: JSC of 10 mA cm2, VOC
of 0.9 V, FF of 0.48, and PCE of 4.4%.93 In 2010, Luscombe
et al. incorporated selenophene into DPP-based molecules as
the donor material in BHJ OPVs;94 the optimized devices
based on an a23:PC61BM (1 : 1) blend showed a PCE of
1.53%, with a JSC of 4.9 mA cm2, VOC of 0.77 V, and FF
of 0.41. Recently Frechet and coworkers reported a series of
DPP-based donors with dierent end groups, and demonstrated that ecient OPV materials can be constructed by
attaching planar, symmetric end groups to electroactive small
molecules.95 pp interaction of molecule a24 dictated tight,
aligned crystal packing, favorable morphology, and promoted
intermolecular connectivity, so OPV devices based on blend of
a24:PC71BM (2 : 1) exhibited a maximum PCE of 4.1% with a
FF approaching 0.6. Marks and coworkers rst implemented
naphtho[2,3-b : 6,7-b 0 ]dithiophene (NDT) in donor materials
for BHJ OPVs.96 The molecule (a25) with NDT as core and
DPP as arms was synthesized and showed high absorption
coecient of 1.1 105 M1 cm1 at maximum absorption
of 624 nm, appropriate HOMO energy level (5.4 eV), and
relatively high hole mobility of up to 7.18 103 cm2 V1 s1.
Combined with the electron acceptor PC61BM, a high
PCE of 4.06% was achieved, with a JSC of 11.27 mA cm2,
VOC of 0.84 V, and FF of 0.42, by annealing at 110 1C for
10 min.
Similar to DPP structure, isoindigo (ID) and perylene
diimide (PDI) both have symmetrical lactam structure with
strong electron withdrawing property. Reynolds et al. reported
synthesis of a26 based on ID as core and bithiophene as arms
and application in solution processed BHJ OPVs as donor
material.97 After annealing at 110 1C, the device based on
a26:PC61BM (1 : 1) gave a PCE of 1.76%; the PCE was
increased to 2.15% by adding a polydimethylsiloxane additive,
due to more favorable morphology.98 Ko and coworkers
reported annulated thiophene PDI linked with triphenylamine
through a bithiophene bridge (a27),99 and BHJ OPV based
on a27:PC61BM (1 : 2) showed JSC of 5.94 mA cm2, VOC of
0.776 V, FF of 0.308 and PCE of 1.42%.
Frechet and coworkers reported a series of multifunctional
linear quinacridone (QD)-based molecules which showed intense
absorption in the visible spectral region, and the absorption
range and intensity were well-tuned by the interaction between
the QD core and the incorporated thiophene arms.100 A
solution processed thin lm of a28:PC71BM (1 : 2) showed
bicontinuous nanophase separated morphology, which was
feasible for exciton dissociation and charge transport. a28-based
device gave a PCE of 2.22%, under an AM1.5 simulated solar
illumination.
In dyes, Pc, MC, and DPP-based molecules have exhibited
very high performance in OPVs with PCE values over 6%,
which can be partially attributed to the strong absorption of
these materials. Interestingly, some dyes (e.g., BODIPY and
MC) with very similar structures can show very dierent and
complementary absorption spectra while retain compatibility
of other properties. Thus, multicomponent devices can be
fabricated by mixing two dyes as double-donors with fullerene
acceptor, and better device performance can be achieved, which
may deserve further attention.
Chem. Soc. Rev.
View Online

Fused acenes
In organic eld-eect transistors (OFETs), fused acenes, such
as pentacene and tetracene, have been extensively studied as a
p-type semiconductor, and especially, pentacene is well known
to exhibit extremely high hole mobility (over 1 cm2 V1 s1).101,102
The high mobility is a key factor to enhance the PCEs of OPV
devices. This type of materials has been successfully applied in
vacuum deposited bilayer or solution processed BHJ OPVs,
due to their high hole mobility, broad absorption and good
thermal stability. Table 2 provides a summary of electronic
properties as well as OPV data for representative fused acene
donors (Fig. 3).
In 2004, Kippelen et al. rst fabricated an ecient OPV
based on a bilayer heterojunction of polycrystalline pentacene (b1)
and C60.103 Under illumination of broadband light 100 mW cm2,
the device exhibited a JSC of 15 mA cm2, VOC of 0.36 V, FF
of 0.50, and PCE of 2.7%. Obviously, in this device the most
limiting factor is the low VOC. JSC and PCE were projected to be
around 8.2 mA cm2 and 1.5% under AM1.5, 100 mW cm2.
In 2005, Yang et al. fabricated bilayer heterojunction OPVs
with tetracene (b2)/C60 as the photoactive layer.104 The PCEs
of the devices were 2.3% under AM1.5 solar illumination at
100 mW cm2.
Researchers have tried to use the fused acenes for applications in solution processable BHJ OPVs by properly functionalizing with solubilizing groups such as triisopropylsilylethynyl
(b3).105 Unsubstituted pentacene adopts a herringbone motif
in solid state, while 6,13-bis(triisopropylsilylethynyl)pentacene
exhibits a structural improvement in solid state, promoting
face-to-face instead of face-to-edge (herringbone) packing,
leading to close cofacial p-stacking.36,106 Such modication oers
tunability of the p-orbital overlap and therefore control of intrinsic
charge carrier mobility, an important parameter for OPV applications. b3 can be crystallized in lm and absorb farther into the red
than pentacene, theoretically leading to higher photocurrent and
PCE. Unfortunately, b3 rapidly undergoes a DielsAlder reaction with fullerene derivatives in solution, and b3-fullerene
adduct ineectively supports photoinduced charge transfer.
Hereby, Anthony, Malliaras and coworkers fabricated a bilayer
device (spin-coated b3 layer and vacuum-deposited C60 layer),
Table 2
Optical and electronic properties, mobilities, and OPV performance of fused-acene-based donors
lmaxa/nm
b1
b2
b3
b4
b5
b6
b7
b8
b9
b10
b11
b12
b13
where adduct formation can be minimized. After optimization

of photoactive layer thickness, incorporation of exciton-blocking
layer, and thermal annealing, PCE reached a peak value of
0.5%.105 Triethylsilylethynyl-substituted anthradithiophene
(b4) exhibited an absorption cuto of 575 nm in lm and a
high hole mobility of 0.11 cm2 V1 s1.107 As-cast b4:PC61BM
(7 : 3) lm was fairly amorphous and did not generate large
photocurrent. Solvent (dichloromethane) vapor annealing of
these blends led to the formation of spherulites, which is
consisted of a network of b4 crystallites dispersed in an amorphous
matrix composed primarily of PC61BM. The spherulite covered
fraction of the lm appeared rough with submicrometer,
needle-like crystals, which led to a marked improvement in
photocurrent generating capacity. The generated photocurrent
was proportional to the area covered by spherulites. Devices
with 82% spherulite coverage gave the best PCE of 1.0%, with
a JSC of 2.96 mA cm2, VOC of 0.84 V and FF of 0.40.107
Thompson et al. synthesized triethylsilylethynyl-substituted
tetracene monomer (b5) and dimer (b6).108 The PCE of bilayer
OPV device based on b5 and C60 was 0.5%, with VOC of 1.06 V,
JSC of 1.48 mA cm2, and FF of 0.34. The VOC (0.31 V) for the
dimer (b6) based device was substantially lower than that for
the monomer based device, leading to lower PCE (0.2%), and
the main reason might be that b6 has higher HOMO energy
level (5.16 eV) than that (5.36 eV) of b5.
In 2008, Marrocchi and coworkers reported BHJ OPV
devices based on an anthracene derivative (b7):PC61BM
(1 : 1.17) blend with a PCE of 1.12%.109 They found that an
acetylenic spacer yielded signicantly better OPV performance
than an olenic spacer in this system.110 The optimized OPV
device based on b7:PC61BM (2 : 1) showed a JSC of 3.1 mA cm2,
VOC of 0.89 V, FF of 0.45, and overall improved PCE of 1.27%
upon thermal annealing at 60 1C.111 In 2010, Chung et al.
reported triisopropylsilylethynyl anthracene derivative substituted with bithiophene (b8).112 The BHJ OPVs were fabricated
by blending b8 with PC61BM (1 : 14). As varying the blending
ratio, the blend lm morphology changed from obvious phasesegregated crystalline domains at 1 : 1 ratio to homogeneous,
nearly amorphous phases at 1 : 4 ratio. At the ratio of 1 : 4,
BHJ OPVs yielded a PCE of 1.4%, higher than that for
other ratios, revealing that well-mixed homogeneous phases,
520
535
612
503
537
620
368
375
Egopt/eV
1.77
2.14
1.65
2.16
mhb/cm2 V1 s1
0.11 (O, N)
2.25
2.19
2.0
1.90
0.07 (O, N)
104105 (S, B)
2.87
2.51
2.3103 (O, N)
HOMOc/LUMO/eV
5.15/2.98
5.36/2.76
5.16/3.00
5.51/3.00
5.3/2.8
5.1/3.0
5.46/3.60
5.25/2.64
5.03/2.6
5.28/2.77
JSC/mA cm2
Active layerd
b1/C60
b2/C60
b3(sol)/C60
b4:PC61BM (7 : 3)
b5/C60
b6/C60
b7:PC61BM (1 : 1.17)
b8:PC61BM (1 : 4)
b9:PC61BM (1 : 1)
b10:PC71BM (1 : 1)
b11:f3 (2 : 3)
b12:PC61BM (1 : 2)
b13:PC71BM (1 : 2)
15
7.0
1.9
2.96
1.48
1.73
1.37
4.55
6.55
5.41
3.35 102
2.68
6.37
VOC/V
0.363
0.58
0.47
0.84
1.06
0.31
0.762
0.78
0.83
0.80
0.69
0.90
1.0
FF
0.50
0.57
0.52
0.40
0.34
0.37
0.44
0.40
0.41
0.45
0.4
0.61
0.38
PCEe (%)
f
2.7
2.3
0.5
1.0
0.5
0.2
1.12g
1.40
2.25
1.95
1.95h
1.46
2.5
Ref.
103
104
105
107
108
108
109
112
113
114
115
116
117
a
In lm. b O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. c From electrochemistry. d Donor/acceptor: bilayer by
vacuum deposition unless stated otherwise; donor:acceptor: blend by solution process; sol: solution process. e AM1.5, 100 mW cm2 unless stated
otherwise. f Broad band light 100 mW cm2. g 41 mW cm2. h At 490 nm, 0.47 mW cm2.
Chem. Soc. Rev.
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Fig. 3
Chemical structure of fused acene donors.
rather than highly crystalline phases, resulted in improved

PCE by allowing for ecient charge separation.
In 2009, Watkins and coworkers reported a new class of
organic semiconductors based on dibenzo[b,def]chrysene (DBC).113
In contrast to well-studied pentacenes, DBC derivatives did
not undergo cycloaddition reactions with fullerenes. In the
BHJ OPVs, one successful result was obtained by using a mixture
of triethylsilylethynyl-substituted DBC (b9) and PC61BM spincasted from chloroform solution. Casting solvents played an
important role in determining crystallinity and morphology.
High boiling point solvent such as chlorobenzene led to larger
scale of phase separation, and reduced interfacial area, resulting
in very low device eciency. Spin-casted BHJ lms from low
boiling point solvent such as chloroform showed phase separation at the nanoscale, which beneted more ecient dissociation
This journal is
of the photogenerated excitons and collection of separated

charges. At high concentration and high spin speed, the BHJ
lms from chloroform have been well modied to enhance the
PCE of OPV devices. Hereby the optimized device showed a
JSC of 6.55 mA cm2, VOC of 0.83 V, FF of 0.41 and PCE of
2.25%. Very recently, triisopropylsilylethynyl-functionalized
dibenzo[def,mno]chrysene (b10) with similar structure to b9
was synthesized and applied to fabricate OPV devices.114 The
primary BHJ OPVs based on b10:PC71BM exhibited a PCE of
1.95%, lower than that of b9.
In 2001 Friend and coworkers used a discotic liquid crystalline hexaperihexabenzocoronene (HBC) derivative (b11) in
combination with a PDI acceptor (f3, Fig. 7) to fabricate
solution-processed OPVs with a PCE of 1.95% at 490 nm
(0.47 mW cm2).115 Recently, Holmes and coworkers reported
Chem. Soc. Rev.

