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Donor–Acceptor Semiconducting Polymers for Organic Solar Cells
Ruvini S. Kularatne, Harsha D. Magurudeniya, Prakash Sista, Michael C. Biewer,
Mihaela C. Stefan
Department of Chemistry, University of Texas at Dallas, Richardson, Texas 75080
Correspondence to: M. C. Stefan (E-mail: mci071000@utdallas.edu)
Received 4 October 2012; accepted 8 October 2012; published online 15 November 2012
DOI: 10.1002/pola.26425
ABSTRACT: This review describes the synthesis and photovoltaic
performance of donor–acceptor (D–A) semiconducting polymers
that have been reported during the last decade. 9,9-Dialkyl-2,7-
fluorene, 2,7-carbazole, cyclopenta[2,1-b:3,4-b0 ]dithiophene,
dithieno[3,2-b:20 ,30 -d]silole, dithieno[3,2-b:20 ,30 -d]pyrrole, benzo [1,2-
b:4,5-b0 ]dithiophene, benzo[1,2 b:4,5 b0 ]difuran building blocks, and
INTRODUCTION Increasing energy consumption and the ris-
ing cost of energy are the driving forces to develop new
technologies to harvest the solar energy. Organic solar cell
technology is a promising candidate for the solar energy con-
version compared to its inorganic counterparts due to its
low cost, light weight, and potential use in flexible devices.1,2
Following the first report of ‘‘two-layer organic photovoltaic
cells’’ by Tang et al., polymer solar cells have undergone
gradual evolution, and power conversion efficiencies above
7% and a highest efficiency of 8.37% have been achieved.3–8
The bulk heterojunction (BHJ) solar cell has become one of
the most successful device structures developed to date.9 In
this device structure, the donor is an electron rich conju-
gated polymer, and the acceptor is a soluble fullerene deriva-
tive. The donor and the acceptor are blended to form a
bicontinuous interpenetrating network, which increases the
donor–acceptor (D–A) interfacial area available for the exci-
ton dissociation. The most used acceptor material in organic
solar cells is [6,6]-phenyl-C61-butyric acid methyl ester
(PC61BM) which is soluble in organic solvents. The morphol-
ogy of the BHJ is critical to the performance of the solar cell.
Excitons, which are coulombically bounded hole–electrons
pair, form on the donor (p-type) semiconductor and diffuse.
However, the excitons must reach the interface of the donor
and acceptor where the charge separation occurs before they
relax back into the ground state, or ‘‘quench,’’ through other
processes. It has been demonstrated that the exciton diffu-
sion length is on the order of 10–20 nm.10,11 As a result, an
ideal junction is a ‘‘BHJ’’ that is interpenetrated, but has con-
nected phase-separated domains.11 This active layer blend is
sandwiched between the high work function indium tin ox-
C 2012 Wiley Periodicals, Inc.
V
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their D–A copolymers are described in this review. V C 2012 Wiley Peri-
odicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 743–768
KEYWORDS: bandgap; bulk heterojunction solar cells; donor–
acceptor polymer; fullerene; functionalization of polymers;
morphology
ide (ITO) anode and the low-work function cathode elec-
trode, such as aluminum.11 The anode is usually coated with
poly(3,4-ethenedioxy thiophene):poly(styrenesulfonate)
(PEDOT/PSS) hole injection layer.11 The hole injection layer
planarizes the ITO and facilitates the collection of holes from
the light-harvesting layer to the anode.11
The charge photogeneration process in BHJ solar cells takes
place in four steps:12–14 (i) upon the irradiation of light on
to the active area, the donor polymer absorbs a photon to
generate excitons; (ii) the excitons subsequently migrate
until they reach the D–A interface; (iii) the excitons dissoci-
ate at the D–A interface into electrons and holes; (iv) the
electrons transfer from the lowest unoccupied molecular or-
bital (LUMO) of the donor to the LUMO of the acceptor and
are collected at the cathode, whereas the holes are collected
at the anode generating photocurrent and photovoltage.
The power conversion efficiency (PCE) (1) is defined as the ra-
tio of the power produced by the solar cell (Pout) and the opti-
cal power of the incident light (Pin). The Pout of a solar cell is
the product of three parameters, that is, short circuit current
density (JSC), open circuit voltage (VOC), and fill factor (FF).15,16
The typical current density (J)–voltage (V) curve of a BHJ solar
cell device is shown in Figure 1. The JSC, or the device photo-
current at zero bias, depends on the photon absorbance of the
active layer, the efficiency of free charge carrier generation,
and the charge collection. The VOC (2), or the photovoltage at
zero current density, depends on the off-set between the high-
est occupied molecular orbital (HOMO) of the donor material
and the LUMO of the electron acceptor fullerene derivative.17,18
The FF (3) depends on the balanced charge transport and
recombination properties of the active layer.19
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Ruvini S. Kularatne received her B.Sc. in Chemistry from University of Peradeniya in Sri
Lanka in 2008. She joined Prof. Mihaela Stefan’s research group in 2009 as a Ph.D. student.
She is currently a fourth year graduate student and her research targets the synthesis of
novel benzodithiophene donor–acceptor polymers for organic solar cell applications.

Harsha D. Magurudeniya received his B.Sc. in Chemistry from University of Peradeniya in Sri
Lanka in 2008. He joined Stefan’s group in 2009 as a Ph.D. student at the University of Texas
at Dallas. He is currently a fourth year graduate student and his research targets the
synthesis of nickel catalysts for the polymerization of bulky monomers using Grignard
metathesis (GRIM) polymerization.

Prakash Sista received an integrated M.Sc. in Chemistry (B.Sc. and M.Sc.) from the Indian
Institute of Technology Bombay in 2003. He has received M.S. in Chemistry from University
of San Francisco in 2008 working on electron transfer reactions of ruthenium complexes. He
received his Ph.D. degree from University of Texas at Dallas in 2011 working in Stefan’s
group.

Michael C. Biewer is an Associate Professor of Chemistry at the University of Texas at Dallas.

He received his Ph.D. degree from Yale University working in the group of J. Michael
McBride. He subsequently worked as a postdoctoral researcher in the group of David M.
Walba at the University of Colorado at Boulder before joining the faculty at the University of
Texas at Dallas.

Mihaela C. Stefan received her Ph.D. degree in Chemistry from Politehnica University
Bucharest. She joined the Department of Chemistry at the University of Texas at Dallas in
2007. She received the NSF Career Award in 2010, the NS&M Outstanding Teacher Award in
2009, and the Inclusive Teaching Diversity Award in 2012. Her research group is developing
novel polymeric materials for organic electronics and drug delivery applications.

Low Band Gap Donor–Acceptor Polymers for Bulk

Heterojunction Solar Cells
Pout ðJSC Þ  ðVOC Þ Figure 2 shows the spectrum of the solar photon flux reach-
PCEðgÞ ¼ ¼ FF  (1)
Pin Pin ing the surface of the earth.20 The photon flux is distributed
1  Donor  over a large range of wavelengths, with a maximum photon
VOC ¼ E HOMO  E PCBM LUMO  0:3V (2) flux around 700 nm. To harvest the maximum amount of so-
e
lar energy, the polymer active layer should absorb a larger
Jmax  Vmax number of incident photons.21 The absorption of the active
FF ¼ (3)
JSC  VOC layer is dependent primarily on the conjugated polymer. The

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FIGURE 1 (a) Structure of a bulk heterojunction solar cell; (b) [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM); (c) current–volt-
age characteristic for dark and light current in a bulk heterojunction (BHJ) solar cell.
mismatch between the absorbance spectra and the solar irra-
diance spectrum is one of the main reasons for the low PCEs
of organic photovoltaics.22 The onset of the absorption spec-
tra of a conjugated polymer is a measure of its bandgap. As
shown in Figure 2, due to the relatively large band gap of
poly(3-hexylthiophene) (P3HT), a widely used photovoltaic
material, its absorbance only covers the wavelength range of
300–600 nm of the solar spectrum.2,11,16,23–26 The absorp-
tion spectrum of P3HT matches poorly with the solar emis-
sion spectrum, resulting in a collection of a maximum of
20% of the solar photons.10,11 Therefore, the ideal situation
would be to design conjugated polymers with lower bandg-
aps that will absorb photons at wavelengths above 700 nm
and thus higher current and higher PCEs could be
obtained.22,27 Two commonly used approaches to generate
low bandgap polymers are (i) converting aromatic moieties
to quinoid structures along the polymer backbone5,28 and
(ii) synthesizing D–A polymers.15,22,29
FIGURE 2 The solar spectrum (green line) and the solid state
UV–vis absorption spectra of (a) poly(3-hexylthiophene) (red
line); (b) poly{4,8-bis(4-decylphenylethynyl)benzo[1,2-b:4,5-
b0 ]dithiophene}(blue line).
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In this review, we address only the D–A approach. As shown
in Figure 3, the synthesis of D–A polymers results in a lower
bandgap due to the orbital mixing of the donor and the
acceptor units. The higher energy of the donor group and
the lower energy of the acceptor unit results in a reduced
bandgap (Fig. 3). The alternation of the electron donating
and the electron withdrawing components also increases the
double bond character between the units. Thus, the conju-
gated polymer backbone adopts a more planar configuration,
facilitates p-electron delocalization along the polymer back-
bone, and decreases the bandgap.30 This class of D–A poly-
mers, where the HOMO is mainly located on the donor unit
and the LUMO is located on the acceptor unit, is susceptible
to tuning of the HOMO and LUMO energy levels by attaching
electron withdrawing groups on the acceptor and electron
donating groups on the donor unit.31,32 However, the tuning
of the HOMO and LUMO energy levels, plays a major role not
only in increasing the JSC but it also affects the VOC. A deeper
HOMO level is needed to achieve higher VOC values (2).18
Thus, narrowing the bandgap without sacrificing the efficient
charge separation and the VOC is a major hurdle in achieving
high efficiency polymer solar cells.
The morphology of the active layer is also a crucial factor in
achieving high PCEs in solar cells because an efficient charge
transfer, transport, and collection strongly depend on the
FIGURE 3 Orbital mixing in donor–acceptor semiconducting
polymers.
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FIGURE 4 Donor building blocks for the synthesis of donor–acceptor semiconducting polymers.
nanoscale morphology of the active layer.33–35 Therefore, if the
size of the domains is too large, the excitons will be lost due
to exciton decay. By contrast, if the size of the domains is too
small, the recombination of charge carriers will be enhanced.15
Moreover, for an efficient charge collection, the donor polymer
and acceptor PCBM domains should have a percolated path-
way toward the anode and the cathode. To achieve the best
morphology for a particular conjugated polymer, studies of the
solvent effects, polymer:fullerene ratio effects, annealing
effects, different types of additives, and the ratio of donor poly-
mer/additive are required.36–38 It is apparent that JSC, VOC, and
FF values of a BHJ solar cell are governed by the active layer
donor:fullerene blend. Therefore, the components of the active
layer, that is, donor polymer and fullerene acceptor, and the
morphology of the active layer are crucial factors that influ-
ence BHJ solar cell device performance.
This review describes the D–A semiconducting polymers that
have been reported in the last decade. Additionally, this
review also summarizes the photovoltaic performance of the
D–A polymers and the effect of the morphology on the de-
vice performances. Several reviews on band-gap engineering
and D–A polymers for organic solar cells have been previ-
ously published.35,39–48
The following donor building blocks will be described in this
review: 9,9-dialkyl-2,7-fluorene (FL), 2,7-carbazole (CZ),
cyclopenta[2,1-b:3,4-b0 ]dithiophene (CPDT), dithiene[3,2-
b:20 ,30 -d]silole (DTS), dithieno[3,2-b:20 ,30 -d]pyrrole (DTP),
benzo[1,2-b:4,5-b0 ]dithiophene (BDT), and benzo[1,2-b:4,5-
b0 ]difuran (BDF) (Fig. 4).
Fluorene Donor–Acceptor Polymers
FL has been incorporated as a weak donor unit in various D–
A polymers for organic solar cells. In this tricyclic unit, the
rigid biphenyl ring provides a planar backbone while the car-
bon at the C-9 position allows for the attachment of different
substituents, which can provide enhanced solubility and a
good packing in solid state. Polyfluorenes give rise to a low-
lying HOMO level and can self-organize as anisotropic liquid
crystalline structures at elevated temperatures, thus giving ac-
ceptable hole mobilities and provide good VOC and JSC.49,50
However, an inherent disadvantage of polyfluorenes is the ab-
sence of absorption at short wavelengths due to their rela-
tively large bandgaps (2.8–3.0 eV).51 Extensive research has
been directed towards the lowering of the bandgap by synthe-
sizing D–A copolymers. Benzothiadiazole, various quinoxalines,
and pyrazine have been used as acceptors to generate D–A
copolymers (Fig. 5). The optical and electronic properties of
FL D–A copolymers are summarized in Table 1.
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In 2003, Anderson et al. reported a D–A copolymer contain-
ing FL donor and benzothiadiazole acceptor with a thiopene
p-bridge (1a).51,61 A variety of benzothiadiazole-FL D–A poly-
mers have been synthesized by Suzuki cross-coupling poly-
merization with varying length of alkyl substituents attached
on the FL donor unit (1a–1f).51 The variation of the alkyl
substituents from linear to branched improved the solubility
of the final polymers, and molecular weight increased from
Mn5K for polymers 1a–1d to Mn 20K for the polymers
1g–1f. However, the length of the alkyl substituents on the
9-position of the FL unit had a negligible influence on the
conjugation of the polymer backbone. The HOMO/LUMO
energy levels of the polymers were almost identical. All the
polymers had a HOMO level of 5.50 eV and an optical
bandgap of 1.9 eV. The photovoltaic properties of the
copolymers 1a–1g (Fig. 5) were evaluated in BHJ solar cells
using PC61BM acceptor. For the BHJ with 1g: PCBM ¼ 1:4
weight ratio, a PCE of 2.2% was reported. For polymers 1a–
1d, PCE values of 1.5% were recorded. Further optimiza-
tion for polymer 1c gave a PCE of 2.7% with 1c:PC71BM ¼
1:3 weight ratio, and JSC of 6.2 mA cm2.52 Yang et al.
reported a PCE of 4.5% for 1f at 1f: PC71BM ¼ 1: 3 weight
ratio (JSC ¼ 9.1 mA cm2, VOC ¼ 0.97 V and a FF ¼ 0.51).62
The high carrier transport in the active layer with a hole mo-
bility of 3  105 cm2 V1s1 and the higher molecular
weight are the factors that supported this relatively high
PCE.62 The limited solubility, and hence the lower molecular
weights of polymers 1a–1d, was due to the unsubstituted
thiophene–benzothiadiazole–thiophene unit. Li et al. synthe-
sized three D–A FL polymers (2a–2c) by varying the sub-
stituents on the thiophene–benzothiadiazole–thiophene unit,
which allowed the synthesis of high molecular weight poly-
mers (polymer 2a, Mn ¼ 175 kg mol1).52 The hexyl chains
attached to the 4-position of the thiophene ring in polymer
2a lowered the HOMO energy level by 0.1 eV when com-
pared with 1c. However, the photovoltaic performances were
identical with a PCE of 2.2% recorded for the polymer 2a.
Pei et al. synthesized D–A polymer 2d with octyloxy sub-
stituents at the 3-position of the thiophene unit, for which
the HOMO increased by 0.2 eV when compared with 2a and
the bandgap was lowered to 1.78 eV.53 This was attributed
to the electron donating ability of the alkoxy side substitu-
ents. Changing the location of substituents from the thio-
phene to the benzothiadiazole units (2b–2c) had little influ-
ence on the HOMO, absorbance, and the charge carrier
transport properties of the D–A polymers.53 The polymer 2b
at a weight ratio 2b: PCBM ¼ 1:3 gave a PCE of 2.2% and a
JSC of 4.4 mA cm2. Upon changing the solvent from chloro-
form to dichlorobenzene at 2b: PCBM ¼ 1:3 weight ratio the
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FIGURE 5 Fluorene (FL) donor–acceptor semiconducting polymers.

PCE increased to 3.1% with an increase of JSC to 6.7 mA
cm2. The lower PCE observed for the devices prepared
from chloroform was due to the large-scale phase separation
(high RMS values) which is not favorable for an efficient
charge separation and gave lower current densities.52
A variety of D–A FL polymers have been synthesized by
replacing the 2,1,3-benzothiadiazole with various heterocy-
clic acceptor units, such as [1,2,5]thiadiazolo[3,4-g]quinoxa-
line 3a–3c,54 quinoxaline 4a–4c,55,63 5,56 6,57 2,20 -bi-1,3-thi-
azole 7,58 pyrazino[2,3-g]quinoxaline 8,59 and thieno[3,4-
b]pyrazene 9a–9c.56,60 All of these FL D–A copolymers have
been synthesized by Suzuki cross-coupling polymerization.
The use of stronger acceptor [1,2,5]thiadiazolo[3,4-g]qui-
noxaline (polymers 3a–3c), increased the HOMO and the

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TABLE 1 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Fluorene (FL) D–A Polymers

HOMO/ Eg Egopt [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a l (cm2(V s)1) PCBM (V) (mA cm2) FF (%) Refs.

1a – – 1.92 – 1:4c 1.05 3.65 0.44 1.70 51

1b 5.50/3.55 – 1.95 – 1:4c 1.02 3.74 0.36 1.40 51
1c 5.80/3.40 2.40 1.86 1  105d,e 1:4c 1.01 3.55 0.58 2.10 51
5d,e c
1d – – 1.95 1  10 1:4 0.98 2.40 0.60 1.40 51
1e 5.50/3.60 1.90 – 6  106d,e 1:3f 0.95 8.74 0.44 3.50 52
1f 5.50/3.60 1.90 – 3  105d,e 1:3f 0.97 9.10 0.51 4.50 52
2a 5.60/3.63 – 1.97 1  103d,e 1:3f 1.06 4.90 0.41 2.20 52
2b 5.50/3.49 – 2.01 1  102d,e 1:3f 0.97 6.70 0.47 3.10 52
4d,e f
2c 5.40/3.44 – 1.96 4  10 1:3 0.93 6.30 0.48 2.80 52
2d 5.14/3.36 – 1.78 – 1:4c 0.76 4.31 0.48 1.60 53
3a 5.40/3.90 1.50 1.40 – 1:4g 0.61 2.40 0.40 0.59 54
3b 5.10/3.90 – 1.20 – 1:4g 0.58 3.40 0.35 0.70 54
g
3c 5.30/4.00 – 1.30 – 1:4 0.56 2.10 0.32 0.37 54
4a 5.56/3.43 2.10 – 2  105e,h 1:4f 0.97 5.25 0.57 2.90 55
4b 5.61/3.44 2.40 – 4  105e,h 1:4f 0.99 5.21 0.57 2.90 55
4c 5.69/3.43 2.50 – 6  105e,h 1:4f 0.99 4.51 0.54 2.51 55
f
5 5.60/3.40 2.20 1.80 – 1:4 0.66 3.70 0.44 1.10 56
6 5.43/3.55 – 1.88 2  106d,e 1:4f 1.88 7.90 0.48 3.30 57
7 5.53/2.77 2.76 2.21 – 1:4c 0.76 1.76 0.44 0.52 58
8 5.70/3.90 1.80 1.75 – 1:3c 0.81 6.50 0.44 2.30 59
6e,h f
9a 5.60/3.60 2.00 – 8  10 1:6 0.75 3.00 0.40 0.96 56
9b 5.70/3.70 2.00 1.60 – 1:4f 0.64 3.90 0.58 1.40 56
9c 5.60/3.60 2.00 1.60 8  106e,h 1:4f 0.59 8.80 0.42 2.20 56,60
a e
Refer to individual papers for calculations of HOMO/LUMO levels. Polymer PCBM blend.
b f
CV measurements. PC71BM.
c g
PC61BM. BTF70.
d h
SCLC. OFET.

bandgap of the D–A polymers was reduced. However, these
polymers exhibited very poor PCEs in BHJ with PC61BM
acceptor.54 The energy difference between the LUMO of the
D–A polymers (3.90 eV) and the LUMO of PCBM (3.8
eV) was too low for an efficient charge transfer.15,54 There-
fore, PCBM was substituted for a fullerene with a stronger
electron affinity (BTPF60) a LUMO of 4.1 eV, which gave
PCE of 0.70%. for polymers 3a–3c.64,65
The HOMO energy levels were further lowered for the qui-
noxaline-FL D–A polymers 4a–4c,55 and 5.56 Polymers 4a–4c
and 5 exhibited moderate PCEs of 2%. Lee et al. synthe-
sized a D–A polymer (6) with a selenophene spacer instead
of thiophene, which had a HOMO of 5.43 eV and a
bandgap of 1.88 eV, which is lower than that of 4a–4c
polymers.57 This was due to the insertion of selenophene
spacer, which has a stronger electron donating ability when
compared with thiophene. The PCE of polymer 6 was
increased from  2.4% for a blend of 6:PC61BM ¼ 1:4 to
3.3% for a blend 6:PC71BM 1:4. The AFM images showed
that the 6:PC61BM showed a smoother morphology than the
6:PC71BM blends.57 D–A FL polymers with acceptors 2,20 -bi-
1,3-thiazole (7),58 pyrazino[2,3-g]quinoxaline (8),59 and
thieno[3,4-b]pyrazene (9a–9c)56 showed similar HOMO and
bandgaps when compared with 2,1,3-benzothiadiazole-fluo-
rene polymers, and all showed moderate PCE values. The
reported PCE for 7: PC61BM ¼ 1:1 was 0.52% (JSC ¼ 1.76
mA cm2, VOC ¼ 0.76 V, FF ¼ 0.44), and the PCE of polymer
8: PC71BM ¼ 1:3 was 2.30% (JSC ¼ 6.50 mA cm2, VOC ¼
0.81 V, FF ¼ 0.44). The PCEs of 9a–9c with PC71BM varied
between 0.96% for 9a: PC61BM ¼ 1:6 to 2.20% for 9c:
PC61BM ¼ 1:3. The increased PCE was attributed to the dif-
ference between the hole mobilities of polymer 9a (l ¼ 8 
106 cm2 V1s1) and 9c (l ¼ 8  104 cm2 V1s1). This
increase of two orders of magnitude in the hole mobilities
significantly affected the JSC values and consequently, the
PCE of the BHJ solar cells.56
2,7-Carbazole Donor–Acceptor Polymers
Another class of fused ring systems that has attracted much
attention in the past few years is the CZ. CZ is an analog to
the FL, in which a nitrogen atom bridges the two phenyl
rings. The inherent advantages of the CZ polymers are their
excellent air stability due to their deep lying HOMO levels