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synthesis of diuorenyl-substituted HBC (b12) and its use in

OPVs. Devices based on a blend of b12:PC61BM (1 : 2) after
thermal annealing at 150 1C generated JSC of 2.68 mA cm2
and PCE of 1.46%.116 Later, they attached oligothiophene to
b12 to yield b13.117 Relative to b12, b13 has extended conjugation and broader absorption. The BHJ OPVs based on
b13:PC71BM (1 : 2) exhibited higher JSC (5.71 mA cm2) and
higher PCE (2.64%) relative to the devices based on
b12:PC71BM (1 : 2) (JSC of 2.53 mA cm2 and PCE of 1.0%).
Most fused acenes possess high crystallinity and relatively
high mobility, and these materials show moderate photovoltaic performance in vacuum deposited bilayer devices.
For solution-processed BHJ devices, high crystallinity of fused
acenes leads to large phase separation scale when blending with
fullerene acceptor, which causes decreased device performance.
Thus, tuning the crystallinity of fused acenes by modifying their
substituent groups is necessary to achieve high performance
BHJ devices based on fused acenes.
Oligothiophenes
Oligothiophenes, including one-dimensional, two-dimensional
and three-dimensional conjugated systems, are one of the largest
families of organic semiconductors, and have been widely used
in OPVs due to their high charge-carrier mobility and facile
synthesis to tune energy levels.118 Table 3 summarizes electronic
properties as well as OPV data for representative one, two and
three dimensional oligothiophenes (Fig. 4).
BHJ OPVs based on blend of a-sexithiophene (c1) and C70
were fabricated by the vacuum coevaporation method.119
Since c1 was easy to aggregate and crystallize, it was dicult
to mix homogeneously c1 and C70 at a blend ratio of 1 : 1 (w/w),
leading to insucient formation of carrier transport network
and charge separation. When c1:C70 ratio was 1 : 5 (w/w),
excessive C70 prevented c1 from crystallization, leading to
Table 3
c1
c2
c3
c4
c5
c6
c7
c8
c9
c10
c11
c12
c13
c14
c15
c16
c17
c18
c19
c20
c21
a
d
e
formation of amorphous structure, so that charge separation

eciency was improved and desirable carrier transport interpenetrating network was formed. After thermal annealing at
140 1C for 20 min, the OPV devices exhibited a PCE of 2.38%.
However, narrow absorption and relatively high HOMO level
of c1 limited JSC and VOC of OPVs, respectively. To achieve
high-eciency OPVs, conjugated oligothiophenes with low
band gap, broad absorption and appropriate energy levels
are required. One successful approach is to introduce electron
withdrawing units into the conjugated backbone to form DA
oligothiophenes with highly polarizable p-electron systems,
which can extend the absorption spectrum of the donor toward
longer wavelengths by an intramolecular charge transfer and
thus have a good match with the solar spectrum.
The dicyanovinyl (DCV) group has strong electron-withdrawing
properties leading to ecient intramolecular charge transfer.
Some DCV-substituted oligothiophenes have been synthesized and applied in vacuum-deposited and solution-processed
OPVs.120126 In 2006, Bauerle, Leo and coworkers fabricated
bilayer heterojunction OPVs based on terminally DCV-substituted
oligothiophenes bearing butyl side chains (c2) as donor and
C60 as acceptor.120 Due to low HOMO level and red-shifted
absorption of c2, these OPVs aorded PCEs of up to 3.4%,
with high VOC of 0.98 V, JSC of 10.6 mA cm2 at 118 mW
cm2 simulated sunlight. Later, they used selenophene instead
of thiophene in c2 to synthesize a series of c2 analogs.
Selenophene-containing oligomers showed slightly lower performance due to lower degree of donor/acceptor phase separation
compared to c2 in BHJ OPVs, but PCE was still in a good range
of 2.53.1%.123 Recently, they synthesized a series of terminally
DCV-substituted oligothiophenes without solubilizing side
chains via a novel convergent approach and used them as
electron donors in vacuum-processed bilayer heterojunction
and BHJ OPVs.124 OPV devices incorporating c3 and C60
showed PCEs of up to 2.8% for bilayer heterojunction
Optical and electronic properties, mobilities, and OPV performance of oligothiophene-based donors
lmaxa/nm
Egopt/eV
573
579
614
580
618
563
650
503
548
415
720
720
390
426
450
535
495
400
390
399
1.77
1.68
1.68
1.74
1.69
1.83
1.73
2.00
1.87
1.9
1.51
1.5
2.13
2.1
2.06
1.74
2.28
2.65
mhb/cm2 V1 s1
1.5 104 (S, N)

3.3 104 (S, N)
1.5 104 (S, N)
4.5 104 (S, N)
1.8 104 (S, N)
2.5 104 (S, N)
0.12 (O, N)
1.1 104 (O, N)
HOMOc/LUMO/eV
Active layerd
JSC/mA cm2
VOC/V
FF
PCEe (%)
Ref.
5.3(U)/3.1
5.6(U)/
5.43/3.87
5.13/3.42
5.13/3.29
5.21/3.68
5.11/3.54
4.95/3.26
5.50/3.34
5.65/3.64
5.28/3.38
5.16/3.60
5.2/3.6
5.26/2.66
5.29/3.16
c1:C70 (1 : 5) (vac.)
c2/C60
c3:C60 (2 : 1) (vac.)
c4:PC61BM (1 : 1.4)
c5:PC61BM (2 : 1)
c6:PC61BM (2 : 1)
c7:PC61BM (2 : 1)
c8:PC61BM (1 : 0.8)
c9/C60
c10/C60
c11:PC71BM (1 : 4)
c12:PC71BM (3 : 2)
c13:PC71BM (7 : 3)
c14:PC61BM (1 : 1.2)
c15:PC71BM (1 : 2)
c16:PC61BM (1 : 4)
c17:PC61BM (1 : 4)
c18:PC71BM (1 : 4)
c19:PC61BM (1 : 2)
c20:PC61BM (1 : 3)
c21:PC61BM (1 : 3)
9.2
10.6
11.1
12.4
10.74
13.98
9.77
11.51
3.1
4.7
8.45
10.9
14.4
3.65
4.61
3.35
2.5
4.79
4.19
1.13
1.33
0.58
0.98
0.97
0.88
0.86
0.92
0.93
0.80
0.98
1.00
0.82
0.7
0.78
0.85
0.94
0.94
0.93
0.93
0.97
0.85
0.51
0.45
0.49
0.49
0.34
0.55
0.47
0.60
0.64
0.57
0.67
0.43
0.42
0.59
0.26
0.36
0.40
0.47
0.37
0.42
0.24
0.27
2.38
3.4f
5.2
3.7
5.08
6.10
5.44
5.84
1.73
3.15
3.0
3.2
6.7
0.80
1.54
1.3
1.12
1.64
1.72
0.29g
0.20h
119
120
124
126
127
14
128
129
133
133
134
135
15
136
137
138
140
145
147
148
149
5.4/3.3
5.1/3.2
5.28/3.07
In lm. b O and S: measured by OFET or SCLC method, N: in neat lm. c From electrochemistry unless stated otherwise, U: from UPS.
Donor/acceptor: bilayer by vacuum deposition; donor:acceptor: blend by solution process unless stated otherwise; vac: vacuum deposition.
AM1.5, 100 mW cm2 unless stated otherwise. f 118 mW cm2. g 80 mW cm2. h 99 mW cm2.
Chem. Soc. Rev.
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Fig. 4
This journal is
Chemical structure of oligothiophene donors.
Chem. Soc. Rev.

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and 5.2% for BHJs under simulated AM1.5 100 mW cm2