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FIGURE 6 Carbazole (CZ) donor–acceptor semiconducting polymers.
and their propensity to form charge-transfer complexes.66
However, due to strong interchain interactions and the pla-
nar polymer backbone, the CZ polymers suffer from limited
solubility causing inconveniences in device fabrication, which
results in lower PCEs.66 A variety of CZ D–A polymers have
been synthesized using Suzuki cross-coupling polymeriza-
tion, among which a few selected D–A copolymers are shown
in Figure 6. Optical bandgaps, the HOMO/LUMO energy lev-
els, and the photovoltaic performances of CZ D–A polymers
are summarized in Table 2.
Leclerc et al. synthesized the first CZ D–A copolymer (10a)
which had a low-lying HOMO of 5.45 eV, a low-lying LUMO
of 3.60 eV, and a bandgap of 1.88 eV.67 A preliminary PCE
of 3.6% was measured for the polymer 10a at a weight ratio
of 10a:PC61BM ¼ 1:4 (JSC ¼ 6.8 mA cm2, VOC ¼ 0.86 V, FF
¼ 0.56).66 Upon further optimization of the molecular weight
of the polymer, the polymer/PCBM blend ratio, and the thick-
ness of the active layer, a PCE of 4.35% was obtained (JSC ¼
9.42 mA cm2, VOC ¼ 0.90 V, FF ¼ 0.51) for the polymer
with Mn ¼ 20 kg mol1 (10a:PC61BM ¼ 1:2; active layer
thickness ¼ 60 nm).76 Upon replacing PC61BM to PC71BM,
for the polymer 10a:PC71BM 1:2 with an active layer thick-
ness of 70 nm, the PCE was further increased to 4.57% (JSC
¼ 10.22 mA cm2, VOC ¼ 0.89 V, FF ¼ 0.51). Heeger et al.
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optimized the conditions with several adjustments, adding a
titanium oxide as an optical spacer and a hole blocking layer
sandwiched between the active layer and the aluminum
layer; by increasing the blend ratio to polymer 10a:PC71BM
¼ 1:4; and changing the solvent form chloroform to dichloro-
benzene. These changes resulted in an increase of PCE to
6.2% (JSC ¼ 11.9 mA cm2, VOC ¼ 0.88 V, FF of 0.66).77
Moreover, under these conditions, the BHJ solar cell device
had an internal quantum efficiency of 100% indicating that
nearly every absorbed photon led to a separated pair of
charge carriers, all of which were collected at the electro-
des.77 More recently, Cao reported a high PCE of 8.37% for
D–A polymer 10a, by incorporating an alcohol/water soluble
poly[(9,9-bis(3-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-
2,7-(9,9-dioctylfluorene) as a cathode interlayer in a BHJ so-
lar cell with PC71BM.8
A D–A polymer CZ-oxadiazolo[3,4-c]pyridine (10c), which is
structurally similar to polymer 10a, showed a HOMO of
5.55 eV which is 0.10 eV lower than the polymer 10a, and
had a smaller bandgap of 1.67 eV.66 Despite a lower HOMO,
a low PCE of 0.7% was measured, most likely due to the
lower hole mobility of the polymer 10c.66 The polymer 10b,
in which the sulfur of [2,1,3]-benzothiadiazole was replaced
by an oxygen atom, showed HOMO, LUMO, and optical
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TABLE 2 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of 2,7-Carbazole (CZ) D–A Polymers

HOMO/ Eg Egopt [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a l (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

10a 5.45/3.60 1.85 1.88 1  103c,d 1:4e 0.75 15.75 0.70 8.37 8
10b 5.47/3.65 1.82 1.87 1  10 4c,d
1:4f 0.96 3.70 0.60 2.40 67
10c 5.55/3.93 1.62 1.67 4  105c,d 1:4f 0.85 1.40 0.60 0.80 67
4c,d f
10d 5.53/3.80 1.73 1.75 5  10 1:4 0.71 2.90 0.32 0.70 67
10e 5.70/4.15 1.55 1.57 – 1:2f 0.82 1.52 0.38 0.47 68
10f 5.21/3.35 1.86 1.95 3  104g,h 1:2.5e 0.81 9.60 0.69 5.40 69
11 5.52/2.95 2.57 2.57 – 1:2f 0.53 0.74 0.35 0.14 70
12a 5.60/3.59 2.01 2.28 – 1:2e 0.99 1.83 0.41 0.74 71
e
12b 5.52/3.50 2.02 2.07 – 1:2 0.86 7.29 0.54 3.41 72
13a 4.99/3.36 1.63 1.91 1  106g,h 1:2e 0.73 6.08 0.39 1.73 73
13b 5.42/3.44 1.98 1.95 – 1:3e 0.76 7.26 0.40 2.20 74
14 5.42/3.64 1.38 1.13 – 1:2f 0.76 5.35 0.56 2.26 75
4c,d f
15a 5.46/3.42 2.04 2.02 3  10 1:4 0.95 3.00 0.56 1.80 68
15b 5.52/3.67 1.85 1.89 2  105c,d 1:4f 0.90 2.60 0.44 1.10 68
15c 5.76/3.99 1.77 1.79 – 1:2f 0.91 0.86 0.44 0.37 68
15d 5.73/3.88 1.85 1.91 – 1:2f 0.66 0.55 0.35 0.13 68
a e
Refer to individual papers for calculations of HOMO/LUMO levels. PC71BM.
b f
CV measurements. PC61BM.
c g
OFET. SCLC.
d h
Pure polymer. Polymer PCBM blend.

bandgap almost identical to 10a. However, due to its lower
hole mobility (1.0  104 cm2 V1s1) when compared with
the polymer 10a (1.0  103cm2 V1s1) polymer 10b
exhibited a PCE of 2.4% for a weight ratio of 10b:PC61BM ¼
1:4.66 The D–A polymer 10e, which is the pyridazine analog
of polymer 10b, showed a deep-lying HOMO of 5.70 eV, a
deep-lying LUMO of 4.15 eV, and a lower gap of 1.57 eV.
The polymer 10e exhibited very poor performance in the
BHJ solar cells (PCE ¼ 0.47%). This was attributed to the
low LUMO level, which prevented an efficient charge transfer
to the PC61BM.68
Zhang et al. synthesized D–A polymer 10f with an electron
donating alkoxy group attached to the acceptor moiety which
increased the HOMO by 0.2 eV when compared with the
polymer 10a.69 Polymer 10f exhibited an initial PCE of
2.75% (JSC ¼ 8.0 mA cm2, VOC ¼ 0.74 V, FF ¼ 0.55) which
was increased to 5.4% upon addition of 1,8-diiodooctane
(DIO) additive (JSC ¼ 9.6 mA cm2, VOC ¼ 0.81 V, FF ¼
0.69).69 The reported high FF indicated that a balanced
charge transport could be achieved by improving the mor-
phology of the active layer blend upon the addition of DIO
additive.69
D–A copolymers of CZ have been synthesized by Suzuki
cross-coupling polymerization by varying the acceptor units,
such as 4,7-bis(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole
(11),70 1,3-bis(thien-2-yl)thieno[3,4-c]pyrrole-4,6-dione
(12a–12b),71,72 5,8-dithien-2-yl-2,3-diphenyl quinoxaline
(13a–13b),73,74 3,6-dithien-2-yl-2,5-di(2-ethylhexyl)-pyr-
rolo[3,4-c]pyrrole-1,4-dione (14)75 and 5,8-bisthien-2-yl-pyr-
azino[2,3-d]pyridazine (15a–15d).68 Among these D–A poly-
mers, 12a and 13b showed good PCEs. The polymer 12a
exhibited an initial PCE of 1.75% (JSC ¼ 4.77 mA cm2, VOC
¼ 0.86 V, FF ¼ 0.43) for a weight ratio of 12a:PC71BM ¼
1:2.72 After changing the solvent from chloroform to dichlor-
obenzene and addition of 3.0% DIO, the PCE of the polymer
12a increased to 3.41% (JSC ¼ 7.29 mA cm2, VOC ¼ 0.86 V
and FF ¼ 0.54). The morphology of the polymer:PCBM
blends varied from large phase separated domains to smooth
films with no large phase separation obtained by changing
the solvent for chloroform to dichlorobenzene and addition
of DIO (Fig. 7). This change of morphology-generated differ-
ences in the photovoltaic performance with a smoother sur-
face promoting an efficient charge transport between the do-
nor and PC71BM acceptor, which enhanced both JSC and
PCE.72
For the polymer 13a, the PCE increased from 0.59 to 1.73%
on changing the fullerene acceptor from PC61BM to PC71BM.
This enhancement of the photovoltaic performances was
attributed to the change in the blend morphology, as well as
the improved light absorption of the active layer in the visi-
ble region due to the presence of the PC71BM fullerene
acceptor.73,74
Donor–Acceptor Copolymers of Bridged Bithiophene
Donors
Cyclopenta[2,1-b:3,4-b0 ]dithiophene, dithieno[3,2-b:20 ,30 -
0 0 0
d ]silole, and dithieno[3,2-b:2 ,3 -d] pyrrole are the bridged
bithiophene donor building blocks described in this section.
Because of the high bandgaps measured for the polymers

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FIGURE 7 AFM height images of polymer 12b with PC71BM blend spin-coated with different solutions (image size: 4  4 lm2).
72
C 2011 American Chemical Society.
Copyright V

with fused dibenzene analogs, such as FL and CZ, their cor-
responding D–A copolymers showed lower PCE values. These
D–A polymers were not ideal for efficient light harvesting. To
address this bandgap challenge, the thiophene analogs of the
fused dibenzene units were developed.78 The fused thio-
phene analogs can produce D–A copolymers with higher pla-
narity because the repulsion caused by the protruding
hydrogen atoms of the phenyl groups with their neighboring
units is relieved by replacing the phenyl with the thiophene
units as demonstrated by DFT calculation (Fig. 8).79
Cyclopenta[2,1-b:3,4-b0 ]dithiophene D–A Polymers
The thiophene analog of FL, cyclopenta[2,1-b:3,4-
b0 ]dithiophene (CPDT), is obtained by fusing two thiophene
rings with one sp3 C atom. CPDT is much more electron rich
than FL and hence has a stronger orbital mixing with the
acceptor units. The CPDT is a versatile building block for a
variety of functional conjugated polymers, because the 4-car-
bon of the CPDT can be functionalized with a wide range of
substituents to fine tune the electronic properties of the
resulting copolymers.78 The structure of CPDT D–A reported
polymers are shown in Figure 9. The optical and electronic
properties of CPDT D–A polymers are summarized in
Table 3.
In 2005, Brabec et al. synthesized the first CPDT D–A copoly-
mers by Stille cross-coupling polymerization to generate
polymer 16a with a HOMO of 5.30 eV and bandgap of 1.40
eV, which exhibited a PCE of 3.5% (JSC ¼ 11.8 mA cm2 for
a weight ratio of 16a:PC61BM ¼ 1:3).91 However, due to the
unfavorable phase separation of the polymer fullerene blend,
high PCEs were not measured for this polymer.84 Bazan
et al. further optimized the device performances of the poly-
mer 16a with 16a:PC71BM ¼ 1:3 with a processing additive
1,8-octanedithiol at 25 mg mL1 and obtained a PCE of 5.5%
with a JSC of 16.2 mA cm2.38 One factor for the improve-
ment of this PCE is that the alkane dithiols influence the
physical interactions between the polymer chains and/or
between polymer and fullerene phases (Fig. 10).38
Neher et al. further improved the PCE of CPDT-2,1,3-benzo-
thiadiazole D–A polymer (16b) to 6.16% by attaching a fluo-
rine atom to the 2,1,3-benzothiadiazole acceptor unit.80 The
incorporation of the fluorine atom simultaneously lowered
the HOMO and LUMO of the D–A polymer, while no effect on
the optical bandgap was observed.92–94 The HOMO and
LUMO of the polymer 16a were 5.02 and 3.58 eV,
whereas that of the polymer 16b were 5.15 and 3.71 eV,
respectively. The photovoltaic measurements for the polymer
16b showed a VOC 130 mV higher than that of 16a, which
was attributed to the increase in the polymer ionization
energy upon fluorine attachment.80 JSC increased to 14.08
mA cm2 for 16b:PC71BM ¼ 1:3 with 2.5% DIO giving a PCE
of 6.16%. The fluorine substituent promoted the formation

FIGURE 8 Torsion energy curves of the D–A polymers backbone units calculated with B3LYP/6-311G(d,p) for the monomer model
(top). The minimum-energy structures indicated by the red arrows in the torsion energy curves. Color code: gray (C), black (H),
79
blue (N), and yellow (S). Copyright V
C 2011 American Chemical Society.