illumination.
In 2010, Chen and coworkers reported the synthesis of a
DCV-substituted oligothiophene with six solubilizing side chains
(c4) and application in solution-processed BHJ OPVs.125,126
Absorption spectra of c4 lms showed good solar spectral
coverage. Hole mobility of pristine c4 was 1.5 104 cm2 V1 s1
measured by the space charge limited current (SCLC) model.125
Under illumination of 100 mW cm2, the devices based on
c4:PC61BM blend (1 : 1.4) displayed a PCE of 3.7%, with JSC
of 12.4 mA cm2, VOC of 0.88 V, and FF of 0.34.126 Carefully
designing and controlling the position and density of dierent
alkyl side or end chains can not only increase solubility of
materials in organic solvents for spin-casting devices but also
improve their packing structure and solid-state miscibility
with fullerenes. Recently, Chen and coworkers designed and
synthesized a series of oligothiophenes end-capped with electronwithdrawing alkyl cyanoacetate groups instead of DCV and
investigated the correlation between these dierent end groups
and their BHJ device performance.127 OPVs based on
c5:PC61BM (2 : 1) exhibited a PCE of 5.08%, with a JSC of
10.74 mA cm2 VOC of 0.86 V and FF of 0.55. Compared to c4
with DCV end group, c5 with alkyl cyanoacetate end group
gave higher PCEs. The better PCEs beneted from improved
FF (over 50%), which came from better lm quality and
morphology. Later, 3-ethylrhodanine was introduced as an
end acceptor group to synthesize oligothiophene c6.14 c6
showed stronger solar absorption than c5, which is benecial
to improving the JSC. A very high PCE of 6.10% was obtained
by using a blend of c6:PC61BM as the active layer, with a
remarkable JSC of 13.98 mA cm2 and VOC of 0.92 V. Meanwhile, they replaced the central thiophene unit in c5 with a
more electron-rich and planar structure such as benzodithiophene and dithienosilole to synthesize c7 and c8. Improved
mobility and absorption of c7 and c8 led to enhanced PCEs
(5.44% for c7128 and 5.84% for c8129). The high PCE values
5.086.10% of c5c8 based devices suggest that the oligothiophenes with electron-withdrawing end groups are very promising donor materials for solution processed BHJ OPVs. In
addition, Roncali et al. synthesized a series of symmetrical and
unsymmetrical septithiophenes end-capped with DCV and
thiobarbituric (TB) electron-withdrawing groups, and investigated their photovoltaic properties in bilayer OPVs based on
spin-coated donor layer and vacuum-deposited C60 acceptor
layer.130 They found an interesting phenomenon that breaking
the symmetry of the donor structure can lead to a signicant
increase of VOC, which may be attributed to the intermolecular
interactions and molecular orientation.
Other electron withdrawing units such as benzothiadiazole
(BT), thiadiazolopyridine (TP) and triuoroacetyl (TFA) were
also introduced into oligothiophene systems.131135 Bauerle and
coworkers reported two linear oligothiophenes c9 and c10 endcapped with BT and TP acceptor units, respectively.133 Bilayer
heterojunction OPVs based on c10 and C60 showed a higher PCE
(3.15%) with a very high FF (0.67) compared to that of c9-based
devices (1.73%). The excellent FF, which is among the highest
values reported for small molecule-based OPVs, might be due to
better stacking in thin lm caused by intermolecular hydrogenbonding interactions by the nitrogen atom of the pyridine ring.
Chem. Soc. Rev.
In 2010, Frechet and coworkers reported a series of platinumacetylide linear oligothiophenes containing a thienyl-BT-thienyl
core, and various oligothiophenes were connected to control the
molecular packing by changing the number of thiophene units
from two to four.134 The best device based on the oligomer with
terthiophene (c11) blending with PC71BM (1 : 4) after annealing
at 70 1C for 30 min exhibited a JSC of 8.45 mA cm2, VOC of
0.82 V, FF of 0.43, and PCE of 3.0%. Recently, Bazan and
coworkers introduced dithienosilole (DTS) in oligothiophenes.135
The DTS-containing oligothiophenes showed broad absorption
extending beyond 700 nm, due to intramolecular charge transfer.
After annealing at 110 1C for 2 min, BHJ OPVs based on
c12:PC71BM (3 : 2) showed a JSC of 10.9 mA cm2 and PCE of
3.2%. Later, Heeger, Bazan and coworkers synthesized one
novel isomeric compound (c13) of c12, and used it to fabricate
solution processed BHJ OPVs.15 Compound c13 exhibited
strong optical absorption, especially from 600 to 800 nm,
and a high hole mobility of ca. 0.1 cm2 V1 s1 measured by
organic eld-eect transistor (OFET). Under AM1.5 irradiation (100 mW cm2), a record PCE of 6.7% was achieved for
small-molecule donor based BHJ devices from c13:PC71BM
(7 : 3, w/w). This high eciency was obtained by adding
remarkably low percentage of solvent additive (0.25% v/v of
1,8-diiodooctane) during the lm-forming process, which led
to decreased domain sizes in the BHJ layer. Additionally, the
low fraction of fullerene in BHJ layer is surprising and
interesting. The high performance at such a low fullerene
concentration indicated that the crystalline donor may render
the fullerene acceptor to form percolated pathways to the
electrode. Moreover, it seems that lower fullerene concentration has some connection with the small amount of additive
required to achieve optimized BHJ morphologies.
Aside from linear oligothiophenes, two-dimensional oligothiophene systems have also been reported. Early in 2006, Liu,
Tian and coworkers reported X-shaped conjugated systems
with four linear oligothiophene arms connected to a central
thiophene core.136 c14 with the longest arms had the lowest
bandgap with an absorption onset of 520 nm; the blend of c14
and PC61BM exhibited the smallest feature size in AFM
images. BHJ OPVs based on c14:PC61BM gave a PCE of
0.80% under simulated solar illumination. Recently, Zhan and
coworkers reported a new X-shaped oligothiophene (c15) with
four longer arms than c14.137 Owing to the longer conjugation,
c15 exhibited red shifted absorption with the maximum at
426 nm and the onset of 582 nm in lm relative to c14.
BHJ OPVs based on the blend of c15:PC61BM (1 : 2) gave a
VOC of 0.93 V, JSC of 2.71 mA cm2, FF of 0.40, and PCE of
1.02%. Replacing PC61BM with PC71BM led to an improved
JSC of 4.61 mA cm2 and a higher PCE of 1.54%.
In 2006, Kopidakis et al. investigated 1,3,5 and 1,2,4,5substituted phenyl-cored thiophene dendrimers as donor materials
in photovoltaic application.138 Once again, the oligomers with
the longest oligothiophene arms exhibited the best performance.
Although three-armed dendrimers had superior mobility,
four-armed dendrimers enabled solution-cast lm formation
and yielded smaller optical bandgap. The best material (c16)
consisted of a 1,2,4,5-substituted phenyl core with each arm
containing six thiophenes. Solution processed BHJ devices
based on c16:PC61BM (1 : 4) exhibited PCE of 1.3%,
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with a JSC of 3.35 mA cm2, VOC of 0.94 V and FF of 0.40.

However, due to high bandgaps (over 2.3 eV) and poor
morphology, 1,3,5-substituted phenyl-cored thiophene dendrimers did not show promising photovoltaic performance,
which was similar to the work from Roncali et al.139 In an
eort to improve overlap with the solar spectrum, they
reported a thiophene dendrimer that was modied with an
electron-withdrawing group in order to lower the bandgap.140
The dendrimer c17 had an electron-withdrawing tricyanobenzene core and three oligothiophene arms to create a pushpull
structure that lowers LUMO level. Compared to its counterpart without cyano groups and other 1,3,5-substituted phenylcored thiophene dendrimers, the optical absorption onset of
c17 was down to 2.1 eV, attributed to lowering of the LUMO
level. The density functional theory calculations showed that
the optimized geometry of c17 is totally planar and therefore
p-stacking should be favored in lms.141 Planarized structure
led to improved morphology both in neat lms and in blends
with PC61BM. The BHJ OPVs based on c17:PC61BM showed
an improved FF, from 0.28 for that without cyano groups to
0.47, leading to an overall PCE enhancement from 0.40%
to 1.12%.140 The authors attributed the higher FF to the
improved morphology and reduced carrier recombination of
the c17:PC61BM blend.
Extended pushpull oligothiophenes with DCV groups
exhibited narrow optical energy gap, strong absorption and
favorable intermolecular pp interactions in the solid state
and were promising donors for high-eciency photovoltaic
applications.142144 Wong and coworkers synthesized a series
of dendritic oligothiophenes with carbazole and DCV, the
optical bandgap of these molecules in thin lms greatly
reduced to 1.74 eV with strong spectral broadening and a
high ionization potential at ca. 5.5 eV as determined by UPS.
The BHJ OPVs fabricated from dendrimer c18 blended with
PC71BM (1 : 4) showed a PCE of 1.64% with a Voc of 0.93 V
after annealing at 100 1C for 10 min.145
In 2008, Bauerle and coworkers reported promising OPV
results with large, highly branched oligothiophene dendrimers
blended with PC61BM.146,147 The largest dendrimer showed
absorption cuto up to 600 nm. Oligothiophene c19 showed the
best result in BHJ OPV blending with PC61BM, and the optimized
device produced a PCE of 1.72%, with JSC of 4.19 mA cm2,
VOC of 0.97 V, and FF of 0.42.147
One issue with many OPV materials, such as fused acenes
and low dimensional oligomers, is molecular and crystal
orientation. High anisotropy in light absorption and charge
transport is an important concern for the future of OPV
materials, especially the solution processable BHJ materials.
In 2006, Roncali and coworkers sought to overcome the low
dimensionality of planar small molecules via synthesis of three
dimensional oligothiophenes with a tetrahedral silicon core.148
Absorption spectra of these compounds are identical in thin
lm and solution state, indicating an absence of aggregation or
intermolecular p-interactions in the solid state. Within a BHJ,
these molecules are likely to form amorphous hole-transporting
networks that may hinder charge collection. The PCE of device
based on c20:PC61BM (1 : 3) under white light irradiation at
80 mW cm2 is 0.3%, a relatively high value considering the
charge transport limitation and the 440 nm light absorption onset.
This journal is
However, the insucient robustness of the silicon-thiophene

bond was identied as a problem, and in some cases degradation
of the molecules was observed during vacuum sublimation. In
order to solve this problem, they have developed a dierent
approach based on the use of a bithiophene twisted by steric
eect as a core for building three dimensional oligothiophenes.
The steric interactions associated with the xation of bulky
groups at the 3,3 0 -positions of bithiophene produced a dihedral
angle between the thiophene rings, thus generating a tetrahedral
starting unit for the construction of three dimensional systems.149
BHJ OPVs based on c21 and PC61BM in a 1 : 3 (w/w) ratio
under white light irradiation at 99 mW cm2 gave a JSC of
1.33 mA cm2, VOC of 0.51 V, and PCE of 0.20%. The low
PCE was considered in relation with the poor absorption of
c21, the maximum peak was only 399 nm.
One-dimensional oligothiophenes with pullpush structure
exhibited promising OPV performance. Especially, oligothiophenes with electron-withdrawing end groups yielded very high
PCEs up to 6.10% when blending with PC61BM. Meanwhile,
oligothiophenes with fused rings (such as benzodithiophene and
dithienosilole) showed better performance in BHJ devices. On
the other hand, the issue mentioned above in low dimensional
oligomers is molecular and crystal orientation. High anisotropy
in light absorption and charge transport is critical concern for
OPV materials, especially for the solution processable BHJ
materials. Thus, introducing the electron-withdrawing units
and fused rings into three-dimensional oligothiophenes may
produce surprising and superb results in BHJ OPVs.
Triphenylamine derivatives
Triphenylamine (TPA) has been regarded as a promising unit
for organic semiconductor materials due to its good holetransporting and electron-donating capabilities.53,150 TPAbased small molecules, including pushpull molecules with
TPA as the terminal group and star-shaped molecules with
TPA as core have been widely investigated for application in
OPVs, and they have exhibited good photovoltaic performance. Table 4 provides a summary of electronic properties
as well as OPV data for representative linear and star-shaped
TPA-based donors (Fig. 5).
Li and coworkers reported a series of TPA-based linear
pushpull chromophores with benzothiadiazole (BT) pull
moieties.151,152 Early in 2006, they synthesized a DAD
molecule d1 with TPA as the donor, BT as the acceptor and
vinylthiophene as the bridge, and the solution-processed BHJ
OPVs based on d1:PC61BM (1 : 1) blend showed a PCE of
0.26%.151 Replacing thiophene in d1 with 4-hexylthiophene
(d2) or 4-hexylthieno[3,2-b]thiophene (d3) led to higher PCEs
(1.44%) due to better lm formation caused by alkyl chains.152
Zhan and coworkers synthesized d4, similar to d2 but without
a vinyl group.153 BHJ OPVs based on d4:PC71BM (1 : 3) gave a
higher Voc (0.93 V) and higher PCE (2.21%) relative to
d2:PC71BM (1 : 3).154 They used 1% 1,8-octanedithiol (ODT)
as additive to further improve PCE to 2.86%. This 30% PCE
enhancement was attributed to aggregated domain formation,
enhanced absorption, improved hole mobility, and more
balanced charge transport. Later, they replaced benzothiadiazole
in d4 with thiazolothiazole to synthesize d5; BHJ OPVs
Chem. Soc. Rev.
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Table 4
Optical and electronic properties, mobilities, and OPV performance of TPA-based donors

lmaxa/nm Egopt/eV mhb/cm2 V1 s1

d1
d2
d3
d4
d5
d6
d7
d8
d9
d10
d11
d12
d13
d14
d15
d16
d17
d18
d19
d20
d21
d22
d23
d24
d25
d26
d27
560
569
581
534
436
508
498
536
592
542
684
550
587
435
1.8
1.73
1.64
2.03
2.31
2.09
1.88
1.79
1.7
1.91
544
540
538
1.91
1.84
1.78
538
563
585
486
541
529
1.78
1.78
1.9
1.83
1.65
2.14
1.86
1.96
HOMOc/LUMO/eV Active layerd
5.1/3.3
5.14/3.37
5.10/3.42
5.16/2.99
5.39/2.91
5.4(U)/
(S, N) 5.14/2.76
5.16/3.37
1.04 104 (S, N)