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FIGURE 9 Cyclopenta[2,1-b:3,4-b0 ]dithiophene donor–acceptor semiconducting polymers.
of polymer rich phases and introduced fluorophobicity for
the PC71BM, which led to an improvement of the phase sepa-
ration to generate larger donor/PC71BM domains. Moreover,
fluorination induced higher charge carrier generation and
reduced geminate recombination, thereby increasing the JSC
and FF of the polymer/PC71BM blends.80,95
Yang et al. synthesized a CPDT-2,1,3-benzoselenodithiophene
D–A polymer 16d which had a HOMO of 0.08 eV lower than
that of 16a.78 The bandgap was also decreased to 1.35 eV,
which is 0.1 eV lower than polymer 16a. Despite these
improvements, a lower PCE of 0.66% was measured for the
polymer 16d. The hole and electron mobilities of polymer
16d were 2.5  105 cm2 V1s1 and 2.1  104 cm2
V1s1, respectively. However, the electron mobility of the
blend was one order of magnitude higher than the hole mobil-
ity, and this imbalance contributed to lowering of the PCE.82
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A variety of CPDT D–A polymers have been synthesized by
replacing the 2,1,3-benzothiadiazole acceptor, and depending
on the acceptor strength, the HOMO and the LUMO energy
levels and the optical bandgaps have been varied (Fig. 9).
Thieno[3,4-c]pyrrole-4,6-dione (19),85 bis(bithienyl)-4,40 -
dihexyl-2,20 -bithiazole (23)87 and 3,6-bis(4-hexylthienyl-2-
yl)-s-tetrazine (24a–24e)88,89 acceptors have been used to
generate CPDT D–A polymers that showed better performan-
ces in BHJ solar cells with PCEs of 3%. For example, poly-
mer 19 reported by Guo et al. had a HOMO of 5.26 eV,
which was 0.14 eV lower than the polymer 16a. Polymer 19
exhibited a PCE of 3.15% (JSC ¼ 8.29 mA cm2, VOC ¼ 0.76
V, FF ¼ 0.50) with PC71BM.85 Polymer 24e had a low HOMO
level of 5.37 eV and a bandgap of 1.86 eV.89 This HOMO is
0.35 eV lower than that of 2,1,3-benzothiadiazole analog
(16a). Polymer 24e:PC71BM ¼ 1:3 gave a PCE of 1.03% (JSC
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TABLE 3 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Cyclopenta[2,1-b:3,4-b0 ]dithiophene (CPDT)
D–A Polymers

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

16a 5.02/3.58 – 1.45 1.4  103c,d 1:3e 0.61 11.46 0.50 3.59e 80
e
16b 5.15/3.71 – 1.44 1.0  10 4c,d
1:3 0.74 14.08 0.58 6.04e 80
16c 5.12/3.87 – 1.25 – 1:2f 0.37 15.50 0.48 2.70g 81
16d 5.10/3.34 1.76 1.37 2.9  104c,d 1:3f 0.49 3.91 0.38 0.66 82
16e – – 1.47 – 1:3h 0.78 5.20 0.60 2.50 83
17a 5.12/3.39 1.73 – 2.0  10 4c,d
1:3h 0.60 – 0.42 2.10 84
17b 5.09/3.25 1.84 1.46 3.4  104c,d 1:3f 0.55 6.63 0.36 1.34 82
18 – – 1.53 – 1:3h 0.83 6.40 0.39 2.00 83
3c,d f
19 5.26/3.59 – 1.67 8.9  10 1:2 0.76 8.29 0.50 3.15 85
20a 5.06/3.46 1.60 1.79 1.1  104c,d 1:1h 0.69 7.14 0.45 2.23 86
20b 5.05/3.47 1.58 1.78 1.1  104c,d 1:1h 0.60 6.08 0.44 1.60 86
21a – – 1.54 – 1:3h 0.61 5.20 0.39 1.10 83
21b – – – 1.0  104c,d 1:3h 0.64 – 0.48 0.74 83
6c,d h
22a 5.20/3.44 1.76 1.89 2.0  10 1:1 0.69 4.83 0.33 1.12 86
22b 5.24/3.43 1.81 1.86 2.0  106c,d 1:1h 0.68 2.54 0.34 0.59 86
22c 5.40/3.57 1.83 1.96 5.4  104i,j 1:1h 0.73 6.34 0.53 2.45 87
23 5.07/3.55 1.52 1.84 5.2  104i,j 1:2h 0.70 8.00 0.53 3.04 87
f
24a 5.34/3.53 1.81 1.72 – 1:2 0.78 4.73 0.30 1.11 88
24b 5.35/3.52 1.83 1.61 – 1:2f 0.74 11.10 0.47 3.89e 88
24c 5.26/3.46 1.80 1.60 – 1:2f 0.60 9.08 0.37 2.02e 88
24d 5.35/3.52 1.83 1.66 – 1:2f 0.81 9.44 0.38 2.93 88
24e 5.37/3.51 1.86 1.60 – 1:2f 0.75 12.50 0.59 5.53e 89
h
25 5.10/2.98 2.21 1.18 – 1:3 0.18 0.90 0.38 0.10 83
26 – – 1.24 – 1:3h 0.55 3.20 0.51 1.21 90
a f
Refer to individual papers for calculations of HOMO/LUMO levels. PC71BM.
b g
CV measurements. BTF70.
c h
OFET. PC61BM.
d i
Pure polymer. SCLC.
e j
Additives (refer to the individual papers for the name of the Polymer PCBM blend.
additives).

¼ 4.83 mA cm2, VOC ¼ 0.60 V, FF of 0.35), which increased
to 5.53% on addition of DIO additive (JSC ¼ 12.5 mA cm2,
VOC ¼ 0.75 V, FF ¼ 0.59).88 The morphology of the polymer
blend was demonstrated to play a pivotal role in the device
performances. Upon the addition of the processing additive
DIO, which has a higher boiling point than that of the host
solvent and a good solubility only for the PC71BM, the tend-
ency of PC71BM to crystallize was reduced due to the slower
evaporation of DIO when compared with the host solvent.88
Dithieno[3,2-b:20 ,30 -d]silole D–A Copolymers
Another fused-ring thiophene donor building block that
attracted much attention in the past few years is DTS, in
which the C atom at the 4-position has been replaced with a
silicon atom. DTS D–A polymers have lower LUMO levels and
have shown better performances in optoelectronic devices
when compared with CPDT analogs. The changes in the elec-
tronic properties are due to the effective orbital mixing of
the SiAC p* orbital with the p* orbital of the butadiene frag-
ment allowing for a low-lying LUMO and a low bandgap.96,97
Moreover, the introduction of silicon stabilizes the diene
HOMO when compared with the carbon counterpart, enhanc-
ing the ambient stability of the silole polymers.98 A variety
of DTS D–A copolymers with different acceptor units have
been synthesized by Stille or Suzuki cross-coupling polymer-
izations (Fig. 11). The optical and electronic properties of
DTS D–A copolymers are summarized in Table 4.
In 2007, Tao reported the first DTS D–A copolymer containing
4,7-bis(2-thienyl)-2,1,3-benzothiadiazole as acceptor unit
(29a).107 However, this polymer showed a very poor PCE of
0.18% which was due to the low molecular weight and the
low solubility of the polymer.107 In 2008, Hou reported poly-
mer 27 which had a HOMO of 5.05 eV and a LUMO of
3.27 eV.29 This polymer exhibited a PCE of 3.7% (JSC ¼ 10.9
mA cm2, FF ¼ 0.50) for PC71BM 1:1 weight ratio.29 Upon
annealing, the devices at 140  C, the PCE of the polymer 27

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FIGURE 10 AFM topography images (10  10 mm2) of films cast from chlorobenzene with 24 mg mL1 of progressively longer
alkyl chains. (a) No additive; (b) 1,4-butanedithiol; (c) 1,6-hexanedithiol; (d) 1,8-octanedithiol; (e) 1,9-nonanedithiol. The height
scale is 15 nm for all images. Reprinted with permission from Nature Materials.38
increased to 5.1% with an increase in JSC to 13.06 mA cm2
and FF to 0.62. Moreover, the charge carrier mobility of the
polymer 27 was also increased upon annealing. The lengthen-
ing of the CASi bond in comparison to the CAC bond placed
the solubilizing alkyl chains further apart from the thiophene
rings. This allowed a stronger p-stacking interaction, which
enhanced the solid packing leading to a higher charge carrier
mobility, and ultimately higher JSC and PCE.29,108
Kim et al. synthesized polymers by varying the length of the
alkyl chain substituents on the Si atom (28a, 28b).97 Regard-
less of the different lengths of the alkyl substituents, poly-
mers 28a and 28b exhibited HOMO of 5.55 eV and a
low-lying LUMO of 3.66 eV. The polymers had a high VOC
of 0.90 V. By contrast, the JSC of the polymers showed a
significant difference depending on the alkyl substituent.
Polymer 28a with methyl substituents showed the highest
JSC of 4.29 mA cm2, a VOC of 0.94, and a FF of 0.45, result-
ing in a PCE of 1.84% (28a:P71BM ¼ 1:4 weight ratio).97
Polymer 28b with butyl substituents showed a lower JSC of
2.03 mA cm2, VOC of 0.81 V and a FF of 0.36 resulting in a
PCE of 0.59% (28b:PC71BM ¼ 1:4).97
Yang et al. reported polymers 29a–29c, by varying the sub-
stituents on the silicon atom.98 As mentioned earlier by Tao
et al., the polymer with two hexyl substituents (29a) had
very low solubility in common organic solvents.107 The
HOMO and LUMO levels of polymers 29a and 29b were
quite similar, indicating that the length of the alkyl substitu-
ents does not significantly affect the HOMO/LUMO of the
polymers. Therefore, both the polymers gave similar VOC val-
ues for the polymer: PCBM ¼ 1:1 weight ratio. However,
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polymer 29a gave a PCE of 3.43% with a JSC of 10.67 mA
cm2, VOC of 0.62 V, and a FF of 0.51, while the polymer 29b
gave a PCE of 2.95% with a JSC of 9.76 mA cm2, VOC of 0.60
V, and a FF of 0.50.107 Tao et al. synthesized D–A polymer
30 with thieno[3,4-c]pyrrole-4,6-dione acceptor, which gave
a high PCE of 7.3%.7 Polymer 30 had a deep HOMO of
5.57 eV and a deep-lying LUMO of 3.88 eV. This polymer
achieved a preliminary PCE of 6.2% with a JSC of 10.95 mA
cm2, VOC of 0.90 V, and a FF of 0.63 for 30:PC71BM ¼ 1:2
in dichlorobenzene with 3% DIO additive. Upon changing the
solvent from dichlorobenzene to chlorobenzene, a PCE of
7.3% with a JSC of 12.2 mA cm2, VOC of 0.88 V, and a FF of
0.68 were obtained.7
Li et al. synthesized DTS D–A copolymer containing thiazolo-
thiazole as the acceptor (32a, 32b) and varied the position of
the alkyl substituents on the thiophene spacer group.100,101
Both polymers had similar molecular weights (Mn  6 kg
mol1) and comparable HOMO of 5.04 eV. However, polymer
32b with the alkyl chains substituted at the 4-position of the
thiophene spacer group had a LUMO of 3.41 eV, which is
0.6 eV lower than polymer 32a, for which the alkyl group
was attached at the 3-position of the thiophene unit. Polymer
32b had a higher JSC of 11.25 mA cm2 and a PCE of 5.88%.
Polymer 32a had a JSC of 11.20 mA cm2 and a PCE of
5.59%.101 To investigate the effect of the substituent and the
topology on the photovoltaic properties of the DTS-thiazolo-
thiazole D–A polymers, Jenekhe et al. synthesized polymers
32c–32e.102 Due to the electron donating nature of the alkoxy
substituents of polymer 32e the HOMO increased by 0.1 eV
when compared with 32c and 32d. The polymer 32d with
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FIGURE 11 Dithieno[3,2-b:20 ,30 -d]silole (DTS) donor–acceptor semiconducting polymers.
the ethylhexyl substituents showed the highest PCE of 5.00%
at weight ratio polymer:PC71BM ¼ 1:2. This high PCE was
attributed to the fact that the ethylhexyl substituted polymer
32d had face-on-orientation of the pp stacking in polymer
relative to the substrate, which increased the vertical hole
transport.102 The photovoltaic properties of the polymers 34–
35 were examined by Li et al. in blends with PC71BM and the
PCE of the polymer 35 (PCE ¼ 2.10%) was higher than that
of 34 (PCE ¼ 0.58%).104 The higher PCE of 35 was explained
by the smooth morphology of polymer PC71BM blend.104 A
similar effect was observed for polymers 37 and 38 reported
by Li et al. where the polymer with thiophene spacer exhibit
higher PCE of 3.80% when compared with polymer 37 which
gave a PCE of 1.64%.106
Dithieno[3,2-b:20 ,30 -d]pyrrole Donor–Acceptor
Copolymers
Another class of structurally related analogs of CPDT is
dithieno[3,2-b:20 ,30 -d]pyrrole (DTP), in which the nitrogen
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HIGHLIGHT
atom is substituted at the 4-position. As discussed earlier,
the atom substituted at the 4-position plays a pivotal role in
the electronic properties of the resulting polymer. When the
nitrogen is substituted at the 4-position due to its stronger
electron donating ability, the HOMO of the polymer is
increased and the bandgap is reduced. However, due to the
higher HOMO level, DTP D–A polymers are not stable in air
and can be easily oxidized.109,110 DTP D–A copolymers with
various acceptor units have been synthesized by Stille cross-
coupling polymerization and their structures are shown in
Figure 12. The optical and electronic properties of DTP D–A
copolymers are summarized in Table 5.
Wang et al. synthesized a series of benzothiadiazole DTP
copolymers with varying alkyl chain substituents on the N
atom. (39a–39c).111 The three polymers have almost the
same HOMO/LUMO energy levels, and optical bandgaps, sug-
gesting that the length of the alkyl chain does not have a sig-
nificant impact on the electrochemical properties of the
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TABLE 4 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Dithieno[3,2-b:20 ,30 -d]silole (DTS) D–A
Polymers

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

27 5.05/3.27 1.78 1.45 3.0  103c,d 1:1e 0.68 12.70 0.55 5.01 29
28a 5.63/3.80 – 1.83 1.7  10 5c,d
1:4e 0.94 4.29 0.45 1.84 97
28b 5.53/3.66 – 1.87 5.7  107c,d 1:4e 0.81 2.03 0.36 0.59 97
29a – – – – – – – – – 98
29b 5.02/3.19 1.93 1.51 3.0  106d,f 1:1e 0.62 10.67 0.51 3.43 98
29c 4.99/3.17 1.82 1.53 3.6  10 6c,d
1:1e 0.60 9.76 0.50 2.95 98
30 5.57/3.88 1.69 1.73 1.0  104c,d 1:2e 0.88 12.20 0.68 7.30g 7
31 5.18/3.09 2.09 1.85 3.1  104d,f 1:2e 0.68 7.85 0.53 2.86 99
32a 5.06/2.81 2.26 1.81 3.6  103d,f 1:1e 0.77 11.9 0.61 5.59 100
32b 5.04/3.41 1.63 1.76 7.8  10 2f,h
1:1.3e 0.73 11.25 0.71 5.88 101
32c 5.10/2.29 – 1.73 1.0  102c,d 1:2e 0.62 10.20 0.62 4.10 102
32d 5.10/3.30 – 1.79 3.0  10 2c,d
1:2e 0.65 12.60 0.61 5.00 102
32e 5.00/3.00 – 1.82 1.2  101c,d 1:2e 0.56 7.50 0.49 2.10 102
4c,d e g
33 5.09/3.29 1.80 1.92 7.2  10 1:2 0.62 5.98 0.55 2.03 103
34 5.25/3.00 2.26 2.03 – 1:2e 0.73 2.39 0.33 0.58 104
35 5.19/3.01 2.18 1.93 – 1:2e 0.83 6.27 0.40 2.10 104
36 5.42/3.46 1.96 1.65 – 1:2e 0.88 9.24 0.64 5.21 105
e
37 5.09/2.76 2.33 1.81 – 1:1 0.71 5.65 0.40 1.64 106
38 5.05/2.81 2.24 1.78 – 1:1e 0.63 9.52 0.63 3.80 106
a f
Refer to individual papers for calculations of HOMO/LUMO levels. SCLC.
b g
CV measurements. Additives (refer to the individual papers for the name of the
c
OFET. additives).
d h
Pure polymer. Polymer PCBM blend.
e i
PC71BM. PC61BM.

polymers. However, the PCE of the polymers improved with (39c) gave the highest PCE of 2.80% with a JSC of 11.9 mA
increasing the alkyl chain length, due to the enhanced film cm2 (VOC ¼ 0.54 V, FF ¼ 0.44). Wang et al. reported that
morphology. The polymer with pentyl chain substituents with the decrease in the length of the alkyl chains, the

FIGURE 12 Dithieno[3,2-b:20 ,30 -d]pyrrole (DTP) donor–acceptor semiconducting polymers.

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TABLE 5 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Dithieno[3,2-b:20 ,30 -d]pyrrole D–A Polymers

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

39a 4.89/3.08 1.72 1.41 – 1:3c 0.43 6.19 0.50 1.11 111
39b 4.86/3.07 1.79 1.42 – 1:3c 0.43 11.10 0.43 2.06 111
39c 4.81/3.08 1.73 1.43 – 1:3c 0.54 12.03 0.44 2.80 111
4d,e c
40a 4.80/3.40 1.41 1.50 1.6  10 1:1 0.29 1.20 0.33 0.17 112
40b 5.00/3.43 1.57 1.46 – 1:2f 0.52 9.47 0.53 2.18 112,113
40c 5.07/3.13 1.94 – 3.0  102d,e 1:1f 0.40 2.88 0.37 0.43 109
41 4.90/3.20 1.70 1.41 1.2  104d,e 1:3c 0.51 3.60 0.39 1.30g 112
42 4.90/3.70 0.87 1.20 2.2  103d,e 1:1c 0.27 1.70 0.36 0.22 112
a e
Refer to individual papers for calculations of HOMO/LUMO levels. Pure polymer.
b f
CV measurements. PC71BM.
c g
PC61BM. Additives (refer to the individual papers for the name of the
d
OFET. additives).

morphology of the thin films varied from larger domains For the DTP D–A copolymers, the optical bandgaps are rela-
(400–900 nm) with large phase separation to smaller tively low, but the LUMO and the bandgaps depend on the
domains (50 nm) with uniform phase separation.111 choice of the acceptor unit. However, the HOMO of the DTP

FIGURE 13 Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) donor–acceptor semiconducting polymers (alkyl and alkoxy substituents,
43a-48e).

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TABLE 6 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) D–A
Polymers (Polymers 43a248e)

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

43a 4.90/3.20 1.70 1.62 4.70  104c,d 1:1.2e 0.56 15.10 0.63 5.60 117
43b 4.94/3.22 1.72 1.59 4.00  10 4c,d
1:1f 0.66 12.80 0.66 5.10 93
43c 5.04/3.29 1.75 1.60 7.10  104c,d 1:1f 0.72 13.90 0.58 5.85g 93
43d 5.12/3.31 1.81 1.63 7.70  104c,d 1:1f 0.74 13.00 0.61 6.10g 93
4c,d f g
43e 5.01/3.24 1.77 1.62 4.00  10 1:1 0.66 10.70 0.58 4.10 93
43f 5.01/3.13 1.88 1.61 2.60  104c,d 1:1f 0.62 7.74 0.47 2.26 93
44a 5.15/3.31 1.93 1.68 – 1:1.5e 0.74 14.50 0.69 7.40g 5
e
44b 5.41/3.60 1.81 1.75 – 1:1 0.68 11.00 0.43 3.30 95
44c 5.48/3.59 1.89 1.73 – 1:1e 0.68 9.10 0.39 2.70 95
45 5.12/3.55 1.57 1.61 2.00  10 3d,h
1:1e 0.70 14.70 0.64 6.58 118
46a 5.10/3.19 1.91 – – 1:1f 0.68 2.97 0.44 0.90 78
46b 4.88/3.33 1.55 – – 1:1f 0.55 1.05 0.32 0.18 78
46c 5.34/3.45 1.57 – – 1:1e 0.89 12.43 0.51 5.65g 119
46d 4.08/3.64 1.57 – – 1:1f 0.59 1.99 0.38 0.56 121
47a 5.23/3.38 – 1.85 4.30  10 7c,i
1:3f 0.84 6.28 0.37 1.95 120
47b 4.80/3.25 – 1.55 2.50  105c,i 1:3f 0.40 5.27 0.61 1.28 120
47c 5.20/3.60 1.60 1.64 2.00  105c,i 1:2f 0.75 5.25 0.59 2.90 121
3c,i e
47d 5.17/3.61 1.56 1.64 7.20  10 1:2 0.76 8.96 0.59 4.02 122
47e 5.23/3.57 1.75 1.66 – 1:3f 0.68 3.48 0.47 1.11 123
47f 5.26/3.56 1.76 1.70 – 1:3f 0.74 4.50 0.44 1.92 123
47g 5.29/3.53 1.77 1.76 – 1:3f 0.71 8.60 0.51 3.15 123
f
47h 5.25/3.53 1.77 1.72 – 1:3 0.72 3.95 0.37 1.04 123
47i 5.23/3.53 1.75 1.70 – 1:3f 0.71 2.19 0.33 0.51 123
48a 5.26/2.96 2.30 1.70 3.80  105c,i 1:1f 0.81 9.70 0.55 4.31 124
48b 5.33/3.17 2.16 1.70 1.60  105c,i 1:1f 0.83 7.79 0.59 3.85 124
f
48c 5.47/3.44 2.03 1.51 – 1:1 0.85 12.78 0.58 6.11 125
48d 5.40/3.13 2.27 1.70 – 1:1f 0.87 10.03 0.57 4.70 6
48e 5.54/3.33 2.21 1.70 – 1:1f 0.91 12.91 0.61 7.20 6
a f
Refer to individual papers for calculations of HOMO/LUMO levels. PC61BM.
b g
CV measurements. Additives (refer to the individual papers for the name of the
c
SCLC. additives).
d h
Pure polymer. OFET.
e i
PC71BM. Polymer PCBM blend.

D–A copolymers varied slightly with an average HOMO in
the range of 4.90 eV. Because of this relatively high HOMO,
the VOC of the DTP D–A copolymers in BHJ solar cells are
low, resulting in lower PCE values.
Benzo[1,2-b:4,5-b0 ]dithiophene Donor–Acceptor Polymers
Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) is the most used do-
nor building block for the synthesis of semiconducting
polymers used in OFETs and BHJ solar cells.45,114–116 The
BDT building block offers two advantages: the fused BDT
allows the incorporation of substituents on the central
benzene core while maintaining the planarity of the two
thiophene units, and the symmetric nature of the BDT
monomer eliminates the need of controlling regioregular-
ity during the polymerization.114 Moreover, due to the
large planar conjugated structure of the BDT unit, the
polymer can easily forms pp stacks, which renders high
charge carrier mobility.78 Taking these advantages into
account, many groups have synthesized a variety of BDT
D–A copolymers with tunable bandgaps and HOMO/LUMO
energy levels. The most common strategy is the structural
variation at the 4- and 8-positions of the BDT by the
addition of alkoxy, alkyl, alkylthiophene, and alkylbithio-
phene substituents. Moreover, copolymerization of BDT
with different acceptor monomers generated a plethora
of BDT D–A copolymers. The BDT D–A copolymers were
synthesized by Stille and Suzuki cross-coupling
polymerizations.