1.48 104 (S, N)
3.5 107 (S, B)
1.3 106 (S, B)
1.19 106
5.4(U)/
5.15/3.71
5.46(U)/
5.43/3.57
1.86
2.38
2.9 105 (S, N)

0.011 (O, N)
3.9 105 (S, N)
5.6 105 (S, N)
4.9 104 (O, N)
4.7 105 (S, N)
6.02/
5.50/
5.72/
5.78/
5.28/3.11
5.22/3.34
5.03/3.42
5.41/3.37
5.3/3.27
5.19/3.08
JSC/mA cm2 VOC/V FF
0.867
d1:PC61BM (1 : 1)
d2:PC71BM (1 : 3)
4.84
d3:PC71BM (1 : 3)
5.71
d4:PC71BM (1 : 3)
7.49
d5:PC71BM (1 : 4)
9.39
4.9
d6:PC71BM (1 : 3)
d7:PC71BM (1 : 3)
5.07
5.94
d8:PC71BM (1 : 3)
3.06
d9/C60
9.53
d10:C70 (1 : 1) (vac)
d11/d11:C70 (1 : 1)/C70 14.68
d12/d12:C70 (1 : 1)/C70 12.1
6.32
d13:PC61BM (1 : 2)
2.33
d14/C60
4.10
d15:PC61BM (1 : 3)
1.97
d16/C60
3.65
d17/C60
d18/C60
4.59
1.7
d19/C60
d20:PC61BM (1 : 2)
5.30
d21:PC61BM (1 : 2)
5.83
d22:PC71BM (1 : 3)
9.51
5.21
d23:PC71BM (1 : 2)
7.66
d24:PC71BM (1 : 2)
1.66
d25:PC61BM (1 : 3)
d26:PC61BM (1 : 3)
4.18
8.58
d27:PC71BM (1 : 3)
0.76
0.79
0.74
0.93
0.91
0.92
0.71
0.79
0.97
0.83
0.79
0.95
0.67
0.48
0.66
0.72
0.89
1.15
0.67
0.87
1.07
0.87
0.84
0.88
0.89
0.81
0.85
0.33
0.375
0.34
0.41
0.437
0.41
0.38
0.44
0.33
0.48
0.50
0.56
0.29
0.41
0.30
0.34
0.36
0.28
0.3
0.39
0.31
0.52
0.308
0.439
0.41
0.39
0.327
PCEe (%) Ref.

0.26f
1.44
1.44
2.86
3.73
1.8
1.40
2.06
1.08g
3.82
5.81
6.4
1.23
0.46
0.81
0.49
1.17
1.85h
0.32
1.80i
2.02i
4.3
1.4
3.0
0.61
1.33
2.39
151
152
152
154
155
156
159
159
160
161
162
13
163
165
165
165
165
167
168
169
169
170
171
171
172
173
174
a
In lm. b O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. c From electrochemistry unless stated otherwise,
U: from UPS. d Donor/acceptor: bilayer by vacuum deposition; donor:acceptor: blend by solution process unless stated otherwise; vac: vacuum
deposition. e AM1.5, 100 mW cm2 unless stated otherwise. f 85 mW cm2. g 90 mW cm2. h 80 mW cm2. i 95 mW cm2.
based on d5:PC71BM (1 : 4) after thermal annealing at 110 1C for

10 min aorded JSC of 9.39 mA cm2, VOC of 0.91 V, FF of
0.44, and PCE of 3.73%.155 Bo and coworkers reported a
series of X-shaped TPA-based molecules with BT as core.156
Interestingly, the X-shaped molecules exhibited deeper HOMO
levels and wider bandgaps than corresponding linear molecules. The best X-shaped molecule (d6) blending with PC71BM
showed a JSC of 4.9 mA cm2,VOC of 0.92 V, FF of 0.41, and
PCE of 1.8%, similar to that for its linear counterpart.
Cyano-containing electron withdrawing units, such as dicyanomethylenepyran (DCP),157159 DCV13,160162 and cyanoacetic
acid,163 were also combined with TPA to build pushpull
molecules. In 2007, Li and coworkers designed and synthesized
a DAD molecule (d7) with TPA as the donor, DCP as the
acceptor, and divinylbenzene as the bridge.157 The VOC, JSC,
FF, and PCE of the optimized device based on d7:PC61BM
(1 : 3) reached 0.9 V, 2.14 mA cm2, 0.41, and 0.79%, respectively. Replacing benzene bridge in d7 with thiophene (d8) led
to broader absorption, benecial to generating excitons and
improving the JSC of OPVs.159 The OPV devices based on
d8:PC71BM (1 : 3) blend showed a JSC of 5.94 mA cm2
and PCE of 2.06%, higher than that (1.40%) of devices based
on d7.
In 2011, Roncali and coworkers reported a series of molecules
with TPA as the end group, a DCV dimer as the core and
thiophene as the bridge.160 These compounds showed interesting
light-harvesting properties (absorption onset at ca. 700 nm)
and low-lying HOMO levels. The symmetrical molecule d9
with one thiophene as bridge showed promising performance
in d9/C60 bilayer heterojunction OPVs: JSC of 3.06 mA cm2,
Chem. Soc. Rev.
VOC of 0.97 V, FF of 0.33, and PCE of 1.08%. Lin, Wong

and coworkers reported a molecule (d10) adopting coplanar
diphenylsubstituted dithienosilole as a central p-bridge between
TPA and DCV, with a cuto absorption wavelength of 650 nm;
vacuum deposited planar-mixed heterojunction (PMHJ) OPVs
incorporating C60 or C70 as an acceptor showed an appreciable
PCE of 2.69 or 3.82%, respectively.161 More recently, they
reported a novel DAA molecule (d11) with ditolylaminothienyl as the donor and BT and DCV as acceptors for
vacuum-deposited OPV devices;162 PMHJ OPVs using C70
acceptor delivered very high Jsc of 14.68 mA cm2 and PCE of
5.81%, which was attributed to the solar spectral response
extending to the near-IR region and the ultracompact absorption
dipole stacking of the thin lm. Later, they further developed
DAA molecule (d12) where the pyrimidine acceptor was
employed to replace the BT block in d11.13 The PMHJ
device based on d12 and C70 exhibited a markedly high
spectra-mismatch-corrected PCE of 6.4% with a JSC of
12.1 mA cm2, VOC of 0.95 V, and FF of 0.56. The high
VOC value for d12 is attributed to its low-lying HOMO level
(5.46 eV) acquired by using UPS, which is deeper than that
of d11 (5.30 eV measured by UPS). Compared to d11, the
JSC is slightly lower possibly due to the blue-shifted absorption
of d12. The PCE value of 6.4% is among the highest ever
obtained for organic vacuum-deposited single cells. Pei and
coworkers reported a DAA molecule (d13) with TPA as
donor and BT and cyanoacetic acid as acceptors, which
exhibited broad absorption (300800 nm) in thin lm.164
Solution-processed BHJ OPVs based on d13:PC61BM (1 : 2)
blend gave a moderate PCE of 1.23%.163
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Fig. 5
This journal is
Chemical structure of triphenylamine-based donors.
Chem. Soc. Rev.

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Beneting from its special propeller starburst molecular

structure, three-dimensional, amorphous materials with isotropic
optical and charge-transporting properties could be expected
when combining TPA core with linear p-conjugated arms.
Early in 2006, a series of three-dimensional, star-shaped
molecules with TPA as core for OPVs were rstly reported
by Roncali and coworkers.165168 They synthesized a series of
star-shaped molecules based on a triphenylamine core modied
by various combinations of thienylenevinylene conjugated
branches and electron-withdrawing indanedione or dicyanovinyl
groups (d14d18).165 Compared to d14, d15d18 with electronwithdrawing end groups showed broadening and red shift
of absorption and IPCE spectra as well as down-shifting of
HOMO levels. Under the same conditions, the PCE of vacuumdeposited bilayer OPVs increased from 0.46% (d14) to 1.17%
(d17). Optimized devices based on d18 exhibited a PCE of
1.85% with a very high VOC of 1.15 V.167 In 2006, they
synthesized a star-shaped molecule with TPA as core and
terthiophene as arms (d19).168 d19 exhibited high mobility
(0.011 cm2 V1 s1) but narrow absorption (lmax = 429 nm),
leading to a low PCE (0.32%). Replacing terminal bithiophene
in d19 with one (d20) or two (d21) dicyanovinyl groups extended
absorption bands and lowered HOMO levels as a result of
intramolecular charge transfer,169 resulting in a large improvement of VOC and JSC. The BHJ OPV devices based on d20
or d21:PC61BM (1 : 2) showed PCEs of 1.80 and 2.02%,
respectively.
Recently, Zhan and coworkers reported a new threedimensional, star-shaped, DAD small molecule (d22) with
TPA as the core, BT as the bridge and terthiophene as the
arms.170 Relative to its counterpart d19 without BT, d22
exhibited broader absorption as a result of intramolecular
charge transfer. The d22:PC71BM (1 : 2) blend lm exhibited
nanoscale aggregated domains, which are benecial to charge
separation and enhanced eciency of the OPVs. Without any
post-treatment, the BHJ OPV devices exhibited a JSC of
9.51 mA cm2, VOC of 0.87 V, FF of 0.52 and PCE of
4.3%. The PCE value of 4.3% is among the highest reported
for solution processed BHJ OPVs based on TPA-containing
small molecules, indicating that d22 is a promising three
dimensional donor molecule for OPVs.
To improve absorption and solution processability of d18,
Li and coworkers replaced thiophene with 4,4 0 -dihexyl-2,2 0 bithiophene to give d23.171 Solution-processed BHJ OPVs
based on d23:PC71BM (1 : 2) showed a PCE of 1.4%. To
further extend absorption, they incorporated vinylene bridge
between TPA and bithiophene units in d23 to give d24. The
absorption spectrum of the d24 lm covered a broad wavelength
range in the visible region from 380 to 750 nm, which red-shifted
by ca. 40 nm relative to that of the d23 lm. BHJ OPVs based
on d24:PC71BM (1 : 2) showed a JSC of 7.76 mA cm2, VOC of
0.88 V, FF of 0.439 and PCE of 3.0%, better than that of d23.
In 2008, Li and coworkers synthesized a star-shaped, DA
molecule (d25) with TPA as core, BT as arm and vinylene as
bridge.172 The optimized BHJ device based on d25:PC61BM
(1 : 3) produced a PCE of 0.61%. Attaching vinyl-TPA to d25
as end groups (d26) extended the absorption and the absorption maximum red shifted from 486 to 541 nm.173 The PCE of
BHJ devices based on d26:PC61BM (1 : 3) reached 1.33%,
Chem. Soc. Rev.
higher than that of the devices based on d25 or the corresponding linear molecule. The result indicates that the three
dimensional, star-shaped structure may be benecial to improving
the photovoltaic performance compared to its linear counterpart.
Subsequently, PCE of the devices was further improved to
2.39% by using PC71BM as an electron acceptor and replacing
the terminal group of vinyl-TPA in d26 with 4-hexylthiophene
(d27).174
In materials based on TPA and its analogs, the DAA
structure (e.g., d11 and d12) showed amazing results in PMHJ
OPVs, with PCEs up to 6.4%. Meanwhile, the three-dimensional
pullpush materials based on TPA as core (e.g., d22) also gave
high performance in solution-processed BHJ OPVs with PCEs
up to 4.3%. These results suggest that combining multi
electron-withdrawing units with TPA core to form threedimensional DAA structure may be one good direction
for developing high performance OPV materials.
Small molecular acceptors

As the rapid development of donor materials, including
polymers and small molecules, PCEs of the OPVs have reached
over 8%. The acceptors are of the same importance as the
donors for high performance OPVs. However, research eorts
devoted to the acceptors are much less than those on the
donors. So far, fullerenes and their derivatives still dominate
the acceptors although nonfullerene-based acceptors have
attracted increasing attention in recent years.
Fullerenes and their derivatives
Fullerenes and their derivatives have been widely used in
bilayer heterojunction and BHJ OPVs largely due to their
strong tendency to accept electrons from donor semiconducting
materials and high electron mobilities in the lms even in
composite form.39,40 Additionally, fullerene derivatives readily
form favorable nanoscale morphological network with donors,
which could improve BHJ OPV performance. Table 5 provides
a summary of electronic properties as well as OPV data for
representative fullerene derivatives (Fig. 6).
Generally, C60 (e1) and C70 (e2) were mainly used in vacuum
deposited OPVs as acceptors, while their soluble derivatives
PC61BM (e3) and PC71BM (e4) were mainly used in solution
processed OPVs. C60 was discovered by Kroto et al. in 1985.175
The spherical shape of C60 renders it a good acceptor in any
direction, and this isotropy toward electron transfer is advantageous versus planar molecular structures because it greatly
increases the chance for a benecial alignment with the donor
p-system. Leo and coworkers obtained an over 25% improvement in device performance in ZnPc:C70 BHJ devices over that
using ZnPc:C60.176 The PCE enhancement from 2.27 to 2.87%
was attributed to an increase in photocurrent (from 7.52 to
9.88 mA cm2), due to stronger long-wavelength absorption of
C70 as compared to C60, caused by a relaxation of symmetryforbidden transitions in C70.
PC61BM was rstly synthesized by Hummelen et al. for the
application in photophysical studies toward improvement of
photoinduced electron transfer eciencies in the fabrication of
photodetectors and photodiodes.177 PC61BM has much better
solubility in organic solvents than its parent compound C60.
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Table 5
Optical and electronic properties, mobilities, and OPV performance of fullerene-based acceptors
mea/cm2 V1 s1

e1
e2
e5
e6
e7
e8
e9
e10
e11
e12
e13
1.3 103 (O, N)

7 104 (S, N)
9.0 105 (S, B)
2.0 104 (S, B)
4.0 104 (S, N)
1.1 103 (S, B)
LUMOb/eV
Active layerc
JSC/mA cm2
VOC/V
FF
PCEd (%)
Ref.
3.9
3.9
3.7
3.74
3.72
3.85
3.66
3.63
3.74
3.75
ZnPc:e1 (vac, 1 : 2)
ZnPc:e2 (vac, 1 : 2)
P3HT:e5 (1 : 1.2)
P3HT:e6 (1 : 1)
P3HT:e7 (1 : 1)
P3HT:e8 (1 : 1.2)
P3HT:e9 (1 : 0.6)
P3HT:e10 (1 : 1)
BP/BP:e11/e11
P3HT:e12 (1 : 1)
P3HT:e13 (55 : 45)
7.52
9.88
9.14
10.61
10.79
9.05
10.3
8.64
10.5
10.3
11.3
0.56
0.56
0.724
0.84
0.86
0.87
0.83
0.81
0.75
0.81
0.65
0.543
0.522
0.68
0.727
0.721
0.655
0.62
0.61
0.65
0.63
0.57
2.27
2.87
4.5
6.48
6.69
5.2
5.3
4.2
5.2
5.25
4.2
176
176
188
190
192
193
195
199
200
201
202
a
O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. b From electrochemistry. c donor:acceptor: blend by solution
process unless stated otherwise; vac: vacuum deposition. d AM1.5, 100 mW cm2.
Fig. 6 Chemical structure of fullerene derivative acceptors.
In 1995, Yu et al. invented the BHJ structure for the OPVs

using soluble PC61BM as acceptor blended with conjugated
polymer donor.2 A deciency of PC61BM as a photovoltaic
material is its very weak absorption in the visible region, due
to the high degree of symmetry of C60 which causes the lowestenergy transition formally dipole forbidden. To improve the
visible absorption of PC61BM, Wienk et al. synthesized the
corresponding C70 derivative PC71BM possessing stronger
This journal is
absorption from 400 to 700 nm than PC61BM.178 Since then,

PC61BM and PC71BM have been widely used in the fabrication of BHJ OPVs. So far the BHJ OPVs based on polymer
donors and PC61BM or PC71BM acceptors have PCE values
of over 7%.10,179185 In recent years, some other promising
fullerene derivatives have also been reported.39 PC61BM
analogues with the phenyl ring replaced by thiophene,186 uorene,
or triphenylamine187 units have been synthesized successfully
Chem. Soc. Rev.

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and exhibited PCEs of 4% in solution processed BHJ OPV

devices in combination with regioregular poly(3-hexylthiophene)
(P3HT) donor.
Relatively deep LUMO levels of the PC61BM analogues
lead to VOC loss in OPV devices, and further limit increase in
PCEs. In 2008, Blom and coworkers introduced bisPC61BM (e5),
the bisadduct analogue of PC61BM, as a new fullerene-based
acceptor material in OPVs.188 The cyclic voltammetry measurements showed the LUMO energy level of bisPC61BM was
0.1 V higher than that of PC61BM, so that the device based on
P3HT:bisPC61BM (1 : 1.2) showed a higher VOC of 0.73 V
(0.58 V for PC61BM), ultimately a higher PCE of up to 4.5%
(3.8% for PC61BM).
Li and coworkers developed indeneC60 bisadduct (IC60BA,
e6)189,190 and indene-C70 bisadduct (IC70BA, e7)191,192 which
exhibited 0.17 and 0.19 eV LUMO up-shift, respectively,
relative to PC61BM and PC71BM. Meanwhile, IC60BA and
IC70BA were easier to synthesize and more soluble in common
solvents than PC61BM and PC71BM. The photovoltaic properties of the fullerene derivatives were studied by fabricating
BHJ OPVs with P3HT as donor and the fullerene derivatives
as acceptor. Thanks to the LUMO up-shift, the VOC of the
devices with IC60BA and IC70BA reached 0.84 V, which was
0.26 V higher than that (0.58 V) of the devices with PC61BM as
acceptor, and the PCE values of the devices were up to 5.44
and 5.64%, respectively, which were over 40% enhancement in
comparison with that (3.88%) of the BHJ OPVs based on
P3HT and PC61BM.189,191 After thermal annealing at 150 1C
for 10 min, BHJ OPVs based on P3HT and IC60BA provided a
PCE of 6.48%.190 By additive (3-hexylthiophene) processing,
BHJ OPVs based on P3HT and IC70BA showed a PCE of up
to 6.69%,192 which is the highest value in the OPVs based on
P3HT reported in the literature so far.
Cheng and coworkers reported a new class of diphenylmethano-based C60 bisadduct.193 The plane of the phenyl
groups lying parallel to the fullerene surface sterically protects
and shields the core C60 structure from severe intermolecular
aggregation, rendering it intrinsically soluble, morphologically
amorphous, and thermally stable. The double functionalization raises the LUMO energy level (3.85 eV) by ca. 0.1 eV,
compared to that of PC61BM (3.95 eV). The BHJ devices
based on P3HT:e8 (1 : 1.2) blend after thermal annealing at
140 1C for 10 min exhibited a JSC of 9.05 mA cm2, VOC of
0.87 V, FF of 0.655, and a high PCE of 5.2%. Voroshazi
et al.,194 Kim et al.195 and Wang et al.196 independently
reported novel o-xylenyl C60 bisadduct e9 with a higher
LUMO level (3.66 eV) relative to PC61BM. e9 was successfully used as an electron acceptor with P3HT in BHJ OPVs,
showing a high PCE of 5.31% with a high VOC of 0.83 V.195
Endohedral fullerenes were also conrmed to have much higher
LUMO levels than their corresponding empty-cage fullerenes in
theory197 and experiment.198 Ross et al. synthesized a series of
soluble PCBM-like Lu3N@C80 derivatives, and the LUMO
energy level of Lu3N@C80-PCBH (e10) is 0.28 eV higher than
that of PC61BM.199 The BHJ devices based on P3HT:e10 (1 : 1)
after thermal annealing at 110 1C for 10 min displayed high
VOC of 0.89 V and PCE of 4.2%. This result indicates that this
series of endohedral fullerene derivatives might be another
type of high VOC acceptor for application in OPVs.
Chem. Soc. Rev.
Matsuo et al. synthesized a new fullerene derivative with