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FIGURE 14 Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) donor–acceptor semiconducting polymers (alkyl and alkoxy substituents, 49a-54i).
BDT Donor–Acceptor Polymers Containing Alkyl and
Alkoxy Substituents
Hou et al. first introduced the BDT-conjugated polymers, by
copolymerizing alkoxy-substituted BDT with electron rich
and electron deficient aromatic units. Among these are two
D–A copolymers, polymer 46a with benzo[1,2,5]thiadiazole,
and 46b with benzo[1,2,5]selenadiazole acceptors (Fig.
13).78 The presence of the less electronegative selenium in
polymer 46b increased the HOMO compared to 46a. How-
ever, both polymers exhibited low PCEs (0.90% for 46a;
0.90 and 0.18% for 46b).78 These polymers were tested
without any post-treatment which indicated that BDT could
be a promising candidate for BHJ solar cells. Some of the
alkoxy and alkyl substituted-BDT D–A polymers are shown
in Figure 13, and their electronic properties and photovoltaic
performances are outlined in Table 6.
Yu et al. synthesized a series of BDT copolymers containing
thieno[3,4-b]thiophene carboxylate acceptor with varying
alkyl and alkoxy substituents (43a–43d).93,95 The polymer
43a with a HOMO level of 5.04 eV and an optical bandgap
of 1.62 eV showed a preliminary PCE of 4.76% (JSC ¼ 12.5
mA cm2, VOC ¼ 0.58 V, FF ¼ 0.51) for a weight ratio of
43a: PC61BM ¼ 1:1.95 Upon further optimization by replac-
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HIGHLIGHT
ing the PC61BM with PC71BM for weight ratio 43a: PC71BM
¼ 1:1.2, the PCE increased to 5.6% (JSC ¼ 15.6 mA cm2,
VOC ¼ 0.56 V, FF ¼ 0.63).117 This enhancement of PCE was
attributed to the following factors: (i) the higher absorption
coefficient of PC71BM which improved the light absorption of
the active layer in the visible region; (ii) the high hole mobil-
ity and the balanced carrier mobility in the blend led to a
high FF; and (iii) the interpenetrating network in the blend
film favored the exciton dissociation in the interfacial area
and improved the charge transport.117 When the alkoxy
groups on the 4- and 8-positions of BDT were replaced with
alkyl substituents (43c), the HOMO was lowered by 0.14 eV
and the LUMO was lowered by 0.07 eV, resulting in a higher
bang gap of 1.75 eV when compared with polymer 43a.93
The deeper HOMO level was beneficial to obtain a large VOC
of 0.72 V for the polymer 43c at weight ratio 43c:PC61BM ¼
1:1. A high PCE of 5.10% and a high JSC ¼ 13.90 mA cm2
were measured for 43c.93 The introduction of the electron
deficient fluorine atom on the acceptor unit for polymer 43d
further lowered the HOMO to 5.12 eV and gave a VOC of
0.76 V.93 Upon using a mixed solvent system of DIO and
dichlorobenzene, the PCE of 43d was increased to 6.10%
with an increase of JSC from 9.20 to 13.0 mA cm2. The
change in the morphology of the blends from aggregates
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TABLE 7 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) D–A
Polymers (Polymers 49a254i)

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

49a 5.29/2.87 2.42 1.98 2.90  104c,d 1:2e 0.70 11.14 0.52 4.36 4
49b 5.36/3.05 2.31 2.00 1.00  10 3c,d
1:2e 0.79 11.83 0.72 7.10 4
50 5.30/2.80 2.25 1.99 2.80  103c,d 1:2e 0.76 6.32 0.57 2.72 126
51a – – – – – – – – – 127
4c,d f
51b 5.95/2.63 3.32 1.99 4.70  10 1:1 0.76 0.44 0.25 0.09 127
51c 5.48/2.92 2.56 1.94 1.00  102c,d 1:1f 0.82 6.64 0.47 2.54 127
51d 5.17/2.92 2.25 – 1.40  104c,d 1:2f 0.74 8.71 0.50 3.20g 128
51e 5.15/2.95 2.20 1.97 6.80  104c,h 1:1f 0.86 7.84 0.57 3.82 129
51f 5.50/2.83 2.67 1.93 6.00  102c,d 1:1f 0.91 3.30 0.38 1.14 127
52a 5.15/3.28 1.87 1.45 3.80  10 4h,i
1:2f 0.71 8.80 0.61 4.10g 130
52b 5.14/3.34 1.80 1.51 5.90  105h,i 1:2f 0.59 3.40 0.46 0.93g 130
52c 5.10/3.31 1.79 1.36 1.60  103h,i 1:2f 0.62 5.20 0.43 1.40g 130
53a 5.56/3.75 1.81 1.80 4.60  104h,i 1:2f 0.85 9.81 0.66 5.50 131
53b 5.42/3.60 1.82 1.84 – 1:2f 0.93 6.58 0.56 3.42g 132
f
53c 5.44/3.58 – 1.84 – 1:2 0.91 10.34 0.51 4.79g 132
53d 5.48/3.78 – 1.70 – 1:2e 0.87 8.10 0.56 3.90g 133
53e 5.57/3.87 – 1.70 – 1:1.5e 0.81 9.70 0.67 5.40g 133
54a – – – – – – – – – 134
54b 5.49/3.70 1.65 1.84 – 1:2e 0.76 2.90 0.43 0.95 134
54c – – – – – – – – – 134
54d 5.48/3.78 1.86 1.88 – 1:2e 0.89 7.60 0.57 3.90 134
e
54e 5.48/3.78 1.76 1.84 – 1:2 0.76 9.00 0.51 3.50 134
54f 5.48/3.78 1.83 1.86 – 1:2e 0.66 1.20 0.26 0.20 134
54g 5.48/3.78 1.86 1.88 – 1:2e 0.87 7.20 0.58 3.60 134
54h 5.48/3.78 1.95 1.89 – 1:2e 0.92 2.30 0.34 0.70 134
f
54i 5.35/3.37 1.98 1.98 – 1:1 0.90 2.40 0.50 1.08 135
a f
Refer to individual papers for calculations of HOMO/LUMO levels. PC71BM.
b g
CV measurements. Additives (refer to the individual papers for the name of the
c
SCLC. additives).
d h
Polymer PCBM blend. OFET.
e i
PC61BM. Pure polymer.

with larger domains to smoother films improved the charge
transport and hence increased the JSC and the PCE.93 The
attachment of fluorine atoms on both the acceptor and BDT
donor unit (44c) further decreased the HOMO to 5.48 eV
and LUMO to 3.59 eV, without affecting the bandgap.95 The
polymer 44c gave a lower PCE of 2.7% when compared with
polymers 43a–44b. The lower PCE was due to the fluorina-
tion which provided a driving force for the phase separation
of the polymer/fullerene blend film with no bicontinuous
network, resulting in a poor charge carrier mobility for poly-
mer 44c (l ¼ 7  105 cm2 V1s1).95
Coffin et al. synthesized polymer 46c for which, due to the
presence of the electronegative oxygen atom, a deeper
HOMO was obtained when compared with 46a.119 A prelimi-
nary PCE of 1.41% was obtained for BHJ with PC71BM.119 A
dramatic increase of PCE to 5.65% was observed upon the
addition of 1-chloronaphthalene (2 wt %) as an additive.119
Several groups have synthesized D–A copolymers by bridging
the BDT and the benzothiadiazole acceptor through a conju-
gated moiety such as thiophene, alkylthiophene, and alkoxy-
thiophene.111–113 A broadening of the absorption spectrum
and improved hole mobility were observed for copolymers
47c–47i. Additionally, the alkyl/alkoxy groups enhanced the
solubility of the D–A copolymers, resulting in higher molecu-
lar weights. The polymer 47b has a higher HOMO level than
the polymers 47c–47i. For polymers 47c–47i the HOMO and
the LUMO have values of 5.25 and 3.53 eV, respec-
tively.121–123 These polymers exhibited PCEs greater than
2% with polymer 47d having the highest PCE of 4.02%.122
You et al. reported BDT D–A copolymers from alkyl-substi-
tuted BDT and benzothiadiazole with thiophene bridging
groups (48a–48e).6,124,125 These polymers showed deep
lying HOMO of 5.40 eV, which are lower than that of the
polymers 47a–47i. These polymers gave high VOC and PCE

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FIGURE 15 Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) donor–acceptor semiconducting polymers (ethynyl substituents, 55a-57c).

of 5%. A high PCE of 7.2% (JSC ¼ 12.91 mA cm2, VOC ¼
0.91 V, FF ¼ 0.61) was measured for polymer 48e for a
weight ratio 48e:PC61BM ¼ 1:1.6 The introduction of fluo-
rine atom lowered the HOMO, enhanced the VOC, JSC, and the
FF of the BHJ due to the balanced charge transport and the
improved active layer morphology.6,95
You et al. synthesized polymers 49a–49b (Fig. 14 and Table
7) by replacing the benzothiadiazole with benzotriazole
acceptor, which gave higher HOMO levels of 5.30 eV
when compared with 48a–48e.4 Polymer 49b with fluorine
substituent, gave a high PCE of 7.1% with PC61BM (JSC ¼
11.83 mA cm2, VOC ¼ 0.71 V, FF ¼ 0.73). Zhan and Li
reported BDT D–A copolymers with thiazole and thiazolo-
thiazole acceptors (50, 51a–51f).127,128 Despite attaching
various thiophene or alkylthiophene units on either side of
the acceptor, the highest PCE achieved was only 3.20%.128

TABLE 8 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) D–A
Polymers (Polymers 55a–57c)

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

55a 5.20/3.61 1.59 – – – – – – – 115

55b 5.00/3.43 1.57 – – – – – – – 115
55c 5.25/3.56 1.69 – – – – – – – 115
55d 5.18/4.19 0.99 – – – – – – – 115
56a 5.58/3.53 2.05 1.67 4.82  104c,d 1:4e 0.74 6.49 0.55 2.91 136
56b 5.64/3.54 2.13 1.95 5.66  104c,d 1:4e 0.83 3.71 0.57 1.82 136
57a 5.30/3.00 2.30 1.94 1.20  103c,d 1:1e 0.89 9.77 0.50 4.33 137
3c,d e
57b 5.42/3.52 1.90 1.67 1.93  10 1:1 0.81 9.62 0.59 4.61 136
57c 5.91/3.52 2.39 2.03 4.34  105c,d 1:4e 0.74 0.68 0.28 0.14 136
a d
Refer to individual papers for calculations of HOMO/LUMO levels. Pure polymer.
b e
CV measurements. PC71BM.
c f
SCLC. OFET.

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FIGURE 16 Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) donor–acceptor semiconducting polymers (thienyl substituents, 58a-65).