Si-containing side chains (e11), which has good thermal stability
and LUMO up-shift relative to PC61BM.200 They fabricated
OPVs with a three-layer structure: an interdigitated BHJ layer
of tetrabenzoporphyin (BP):e11 sandwiched by BP donor and
e11 acceptor layers. The JSC, VOC, FF and PCE of the best
device reached 10.5 mA cm2, 0.75 V, 0.65 and 5.2%, respectively. Recently, Sharma and coworkers synthesized a new
fullerene derivative (e12) from PC61BM; e12 displayed better
solubility in common solvents and stronger absorption in the
lm than PC61BM.201 After optimizing mixed solvents and
subsequent thermal annealing, the best device with P3HT and
e12 showed a JSC of 10.3 mA cm2, VOC of 0.81 V, FF of 0.63,
and PCE of 5.25%. Frechet and coworkers synthesized a
dihydronaphthyl fullerene benzyl alcohol benzoic acid ester
(e13);202 the best BHJ OPV based on P3HT:e13 (55 : 45) after
thermal annealing at 150 1C for 30 min exhibited a JSC of
11.3 mA cm2, VOC of 0.65 V, FF of 0.57, and PCE of 4.2%.
Without question, fullerene derivatives are the most successful
acceptors in the OPVs so far. During the last decade, signicant
advances have been made in fullerene-based acceptors, appropriate chemical modications have up-shifted their inherent
LUMO energy levels, and the cost of fullerene production has
also decreased along with an increase in synthetic yields and
material purity. Nevertheless, there remain incentives to develop
nonfullerene acceptors that will not only retain the favorable
electron accepting and transporting properties of fullerenes, but
also overcome their insuciencies such as the limited spectral
breadth and bandgap variability.
Rylene diimides
On the basis of recent developments in high-performance
electron transporting materials for OFETs, some research
groups have begun investigating nonfullerene acceptors for
use in OPVs. Rylene diimides have attracted interest as alternative acceptor materials since they exhibit excellent photostability, easy alteration of HOMO and LUMO energies, large
absorption coecients, high electron mobilities, electron anities similar to those of fullerenes and each of these properties
can be readily tailored through either variation of substituents
on the imide nitrogen atoms or on the rylene core.203206
Table 6 provides a summary of electronic properties as well
as OPV data for representative rylene diimide related acceptors
(Fig. 7).
Perylene diimides (PDIs) are among the earliest and most
common nonfullerene acceptors investigated in OPVs. Many
early studies of OPVs incorporating PDIs consisted of layered
structures fabricated by vacuum deposition. The rst bilayer
heterojunction OPV was reported by Tang where a PDI-based
small molecule (f1) was used as the acceptor along with CuPc
as the donor.1 When ZnPc was employed as a donor in place
of CuPc in a simple bilayer device, the PCE was improved
from 0.95% to 1.3%.207 Later, the cis-isomer f2 was prepared,
and a bilayer heterojunction device based on CuPc/f2 showed
a PCE of 0.93%, slightly lower than that of f1 (1.1%).208 The
lower eciency was attributed to less ecient packing in
acceptor f2, leading to shorter exciton diusion lengths in
the system.
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Table 6
Optical and electronic properties, mobilities, and OPV performance of rylene diimide-based acceptors
Egopt/eV meb/cm2 V1 s1 HOMOc/LUMO/eV Active layerd
lmaxa/nm

f1
f2
f3 530
f4 542
f5
f6
f7
f8 455
f9
f10
5.8/3.8
5.82/3.69
2.13
2.13
8.8 104
5.6 104
4.6 104
6.0/3.85
5.9/3.8
5.90/3.95
5.78/3.87
5.5/4.1
ZnPc/f1
CuPc/f2
P3HT:f3 (1 : 4)
P3HT:f4 (1 : 4)
P3HT:f5 (1 : 1)
X:f6 (1 : 1)
Y:f7(1 : 3.5)
Z:f8 (1 : 1)
ZnPc/f9
P3HT/P3HT:f10 (1 : 1)/f10
a
In lm. b Measured by SCLC method in blend lm. c From electrochemistry.
blend by solution process. e AM1.5, 100 mW cm2. f 94 mW cm2.
JSC/mA cm2 VOC/V FF
PCEe(%) Ref.
3.66
1.65
1.32
1.74
6.8
6.3
8.30
2.11
3.51
1.3
0.93f
0.25
0.182
0.50
2.85
3.17
3.88
0.54
1.50
0.45
0.36
0.75
0.88
0.95
0.90
0.50
0.82
0.34
0.38
0.38
0.47
0.53
0.52
0.51
0.52
207
208
209
211
212
213
214
215
216
217
Donor/acceptor: bilayer by vacuum deposition; donor:acceptor:
Fig. 7 Chemical structure of rylene diimide acceptors.
BHJ OPVs based on solution processed blends of PDI-based

materials with appropriate donor materials are attracting increasing
attention. Solution processable PDI-based acceptors can be
prepared by introducing solubilizing groups, such as alkyl, on
the imide nitrogen atoms. 3-Pentyl substituted PDI (f3) was
prepared and blended with a variety of donors such as P3HT209
and polycarbazole210 to fabricate OPVs by spin coating. By
careful control over the solvent, substrate temperature during
deposition, and annealing temperature and time, the devices
based on P3HT:f3 (1 : 4) lm showed a JSC of 1.65 mA cm2,
VOC of 0.45 V, FF of 0.34, and PCE of 0.25%.209 Nonetheless
the tendency for f3 to form crystalline domains within polymer
matrices limited the eciencies of BHJ devices since the crystalline domains acted as electron traps to decrease photocurrents.
PDIs with longer alkyl substituents on the imide nitrogen
atoms have also been prepared, and when blended with P3HT
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gave low eciencies. For instance, a maximum PCE of 0.18%

was achieved with a P3HT:f4 weight ratio of 1 : 4 after
annealing at 80 1C for 1 h.211 Along with varying substituents
on the imide nitrogen atoms, recent studies have also examined
the impact of substituents in the bay regions of the PDIs on thinlm morphology and device performance.211,212 Although the
PDIs with electron donating or withdrawing substituents have
tuned the LUMO energy level over a range of nearly 0.7 eV and
impacted on device VOC, none of these PDI bay-substituted
derivatives yielded higher performance than simple PDIs
without bay-region substituents.211 Very recently, Laquai
et al. demonstrated that the photovoltaic characteristics of
blend lms of P3HT and PDIs are improved upon using a
core-alkylated PDI derivative (f5) instead of the often used
N-alkylated.212 The alkyl-substitution pattern aected the
packing of the PDI and improved the blend aggregation.
Chem. Soc. Rev.

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The optimized device based on P3HT:f5 exhibited a PCE of

0.5%, with JSC of 1.74 mA cm2, VOC of 0.75 V, and FF
of 0.38.
PDI-based small molecular acceptors had no promising
results in OPVs, until Sharma and coworkers developed a series
of high-performance acceptors by attaching tert-butylphenoxy
groups to the bay-region of PDIs and varying the imide
substituent.213215 The acceptors f6f8 with dierent fusedring substituents on the imide exhibited electron mobilities
(Measured by SCLC) of 49 104 cm2 V1 s1 when blended
with small molecular donors X, Y, or Z (Fig. 7). The devices
based on X:f6, Y:f7, and Z:f8 blends gave PCEs of 2.85%,213
3.17%,214 and 3.88%,215 respectively, after annealing and/or
inserting a ZnO layer between the active layer and the cathode.
The PCE of 3.88% is the highest ever reported for nonfullerenebased BHJ OPVs.
Compared to the PDI-based molecules, the smaller fusedring unit naphthalene diimide (NDI) derivatives were less
successful as acceptors in OPVs, because they possess a larger
bandgap and thus absorb poorly in the visible spectrum
(generally at onset less than 400 nm). For example, bilayer
OPVs based on ZnPc/f9 exhibited a PCE of 0.54%, lower
than that (1.3%) of its analog, f1.216 Recently, Jenekhe and
coworkers reported a new nonfullerene acceptor (f10) with
NDI as core and oligothiophene as arms used in BHJ OPVs.
After annealing at 100 1C for 10 min and adding 0.2%
diiodooctane additive, the optimized P3HT:f10 based device
showed a PCE of 1.5%.217,218
Although rylene diimides have strong absorption and high
electron mobility, the performance of OPVs using rylene
diimides as acceptors do not yet rival those of fullerene-based
systems. The planar shapes of rylene diimides may result in
enhanced p-stacking and more quasi one-dimensional electron
transport, compared to the spherical/ellipsoidal molecular
Table 7
g1
g17
g18
g19
g20
g21
Other nonfullerene acceptors

Apart from the rylene-based acceptors, some other n-type
molecules have been reported as the nonfullerene acceptors
for OPVs. Table 7 provides a summary of electronic properties
as well as OPV data for representative other nonfullerene
small molecular acceptors (Fig. 8). One method of increasing
the n-type character of molecules is to introduce electronwithdrawing units, such as uorine and cyano, to the periphery
of the aromatic rings.219 For example, hexadecauorinated CuPc
g1 showed electron mobilities of up to 5 103 cm2 V1 s1 in
OFETs.220,221 When incorporating g1 in bilayer heterojunction
OPVs as an acceptor and sexiphenyl (p-6P) as a donor, a PCE
of 0.18% was obtained.222 Using subphthalocyanine (SubPc)
instead of p-6P led to improved PCE of 0.56%.223 Torres and
coworkers synthesized a series of uorinated SubPc as acceptors
in OPVs.224 Bilayer OPV devices of the acceptors with a variety
of donors, such as pentacene, CuPc, AlClPc, SubPc and SubNc,
were prepared by vacuum evaporation. In these devices, the
SubPc/g2-based device showed the highest PCE of 0.96%, with
JSC of 2.1 mA cm2, VOC of 0.94 V, and FF of 0.49. However,
the PCE value of 0.96% was obviously lower than that (3.0%)
of SubPc/C60-based control device. The moderate eciencies
could be limited by the low electron mobility of the amorphous uorinated SubPc as well as series resistance eects in
the active layer. Jones and coworkers found that replacing
uorinated SubPc (g2) with chlorinated SubPc (g3) led to
Optical and electronic properties, mobilities, and OPV performance of other nonfullerene-based acceptors
lmaxa/nm
Egopt/eV
780
1.5
meb/cm2 V1 s1
HOMOc/LUMO/eV
6.4/4.9
g2
g3
g4
g5
g6
g7
g8
g9
g10
g11
g12
g13
g14
g15
g16
shapes of fullerenes. So when rylene diimide-rich phases do

not have high degrees of long-range order, there can be
multiple orientations of p-stacked phases, which may decrease
long-range mobilities and therefore act as recombination
centers. In this system, introducing bulky side chains can
decrease the molecular planarity and may be helpful to
improve the photovoltaic performance.
700
5.7/3.95
5.29/3.50
5.47/3.64
620
5.34/3.21
710
1.82
490
640
475
1.8
1.15 105 (S)

1.14 104 (S)
2.40
580
410
517
2.34
1.81
1.81
2.18
3
3 10
(O)
6.27/3.92
5.47/3.42
5.9/4.1
6.2/3.6
6.02/3.50
6.0/3.6
5.77/3.35
5.26/3.52
5.9/4.09
6.1/3.5
5.17/3.24
Active layerd
JSC/mA cm2
VOC/V
FF
p-6P/g1
SubPc/g1
SubPc/g2
SubPc/g3
SubPc/g4
P3HT:g5 (1 : 1)
P3HT:g6 (1 : 1)
P3HT:g7 (1 : 1)
P3HT:g8 (1 : 1)
P3HT:g9 (5 : 3)
P3HT:g10 (1 : 1)
P3HT:g11 (1 : 1)
P3HT:g12 (1 : 1)
P3HT:g13 (1 : 1)
P3HT:g14 (1 : 2)
P3HT:g15 (1 : 1)
P3HT:g16 (1 : 1)
POPT:g16 (1 : 1)
P3HT:g17 (1 : 1.4)
P3HT:g18 (1 : 2)
P3HT:g19 (1 : 1)
P3HT:g20 (1 : 2)
P3HT:g21 (1.5 : 1)
0.96
2.54
2.1
3.53
7.8
3.72
1.93
2.44
3.17
1.93
0.24
0.42
0.40
0.94
1.31
0.95
0.84
0.54
0.95
0.80
1.05
0.93
0.55
0.49
0.58
0.54
0.41
0.41
0.43
0.50
0.39
0.21
0.66
5.72
2.36
1.79
3.00
5.50
4.7
2.36
1.93
4.40
3.9
0.78
0.48
0.62
0.67
0.76
0.62
0.96
0.71
0.52
0.76
1.1
0.27
0.57
0.50
0.37
0.48
0.40
0.56
0.52
0.31
0.56
0.4
In lm. b O and S: measured by OFET or SCLC method in neat lm. c From electrochemistry.
donor:acceptor: blend by solution process. e AM1.5, 100 mW cm2. f 80 mW cm2.
Chem. Soc. Rev.
PCEe (%)
Ref.
0.18
0.56
0.96
2.68
4.0
1.29
0.43
1.00
1.26
0.80
0.06f
0.30.4f
0.14
1.57
0.73
0.45
1.10
1.40
2.54
1.00
0.31
1.86
1.7
222
223
224
225
226
228
227
228
228
229
232
233
235
236
237
240
241
241
244
245
246
247
248
Donor/acceptor: bilayer by vacuum deposition;
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Fig. 8 Chemical structure of other nonfullerene acceptors.
improved performance; SubPc/g3-based device showed promising PCEs of 2.68% with very high VOC of 1.31 V.225 After
selective halogenation to tune the energy levels of SubPc, g3
provided sucient interfacial HOMO and LUMO osets for
ecient exciton dissociation, whilst maximizing the interface
gap. Recently, Verreet et al. reported uorinated fused SubPc
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dimer (g4, mixture of two isomers) with strong and complementary absorption to the donor material SubPc.226 The
optimized SubPc/g4-based bilayer device exhibited a high
PCE of 4%, with JSC of 7.8 mA cm2, VOC of 0.95 V, and
FF of 0.54. The PCE of 4% is the highest ever reported for
nonfullerene-based bilayer OPVs.
Chem. Soc. Rev.

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Although pentacene and its derivatives belong to a promising

class of donors in OPVs, Anthony and coworkers demonstrated
that it is possible to switch them from donors to acceptors
in OPVs by lowering their LUMO energy levels through
cyanation.227 Cyanopentacenes g5 and g6 with tricyclopentylsilyl
groups have been synthesized;227,228 the energy levels can be
tuned by varying the number of cyano groups, while the
trialkylsilyl groups control crystal packing and lm morphology.
They found that the HOMO and LUMO energy levels downshifted by ca. 0.14 eV for every cyano group that was introduced
to the pentacene core, and a particularly strongly one-dimensional
sandwich herringbone crystal packing motif yielded devices
with the highest photocurrent. In the initial devices, blended
with P3HT donor, dicyanopentacene g6 exhibited a best PCE
of 0.43%, with JSC of 1.93 mA cm2, VOC of 0.54 V, and FF of
0.41. Reducing the number of cyano from 2 (g6) to 1 (g5) led
to a higher performance: JSC of 3.72 mA cm2, VOC of 0.84 V,
FF of 0.41, and PCE of up to 1.29%.228 The 0.3 V improvement in VOC was attributed to an up-shift of LUMO energy
level caused by a decrease in cyano number. Subsequently,
several other pentacene derivatives with a single electron
withdrawing group were investigated, and the better acceptors
were found to be chloropentacene g7 and triuoromethylpentacene
g8 with PCE of 1.00% and 1.26%, respectively, when blending
with P3HT.228 Recently, anthradithiophene was also converted
into acceptor for OPVs, through the introduction of amide
groups.229 In most literature work, anthradithiophene derivatives were studied as a mixture of syn and anti isomers due to
the great challenge in the preparation of isomerically pure
materials. However, amide groups caused dierent self-assembly
of the syn- and anti-isomers that allowed for the rst time
separation and property evaluation of isomerically pure
anthradithiophenes. Anthony and coworkers evaluated the
acceptor properties of two pure isomers and their mixture in
BHJ OPVs with P3HT as donor; syn-isomer g9 yielded much
better PCE (0.8%) than that of anti-isomer (0.008%) or their
mixture (0.09%) after annealing at 120 1C for 1 min. For
anti-isomer, larger scale aggregation was observed in the blend
lm, while syn-isomer:P3HT blend showed a more uniform
coverage textured with small grains of the acceptor. The
dierence in blend lm morphology is responsible for the
dierence in OPV performance.
As same as CuPc and pentacene, oligothiophenes have also
been widely employed as donors in OPVs. However, thienylS,S-dioxide caused a signicant increase in electron anity of
the oligothiophene system.230234 Barbarella et al. developed a
series of linear and branched thiophene-S,S-dioxide-containing
oligothiophene acceptors for OPVs.232,233 In these studies, due to
the propensity for linear oligothiophene acceptors to crystallize
and form aggregates leading to reduced D/A interfacial area, BHJ
OPVs based on all linear acceptors blending with P3HT showed
very low PCEs, and the asymmetric molecule g10 gave a PCE of
0.06%, higher than the others.232 To suppress crystallization,
V-shaped acceptors were synthesized. Owing to the branched
structure lacking any symmetry elements, these V-shaped
acceptors displayed a low tendency to crystallization and better
lm forming properties than their linear counterparts.233 Thus
for the acceptor g11, devices fabricated from a blend of P3HT
yielded estimated PCE of 0.30.4% by thermal annealing.233
Chem. Soc. Rev.
Cyano is an excellent electron-withdrawing unit in design of

donor and acceptor materials for OPVs. As with the systems
described above, carbazole has also been modied as an
acceptor through cyanation.235 The molecule g12 substituted
with two DCV groups showed broad absorption with the onset of
about 600 nm. By controlling blend ratio, solvent and annealing
conditions, the optimized devices with P3HT:g12 showed a PCE
of 0.14%. The relatively low PCE of OPVs based on g12 is due to
its low electron mobility of 1.15 105 cm2 V1 s1 estimated
by the SCLC method.
Wang and coworkers developed DCV substituted quinacridone
derivatives as acceptors for BHJ OPVs.236 These molecules
exhibited remarkable absorption in the region from 650 to
700 nm. In particular, molecule g13 exhibited a LUMO energy
level of 4.1 eV, small bandgap (1.8 eV) and moderate
electron mobility (1.14 102 cm2 V s1 by SCLC). A device
based on P3HT:g13 exhibited a PCE of 1.57%, with JSC of
5.72 mA cm2, VOC of 0.48 V, and FF of 0.57. However, the
relatively deep LUMO energy level of g13 led to a signicant
loss of photovoltage.
Meredith et al. combined uorene, BT and DCV together to
synthesize a new nonfullerene acceptor (g14), which can be
processed by vacuum deposition or solution processing to give
amorphous thin lms and can be annealed at a modest
temperature to give lms with better order and enhanced
charge transport properties.237 The P3HT:g14 BHJ device
spun cast from dichlorobenzene showed a low PCE of
0.04%, and after annealing at 65 1C for 20 min, the PCE
was improved to 0.73%, which can be attributed to an increase
in electron mobility in the acceptor phase and improvement in
the charge percolation network to the contacts.
Recently, a series of substituted dicyanoimidazole derivatives known as Vinazene have received focused attention as
acceptors in BHJ OPVs.238243 The series of Vinazene-based
molecules displayed a wide range of electronic properties, with
LUMO energy levels ranging from 2.76 to 3.60 eV.238,239
Of these molecules, g15 and g16 containing BT core gave the
most ecient devices when blended with P3HT in BHJ
OPVs.238241 After thermal annealing, g15 and g16 based
devices showed a PCE of 0.45%240 and 1.1%,241 respectively.
For g16, a further improvement in eciency can be achieved
by employing an octylphenyl-substituted polythiophene
(POPT) as the donor. The optimized device at a 1 : 1 blend
weight ratio of POPT:g16 yielded a JSC of 5.5 mA cm2, VOC
of 0.62 V, FF of 0.4, and PCE of 1.4%.241 The higher
performance of POPT could be explained by the ability of
the conjugated phenyl substituent to twist out of planarity,
resulting in a high dissociation eciency. Very recently,
Sellinger et al. synthesized a series of electron-decient molecules
based on a central BT moiety anked with vinylimides and
used for solution processed BHJ OPVs as acceptors.244 Of
these acceptors, phthalimide-BT based molecule (g17) showed
promising photovoltaic performance. BHJ OPVs based on
P3HT:g17 (1 : 1.4) yielded a high VOC of 0.96 V and a maximum
PCE of 2.54%, whereas naphthalimide-BT analog only aorded
0.1% PCE. The high VOC is attributed to the high LUMO level
(3.3 eV) of g17.
DPP-based materials have been proven promising donors
for OPVs; blended with PC71BM acceptors, they yielded PCEs
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up to 4.4%.93 Interestingly, a variety of DPP derivatives with

electron withdrawing end capping groups (such as aldehyde,
triuoromethylphenyl and triuorophenyl) were tested as
acceptors in OPVs.245,246 The inherent electron anity of
DPP moiety was further improved through the introduction
of electron withdrawing groups. Among these compounds,
g18 provided the highest PCE of 1.0%, when blended with
P3HT donor in a BHJ device,245 while aldehyde substituted
DPP g19 showed a lower PCE of 0.31%.246
Very recently, Pei et al. modied the uoranthene-fused
imide scaold to develop a new electron acceptor g20 by
combining with a cyano substituent group.247 The investigation
of the photophysical and electrochemical properties indicates
that LUMO level (ca. 3.5 eV) of g20 both matches the work
function of the LiF/Al cathode and increases VOC of OPV
devices. The preliminary results showed that by thermal
annealing at 100 1C, the solution-processed BHJ OPVs based
on P3HT:g20 (1 : 2) gave a PCE of 1.86%, with relatively high
VOC of 0.76 V, compared to that (0.58 V) of the control device
based on P3HT:PC61BM blend.
Wudl and coworkers reported the use of a 9,9 0 -biuorenylidene
polycycle for small molecule acceptors.248,249 The 9,90 -biuorenylidene structures are particularly eective at stabilizing a negative
charge, due to both steric and electronic eects. But the steric
eect is relieved when the molecule receives an electron and gains
aromaticity. Meanwhile, the LUMO energy level of this system is
easily tuned by substitution on the aromatic periphery. When
blended with P3HT, the asymmetric molecule g21 showed a
decent PCE of 1.7% and a high VOC of 1.10 V.248
Chemical functionalization allows control over absorption
prole and energy levels of nonfullerene acceptors. However,
compared to fullerenes and their derivatives, nonfullerene
acceptors showed lower performance in OPV devices, especially
solution processed BHJ OPVs. The hurdles that remain arise
from active layer morphology and charge transport issues.
While many of these materials showed good electron mobilities
when measured in neat lms, the mobilities in blends with
the donors were generally not as high. The next step in

the development of new nonfullerene acceptors may involve
developing multi-dimensional structures.
Donoracceptor dyad molecules for