Li et al. synthesized BDT and diketopyrrolopyrrole D–A
copolymers 52a–52c (Table 7).130 Polymer 52a gave a PCE
of 4.10% with PC71BM.130 N-Alkylthienopyrroledione has
also used as an acceptor for the synthesis of BDT D–A
copolymers (53a–53e, Table 7). Leclerc et al. synthesized
polymer 53a which showed an initial PCE of 5.5% at weight
ratio 53a:PC71BM ¼ 1:1.131 Frechet et al. further optimized
the device performance by using DIO additive and increased
the PCE to 6.8% (JSC ¼ 11.50 mA cm2, VOC ¼ 0.85 V, FF ¼
0.68).133 Several groups synthesized BDT D–A copolymers
with thienopyrroledione as the acceptor unit and thiophene
or alkylthiophene as the bridging conjugated moiety (54a–
54i).134,135 The efficiencies did not improve with the addi-
tional conjugation along the polymer backbone and the high-
est reported PCE was 3.9% for polymer 54d.134
BDT Donor–Acceptor Polymers Containing Conjugated
Substituents
The choice of the substituents attached to the 4- and 8- posi-
tions of the BDT moiety play a crucial role in controlling the
solubility, molecular weight, optical, and electronic proper-
ties of conjugated polymers. Phenylethynyl, triisopropylsily-
lethnyl, alkylthienyl, and alkylbithienyl substituents were

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TABLE 9 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Benzo[1,2-b:4,5-b0 ]dithiophene (BDT) D–A
Polymers (Polymers 58a–67)

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

58a 5.30/3.44 1.87 1.75 4.0  104c,d 1:1e 0.92 10.77 0.58 5.66 138
58b 5.32/3.58 1.74 1.67 – 1:2e 0.82 12.53 0.55 5.64 139
58c 5.41/3.72 1.69 1.63 – 1:2e 0.86 12.05 0.60 6.21 139
59 5.30/3.20 2.30 2.00 1.7  105f,g 1:3e 0.85 10.40 0.59 5.22h 140
3f,g e h
60 5.09/3.22 1.87 1.58 1.5  10 1:2 0.68 14.59 0.63 6.21 141
61 5.11/3.25 1.86 1.58 2.7  101f,g 1:1.5e 0.74 17.48 0.59 7.59h 141
62 5.19/3.26 1.93 1.58 1.0  106f,g 1:1e 0.80 11.71 0.61 6.00 142
63 5.26/3.08 2.18 1.88 2.4  103f,g 1:1e 0.76 10.94 0.54 4.47h 143
4f,g e
64 5.12/3.45 1.67 1.67 1.0  10 1:2 0.76 10.13 0.64 5.00 144
65 4.75/3.11 1.64 1.49 1.0  103f,g 1:2e 0.63 13.90 0.55 4.80 145
66 5.53/3.57 1.97 1.69 7.3  104c,d 1:3i 0.99 5.36 0.47 2.54 146
67 5.52/3.48 2.04 1.70 9.5  104c,d 1:4i 0.91 3.22 0.45 1.33 146
a f
Refer to individual papers for calculations of HOMO/LUMO levels. SCLC.
b g
CV measurements. Polymer PCBM blend.
c h
OFET. Additives (refer to the individual papers for the name of the
d
Pure polymer. additives).
e i
PC71BM. PC61BM.

attached on the BDT and used as donors to generate D–A
BDT copolymers.
Stefan et al. synthesized a series of BDT D–A copolymers
with electron withdrawing phenylethynyl substituents
attached to the BDT core (55a–55d, Fig. 15 and Table
8).115 The bandgaps of the copolymers varied from 2.3 eV
(55a) to 1 eV (55d) depending on the strength of the
acceptor unit. However, the HOMO was relatively
unchanged and the change in the bandgap was due to the
change in the LUMO of the synthesized D–A copolymers.115
Among these polymers the lowest bandgap of 1eV was
measured for 55d with benzobisthiadiazole as the acceptor

FIGURE 17 3D TMAFM phase images of solar cell devices: (a) polymer 66/PCBM (1:3 w/w) active layer without additives; (b) polymer
66/PCBM (1:3 w/w) active layer with 1,8-diiodooctane; (c) polymer 67/PCBM (1:4 w/w) active layer without additives; (d) polymer 67/
PCBM (1:4 w/w) active layer with 1,8-diiodooctane; scan size 5  5 lm (spin-cast from chloroform). Copyright V C 2012 American

Chemical Society.146

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FIGURE 18 Benzo[2,2-b:4,5-b0 ]difuran (BDF) donor–acceptor semiconducting polymers.

unit.115 Cho et al. reported BDT D–A copolymers 56a–56b
with octyl phenylethynyl substituents on the BDT core.136
Both polymers had deep-lying HOMO of -5.60 eV. These
polymers also had a deep lying LUMO and generated a
downhill driving force for the electron transport in BHJ so-
lar cells.15,136
Zhan et al. and Cho et al. synthesized BDT D–A copolymers
with triisopropylsilylethynyl (TIPS) substituents and thiazo-
lothiazole (57a),137 bithiazole (57b),136 and bisthienylbenzo-
thiadiazole (57c) acceptors.136 For the polymer 57a, an opti-
cal bandgap of 1.94 eV with a HOMO level of 5.30 eV and a
PCE of 4.33% for the 57a:PC71BM ¼ 1:1 weight ratio (JSC ¼
9.77 mA cm2, VOC ¼ 0.89 V and FF ¼ 0.50) was obtained.
The polymer 57b showed a deep-lying HOMO of 5.91 eV,
but this polymer showed lower PCE values due to the lower
LUMO level (-3,52 eV). The polymer 57c showed a PCE of
4.61% for the BHJ device configuration of ITO/MoO3/poly-
mer:PC71BM/ZnO/Al.136
Alkylthienyl and alkylbithienyl were attached to BDT and
used as donor building blocks for the synthesis of BDT D–A
copolymers (Fig. 16 and Table 9). Yang et al. reported the
synthesis of polymer 58a with dialkylthienyl-substituted
BDT and dithienylbenzothiadiazole acceptor.138 This polymer
showed a broader absorption in the visible region, a HOMO
of 5.30 eV, and a bandgap of 1.87 eV. Because of the
deep HOMO a high VOC of 0.90 V was obtained in a BHJ de-
vice for weight ratio 58a:PC71BM ¼ 1:1 (JSC ¼ 10.77 mA
cm2, VOC ¼ 0.92 V, FF ¼ 0.58), resulting in a PCE of
5.66%.138
Dai et al. synthesized polymers 58b and 58c with fluorine
and alkoxy substituents attached on the electron acceptor
unit, respectively.139 The combination of electron rich
alkylthienyl substituted BDT donor moiety and the electron
deficient fluorine on the acceptor unit generated polymer
58b with HOMO of 5.41 eV and a PCE of 6.21%. Since
the presence of the fluorine atom also lowered the LUMO, a

TABLE 10 Optoelectronic Properties, Hole Mobility, and the Photovoltaic Performance of Benzo[2,2-b:4,5-b0 ]difuran (BDF) D–A
Polymers

HOMO/ Eg Egopt l [P]: VOC JSC PCE

LUMO (eV)a (eV)b (eV)a (cm2 V1s1) PCBM (V) (mA cm2) FF (%) Refs.

68a 5.10/3.24 1.86 1.75 8.96  104c,d 1:1.5e 0.78 11.77 0.55 5.01 147
68b 5.11/3.06 – 1.67 6.7  10 2c,d
1:2e 0.69 9.87 0.65 4.45 149
68c 5.19/3.49 – 1.63 2.3  104c,d 1:2e 0.82 5.04 0.70 2.88 149
69 4.99/3.06 – 2.00 3.7  10 3c,d
1:2e 0.44 4.92 0.57 1.24 149
3c,d e f
70 4.98/3.18 1.80 1.58 1.2  10 1:1.5 0.63 13.87 0.59 5.22 150
71 5.21/3.20 2.01 1.58 5.8  102c,d 1:1.5e 0.78 13.04 0.61 6.26f 150
a d
Refer to individual papers for calculations of HOMO/LUMO levels. Polymer PCBM blend.
b e
CV measurements. PC71BM.
c f
SCLC. Additives (refer to the individual papers for the name of the additives).

764 JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 743–768
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bandgap of 1.69 eV was measured for polymer 58b.139 Sev-
eral groups reported the synthesis of alkylthienyl-substituted
BDT with a variety of acceptors such as, thiazolothiazole
(59),140 alkoxycarbonyl-substituted thieno[3,4-b]thiophene
(60),141 alkylcarbonyl-substituted thieno[3,4-b]thiophene
(61),141 naptho[1,2-c:5,6-c]bis[1,2,5]thiadiazole (62),142 ben-
zotriazole (63),143 5,50 -dibenzo-[c][1,2,5]thiadiazole (64),144
and diketopyrrolopyrrole (65).145 Among these, polymer 61
gave the highest PCE of 7.59% (JSC ¼ 17.48 mA cm2, VOC ¼
0.74 V, FF ¼ 0.58) for a weight ratio 61:PCBM ¼ 1:1.5 with
3% DIO additive.141
Stefan et al. reported two BDT D–A copolymers with
bithienyl-substituted BDT and benzothiadiazole and thieno-
pyrroledione as acceptors (66–67).146 Six alkyl substituents
per each BDT repeating unit improved the solubility of poly-
mers and allowed the synthesis of relatively high molecular
weight polymers. Because of the conjugated bithienyl sub-
stituents, both the polymers showed a deep-lying HOMO of
-5.53 eV and a bandgap of 1.70 eV. Because of the deep-
lying HOMO a very high VOC of 1.00 V was measured for
polymer 66 with a PCE of 2.52% for a weight ratio of
66:PC61BM ¼ 1:3 (JSC ¼ 5.36 mA cm2, FF ¼ 0.47).146 How-
ever, for these polymers the addition of the DIO additive
lowered the PCEs. This behavior was attributed to the differ-
ence in morphology of the active area of the polymer/PCBM
blend, which changed from a smooth surface to a rougher
surface with large domains upon the addition of DIO
(Fig. 17).146
Benzo[2,2-b:4,5-b0 ]difuran D–A Polymers
BDF is a structurally similar analog to BDT for which the thi-
ophene is replaced by a furan ring. The smaller radii and the
higher electronegativity of oxygen is expected to give BDF
polymers a good packing, a more planar polymer backbone,
and a deep-lying HOMO.147 The BDF homopolymers showed
average hole mobilities.148 The reported BDF D–A copoly-
mers are shown in Figure 18 and their optoelectronic prop-
erties are summarized in Table 10.
Huo et al. reported the first BDF D–A copolymer (68a),
which showed a HOMO of 5.10 eV and a LUMO of 3.24
eV.147 When compared with the BDT D–A copolymer, BDF
polymers have a lower bandgap. A preliminary PCE of 4.66%
(JSC ¼ 10 .00 mA cm2, VOC ¼ 0.78 V, FF ¼ 0.54) was
obtained for a weight ratio of 68a:PC71BM ¼ 1:1.5. Upon
annealing the BHJ devices at 90  C the JSC increased from
10.00 to 11.77 mA cm2, and a PCE of 5.01% was
obtained.147 The increase of JSC was due to the smoother
morphology obtained after annealing the devices.147 Liu
et al. synthesized a series of BDF D–A copolymers with bis-
thienylbenzothiadiazole (68b), bisthienylbenzooxazole (68c),
and bisthienylbenzotriazole (69) acceptors.149 The polymer
68c showed the lowest HOMO of 5.19 eV with a low
bandgap of 1.70 eV. Polymer 69 had a HOMO of 4.99 eV
and a bandgap of 1.93 eV. The difference in the bandgaps of
68b and 69 was attributed to the weaker electron withdraw-
ing benzotriazole unit when compared with the other
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acceptor unit.149 Among these polymers, 68c had the highest
PCE.149
Two D–A copolymers with thienothiophene acceptor were
synthesized by Huo et al. (70 and 71).150 The polymer with
alkoxy substituted-BDF (70) showed an initial PCE of 4.52%
and upon the addition of 3% DIO, the PCE value was
increased to 5.22%. The lower PCE was attributed to the
larger aggregation of PC71BM with domain sizes varying in
the range of 100–350 nm for blends without DIO. Upon the
addition of DIO, a smoother morphology with smaller do-
main sizes was obtained which resulted in a higher JSC. A
similar effect was observed for the alkylthienyl-substituted
BDF polymer (71) upon the addition of DIO, which resulted
in an increase of PCE from 4.54 to 6.43%.150
CONCLUSIONS
D–A alternating structures have been shown to generate
semiconducting polymers that have a lower bandgap due to
the orbital mixing of the donor and acceptor components.
Various combinations of donor and acceptor building blocks
have been used to generate D–A copolymers with some of
them giving excellent performance in BHJ solar cells with
fullerene electron acceptors. However, not all the D–A combi-
nations generated the expected decrease in the bandgap. A
more judicious selection of the D–A pairs is highly desirable
but currently there are no well-established pairing rules. A
potential guidance in selecting D–A pairs can be provided by
DFT calculations that can give an estimate bandgap, which
ideally should be compared with the experimental values
obtained for the synthesized D–A copolymers.
ACKNOWLEDGMENTS
Financial support for this project from NSF (Career DMR-
0956116) and Welch Foundation (AT-1740) is gratefully
acknowledged. The authors gratefully acknowledge the NSF-
MRI grant (CHE-1126177) used to purchase the Bruker
Advance III 500 NMR instrument.
REFERENCES AND NOTES
1 T. A. Skotheim, J. Reynolds, Handbook of Conducting Poly-
mers, 3rd ed.; CRC Press: Boca Raton, 2006.
2 I. F. Perepichka, D. F. Perepichka, (eds. I. F. Perepichka, D. F.
Perepichka) Handbook of Thiophene-Based Materials: Applica-
tions in Organic Electronics and Photonics; Synthesis and
Theory. Wiley VCH: Weinheim; 2009; Vol 2. Chapter 20.
3 C. W. Tang, Appl. Phys. Lett. 1986, 48, 183–185.
4 S. C. Price, A. C. Stuart, L. Yang, H. Zhou, W. You, J. Am.
Chem. Soc. 2011, 133, 4625–4631.
5 Y. Liang, Z. Xu, J. Xia, S.-T. Tsai, Y. Wu, G. Li, C. Ray, L. Yu,
Adv. Mater. 2010, 22, E135–E138.
6 H. Zhou, L. Yang, A. C. Stuart, S. C. Price, S. Liu, W. You,
Angew. Chem. Int. Ed. 2011, 50, 2995–2998, S2995/1–S2995/16.
7 T.-Y. Chu, J. Lu, S. Beaupreı́, Y. Zhang, J.-R. m. Pouliot, S.
Wakim, J. Zhou, M. Leclerc, Z. Li, J. Ding, Y. Tao, J. Am.
Chem. Soc. 2011, 133, 4250–4253.
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 743–768 765