single-component OPVs
For BHJ OPVs, one of the main problems is ne tuning the
complicated physical interactions between donordonor,
acceptoracceptor, and donoracceptor to obtain an ideal and
stable morphology with a well-dened nanostructure. To solve
this problem, acceptors, such as fullerene, PDI, DCV etc. were
attached to donor molecules, such as oligothiophene, oligophenylenevinylene, and triphenylamine, as pendant side chains
or end groups to form donoracceptor dyad molecules (Fig. 9),
which can be regarded as a molecular heterojunction and used
to fabricate single-component OPVs. Such a structure facilitates
exciton dissociation and homogeneous distribution to prevent
severe phase separation. In recent years, the donoracceptor
dyad molecules showed some promising performance.250
Hashimoto and coworkers developed a series of fullerenedyad molecules for single-component OPVs. In 2009, they
reported synthesis of an oligophenylenevinylene containing
ve phenyl rings with C60 connected to the middle phenyl ring
in the conjugated chain by a polyether linker (h1).251 After
thermal annealing at 150 1C for 1 min under inert atmosphere,
the h1-based single-component OPV device gave JSC of
3.30 mA cm2, VOC of 0.88 V, FF of 0.44 and PCE of
1.28% under white light irradiation at 100 mW cm2. More
recently, the same group reported an oligothiophene containing 8 thiophene rings and an electron-withdrawing DPP unit in
the middle with C60 connected to the DPP unit by a polyether
linker (h2).252 h2 showed a low bandgap and the photocurrent
response was extended to 850 nm, so that a h2-based singlecomponent OPV device gave a high JSC (4.79 mA cm2). This
high JSC together with VOC of 0.51 V and FF of 0.46 led to a
total PCE of 1.1%.
Fig. 9 Chemical structure of donoracceptor dyads.
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In 2009, Geng et al. synthesized a series of extended DA

cooligomers in which substituted uorene-alt-bithiophene
oligomer was selected as donor block and PDI as acceptor
block.253 They found that solvent vapor annealing signicantly
improved the order of the cooligomers with an increase of the
persistent length of the lamellae. After solvent annealing, h3-based
single-component OPV device showed a JSC of 4.49 mA cm2,
VOC of 0.87 V, FF of 0.38 and PCE of 1.50%, which is the best
value reported for a single-component OPV device so far.
TPA-DCV-based star-shaped DA molecule (d17, Fig. 5)
reported by Roncali et al. also exhibited promising results in
single-component OPVs: JSC of 1.7 mA cm2, VOC of 0.70 V,
FF of 0.30, and PCE of 0.40%.167
The fast charge recombination and inecient charge hopping
and transport in single-component OPVs is probably responsible
for the relatively lower PCEs of single-component OPVs
compared to donor/acceptor blend or bilayer solar cells.17
Conclusions and outlook

We have reviewed some representative and promising small
molecule donors, acceptors, and donoracceptor dyad systems
for high-performance bilayer, BHJ, and single-component
OPVs. So far a number of small molecular OPV materials
have been discovered, but most of these materials give relatively
low PCEs. With extensive research and accumulated practical
experience that we have outlined in this review, the guidelines
to pursuing and developing high-performance small molecules
for OPVs are becoming legible. The basic requirements of
specic intrinsic properties necessary for an ideal small
molecular donor, acceptor or donoracceptor dyad materials
include: (a) a low optical bandgap for broad absorption range
matching with solar spectrum and high extinction coecient
for capturing more solar energy; (b) long exciton diusion
lengths for eective migration of excitons to D/A interface;
(c) high hole or electron mobility for accelerating charge
transport, which in turn allows a thicker active layer required
for increased light harvesting, as well as reduces charge
recombination and series resistance; (d) suitable HOMO/LUMO
energy levels to ensure a large VOC and a downhill energy
oset for exciton dissociation. Additionally, easy sublimation,
relatively low molecular weight, excellent thermal stability are
also necessary for vacuum deposited materials, while good
lm-forming property and sucient solubility are also necessary for solution processed materials. Meanwhile, since the
optimal OPV material itself is device application and system
specic, for bilayer heterojunction OPVs, high crystallinity
of the active materials may be benecial to improve the
device performance. On the other hand, for BHJ OPVs, it is
also critical for the active materials that formation of a
bicontinuous interpenetrating network with the optimum
morphology for building two distinct highways for transporting free charge carriers; moderate crystallinity of materials
can improve charge carrier mobility, but high crystallinity
will cause large phase separation scale and low PCE of
devices. Generally, low PCEs in OPV devices may be attributed to the OPV materials violating one or some of the above
criteria, or the device conguration and fabrication below
optimization.
Chem. Soc. Rev.
High-eciency OPVs have been achieved as a result of

innovations of small molecular materials and device fabrication technology, boding a bright future for this exciting
research eld. For further improving the device performance
by modifying the molecular structure of active materials, it is
necessary that deeply understanding the relationships between
chemical structures and optical, electronic and device properties.
To summarize:
(1) Enhancing and extending the absorption of active materials
to match solar radiation is one of the main ways to improve
JSC and eciencies of OPV devices. An OPV molecule with
bandgap o 2 eV is necessary but not sucient for a high PCE.
The oligomers with long conjugation length generally possess
broad and strong absorption. Building the pushpull structure
with electron donating and withdrawing units can create
the intramolecular charge transfer and in turn improve the
molecular absorption. Molecules and oligomers based on
fused-ring blocks such as acenes, dithienocyclopentadiene,
dithienosilole, dithienopyrrole and benzodithiophene could
exhibit relatively low Eg and broad absorption.
(2) Since the VOC of devices is related directly to the
dierence between the HOMO level of the donor and the
LUMO level of the acceptor, a lower HOMO of a donor and a
higher LUMO of an acceptor would help to achieve a higher
VOC. In general, a donor with a HOMO below 5.3 eV or an
acceptor with a LUMO above 3.7 eV tends to give VOC 4 0.8 V.
The energy levels can be tuned by changing the species and
number of substituent group. In general, introducing the
electron-withdrawing units, such as cyano and uorine etc.,
would down-shift the LUMO levels of materials. On the contrary,
the electron-donating units such as TPA and thiophene help to
raise the HOMO levels.
(3) The high hole mobility of donors and electron mobility
of acceptors (4 102 cm2 V1 s2) would help to achieve a
high JSC. Molecules based on fused-ring blocks tend to exhibit
relatively high mobilities. Crystal structure and pp stacking in
the lm are the key factors to determining the mobility of
materials. In addition, the mobilities matching of donor and
acceptor benet also FF and PCE of devices.
(4) For solution processing, the use of long alkyl or alkoxy
side chains has been a common approach. However, the side
chain nature not only aects the solubility, conguration and
intermolecular interaction of the molecules, and also aects
the absorption, energy levels and charge transport properties.
In particular, the side chain aects morphology of blend lms
and nally aects the photovoltaic performance of devices.
It should be stressed that increasing the content of insulating
alkyl side chains relative to the conjugated main chain in the
molecule may result in deterioration in charge transport.
Thereby, balanced choice of a suitable solubilizing group at
an appropriate location is of crucial importance for ne-tuning
the structureproperties relationship.
(5) The morphology and phase separation scale in BHJ lm
is not only related to the nature of materials, but also can be
optimized by carefully controlling the device fabrication
conditions, such as varying spin-casting solvent and speed or
donor/acceptor radio and concentration, thermal annealing,
exposure to solvent vapor, modifying the surface energy of
the blend component and substrate. With optimal morphology
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on the nanoscale, it becomes easy to translate the microscopic

intrinsic properties of the photovoltaic materials into macroscopic OPV device performance.
(6) Merocyanine (MC) dye and TPA-based DAA molecule
donors in combination with C60 or C70 acceptors exhibited
very high performance in vacuum deposited OPVs, while onedimensional oligothiophenes with pushpull structures in
combination with PC61BM or PC71BM exhibited very high
performance in solution processed BHJ OPVs; the best PCEs
were up to 4 6%. Fused acenes exhibited relatively low
eciencies in vacuum deposited or solution processed OPVs
(o 3%). Nonfullerene acceptors (PCE o 4%) do not yet rival
fullerene-based systems in vacuum deposited or solution processed
devices, while donoracceptor dyad molecular heterojunction
(PCE o 1.5%) does not yet rival donor/acceptor bilayer
or bulk heterojunction in vacuum deposited or solution
processed devices.
(7) It should be emphasized that the PCE is more a device
parameter than an intrinsic photovoltaic material parameter.
High eciency achievement is a systematic combination of
material properties with judicious and careful optimization of
the various device fabrication conditions. So far the best
performances (4 6%) of OPVs were achieved from vacuum
or solution-deposited small molecule donors with fullerene
acceptors. An interdisciplinary approach such as novel photovoltaic materials and new advanced device concepts will
probably bring high eciency over 10% and low cost OPVs
to nal commercialization.
Acknowledgements
This work was supported by NSFC (Grants 21025418,
51011130028, 21021091), 973 Project (Grant 2011CB808400),
and the Chinese Academy of Sciences.
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Small Molecule Semiconductors For High Efficiency Organic Photovoltaics

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Cite this: DOI: 10.1039/c2cs15313k

Small molecule semiconductors for high-eciency organic photovoltaics

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Received 18th November 2011

Beijing National Laboratory for Molecular Sciences and Key

Yuze Lin received a BS degree

The Royal Society of Chemistry 2012

stocks are diminishing. The need to develop renewable energy

Xiaowei Zhan obtained a PhD

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on a heterojunction resulting from the contact of an electron

Yongfang Li has been a

OPV device is the predecessor of hybrid planar-mixed molecular

Fig. 1 The architecture structure of bilayer heterojunction (a) and

The Royal Society of Chemistry 2012

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The photoactive materials, including polymeric and small

Small molecular donors

The Royal Society of Chemistry 2012

band gap, and absorption coecient, all greatly aect the

Egopt/eV mhb/cm2 V1 s1

HOMOc/LUMO/eV Active layerd

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5.1 105 (S, N)

JSC /mA cm2 VOC/V FF

PCEe (%) Ref.

polymorph a4 lm has changed to crystalline form that

The Royal Society of Chemistry 2012

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Fig. 2 Chemical structure of dye-based donors.

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Chem. Soc. Rev.

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of donor materials. In 2006, Thompson and coworkers

the individual dyes only. This synergetic eect is attributed to

The Royal Society of Chemistry 2012

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Crystallographic data suggest that the intermolecular stacking

The Royal Society of Chemistry 2012

can be controlled by adjusting annealing temperature; 110 1C

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where adduct formation can be minimized. After optimization

mhb/cm2 V1 s1

Chem. Soc. Rev.

The Royal Society of Chemistry 2012

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Chemical structure of fused acene donors.

rather than highly crystalline phases, resulted in improved

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of the photogenerated excitons and collection of separated

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synthesis of diuorenyl-substituted HBC (b12) and its use in

formation of amorphous structure, so that charge separation

mhb/cm2 V1 s1

1.5 104 (S, N)

Chem. Soc. Rev.

The Royal Society of Chemistry 2012

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Chemical structure of oligothiophene donors.