HIGHLIGHT WWW.POLYMERCHEMISTRY.ORG
8 Z. He, C. Zhong, X. Huang, W.-Y. Wong, H. Wu, L. Chen, S.
Su, Y. Cao, Adv. Mater. 2011, 23, 4636–4643.
9 G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Sci-
ence 1995, 270, 1789–1791.
10 C. J. Brabec, V. Dyakonov, J. Parisi, N. S. Sariciftci, Organic
Photovoltaics: Concepts and Realization. Ser. Mater. Sci., Vol
60., Berlin, Heidelberg: Spinger; 2003; pp 297.
11 C. Brabec, V. Dyakonov, U. Scherf, Organic Photovoltaics;
Materials, Device Physics, and Manufacturing Technologies.
Wiley VCH, Weinheim, 2008; pp 575.
12 R. Koeppe, N. S. Sariciftci, Photochem. Photobiol. 2006, 5,
1122–1131.
13 C. J. Brabec, N. S. Sariciftci, J. C. Hummelen, Adv. Funct.
Mater. 2001, 11, 15–26.
das, J. E. Norton, J. r. m. Cornil, V. Coropceanu,
14 J.-L. Bre
Acc. Chem. Res. 2009, 42, 1691–1699.
15 B. C. Thompson, J. M. J. Fre  chet, Angew. Chem. Int. Ed.
2008, 47, 58–77.
16 J. Chen, Y. Cao, Acc. Chem. Res. 2009, 42, 1709–1718.
17 C. J. Brabec, C. Winder, N. S. Sariciftci, J. C. Hummelen, A.
Dhanabalan, van P. A. Hal, R. A. J. Janssen, Adv. Funct. Mater.
2002, 12, 709–712.
18 M. C. Scharber, D. Mühlbacher, M. Koppe, P. Denk, C. Wal-
dauf, A. J. Heeger, C. J. Brabec, Adv. Mater. 2006, 18, 789–794.
19 P. W. M. Blom, V. D. Mihailetchi, L. J. A. Koster, D. E. Mar-
kov, Adv. Mater. 2007, 19, 1551–1566.
20 http://rredc.nrel.gov/solar/spectra/am1.5/. Accessed on Sep-
tember 28, 2012
21 H. Neugebauer, C. Kvarnstrom, C. Brabec, N. S. Sariciftci, R.
Kiebooms, F. Wudl, S. Luzzati, J. Chem. Phys. 1999, 110,
12108–12115.
22 E. Bundgaard, F. C. Krebs, Sol. En. Mater. Solar Cells. 2007,
91, 954–985.
23 H. D. Magurudeniya, P. Sista, J. K. Westbrook, T. E. Ourso,
K. Nguyen, M. C. Maher, M. G. Alemseghed, M. C. Biewer, M.
C. Stefan, Macromol. Rapid Commun. 2011, 72, 1748–1752.
24 R. D. McCullough, R. D. Lowe, J. Chem. Soc. Chem. Com-
mun. 1992, 70–72.
25 M. C. Iovu, E. E. Sheina, R. R. Gill, R. D. McCullough, Macro-
molecules 2005, 38, 8649.
26 M. C. Stefan, M. P. Bhatt, P. Sista, H. D. Magurudeniya,
Polym. Chem. 2012, 3, 1693–1701.
27 V. Shrotriya, G. Li, Y. Yao, T. Moriarty, K. Emery, Y. Yang,
Adv. Funct. Mater. 2006, 16, 2016–2023.
28 H. A. M. van Mullekom, J. A. J. M. Vekemans, E. E. Havinga,
E. W. Meijer, Mater. Sci. Eng. R. 2001, 32, 1–40.
29 J. Hou, H.-Y. Chen, S. Zhang, G. Li, Y. Yang, J. Am. Chem.
Soc. 2008, 130, 16144–16145.
30 J. Peet, A. J. Heeger, G. C. Bazan, Acc. Chem. Res. 2009, 42,
1700–1708.
31 Z. Zhu, D. Waller, R. Gaudiana, M. Morana, D. Mühlbacher,
M. Scharber, C. Brabec, Macromolecules 2007, 40, 1981–1986.
32 H. Zhou, L. Yang, S. Stoneking, W. You, ACS. App. Mater.
Interfaces 2010, 2, 1377–1383.
33 M. Lenes, L. J. A. Koster, V. D. Mihailetchi, P. W. M. Blom,
Appl. Phys. Lett. 2006, 88, 243502.
34 X. Yang, J. Loos, Macromolecules 2007, 40, 1353–1362.
35 H. Hoppe, N. S. Sariciftci, J. Mater. Res. 2004, 19, 1924–1945.
36 J. K. Lee, W. L. Ma, C. J. Brabec, J. Yuen, J. S. Moon, J. Y.
Kim, K. Lee, G. C. Bazan, A. J. Heeger, J. Am. Chem. Soc.
2008, 130, 3619–3623.
766 JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 743–768
JOURNAL OF
POLYMER SCIENCE
37 A. Pivrikas, H. Neugebauer, N. S. Sariciftci, Sol. Energy
2011, 85, 1226–1237.
38 J. Peet, J. Y. Kim, N. E. Coates, W. L. Ma, D. Moses, A. J.
Heeger, G. C. Bazan, Nat. Mater. 2007, 6, 497–500.
39 J. Roncali, Chem. Rev. 1997, 97, 173–206.
40 T. Kietzke, Adv. OptoElectron. 2007, (Recen Advances in So-
lar Cells), 40285/1–40285/15.
41 J. Roncali, Macromol. Rapid Commun. 2007, 28, 1761–1775.
42 Y. Liang, L. Yu, Polym. Rev. 2010, 50, 454–473.
43 Y. Liang, L. Yu, Acc. Chem. Res. 2010, 43, 1227–1236.
44 F. He, L. Yu, J. Phys. Chem. Lett. 2011, 2, 3102–3113.
45 P. Sista, M. C. Biewer, M. C. Stefan, Macromol. Rapid Com-
mun. 2012, 33, 9–20.
46 Y. Li, Acc. Chem. Res. 2012, 45, 723–733.
47 Z.-G. Zhang, J. Wang, J. Mater. Chem. 2012, 22, 4178–4187.
48 H. Zhou, L. Yang, W. You, Macromolecules 2012, 45,
607–632.
49 H. Sirringhaus, R. J. Wilson, R. H. Friend, M. Inbasekaran,
W. Wu, E. P. Woo, M. Grell, D. D. C. Bradley, Appl. Phys. Lett.
2000, 77, 406–408.
50 M. Grell, D. D. C. Bradley, M. Inbasekaran, E. P. Woo, Adv.
Mater. 1997, 9, 798–802.
51 O. Ingana€s, M. Svensson, F. Zhang, A. Gadisa, N. K. Pers-
son, X. Wang, M. R. Andersson, Appl. Phys. A: Mater. Sci. Pro-
cess. 2004, 79, 31–35.
52 W. Li, R. Qin, Y. Zhou, M. Andersson, F. Li, C. Zhang, B. Li,
Z. Liu, Z. Bo, F. Zhang, Polymer 2010, 51, 3031–3038.
53 C. Shi, Y. Yao, Yang; Q. Pei, J. Am. Chem. Soc. 2006, 128,
8980–8986.
54 X. Wang, E. Perzon, W. Mammo, F. d. r. Oswald, S. Admas-
€ s, Thin
sie, N.-K. Persson, F. Langa, M. R. Andersson, O. Ingana
Solid Films 2006, 511–512, 576–580.
55 L. J. Lindgren, F. Zhang, M. Andersson, S. Barrau, S.
€ m, W. Mammo, E. Perzon, O. Ingana
Hellstro €s, M. R. Ander-
sson, Chem. Mater. 2009, 21, 3491–3502.
€ s,
56 W. Mammo, S. Admassie, A. Gadisa, F. Zhang, O. Ingana
M. R. Andersson, Sol. En. Mater. Solar Cells 2007, 91,
1010–1018.
57 J.-Y. Lee, S.-H. Kim, I.-S. Song, D.-K. Moon, J. Mater. Chem.
2011, 21, 16480–16487.
58 J. Lee, B.-J. Jung, S. K. Lee, J.-I. Lee, H.-J. Cho, H.-K. Shim,
J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 1845–1857.
59 F. Zhang, J. Bijleveld, E. Perzon, K. Tvingstedt, S. Barrau, O.
Ingana€s, M. R. Andersson, J. Mater. Chem. 2008, 18,
5468–5474.
60 F. Zhang, W. Mammo, L. M. Andersson, S. Admassie, M. R.
€ s, Adv. Mater. 2006, 18, 2169–2173.
Andersson, O. Ingana
61 M. Svensson, F. Zhang, S. C. Veenstra, W. J. H. Verhees, J.
€s, M. R. Andersson, Adv.
C. Hummelen, J. M. Kroon, O. Ingana
Mater. 2003, 15, 988–991.
62 M.-H. Chen, J. Hou, Z. Hong, G. Yang, S. Sista, L.-M. Chen,
Y. Yang, Adv. Mater. 2009, 21, 4238–4242.
63 F. Zhang, E. Perzon, X. Wang, W. Mammo, M. R. Ander-
sson, O. Ingana€s, Adv. Funct. Mater. 2005, 15, 745–750.
64 O. Ingana €s, F. Zhang, K. Tvingstedt, L. M. Andersson, S.
€ m, M. R. Andersson, Adv. Mater. 2010, 22, E100–E116.
Hellstro
65 E. Perzon, X. Wang, S. Admassie, O. Ingana €s, M. R. Ander-
sson, Polymer 2006, 47, 4261–4268.
66 N. Blouin, A. Michaud, D. Gendron, S. Wakim, E. Blair,
Neagu-R. Plesu, M. Belleta€ te, G. Durocher, Y. Tao, M. Leclerc,
J. Am. Chem. Soc. 2008, 130, 732–742.
 JOURNAL OF
POLYMER SCIENCE WWW.POLYMERCHEMISTRY.ORG
67 N. Leclerc, A. Michaud, K. Sirois, J. F. Morin, M. Leclerc,
Adv. Funct. Mater. 2006, 16, 1694–1704.
68 D. Gendron, P.-O. Morin, A. Najari, M. Leclerc, Macromol.
Rapid Commun. 2010, 31, 1090–1094.
69 R. Qin, W. Li, C. Li, C. Du, C. Veit, H.-F. Schleiermacher, M.
Andersson, Z. Bo, Z. Liu, O. Ingana € s, U. Wuerfel, F. Zhang, J.
Am. Chem. Soc. 2009, 131, 14612–14613.
70 V. Murugesan, B. R. de, R. Mercier, S. Guillerez, L. Perrin,
Synth. Met. 2012, 162, 1037–1045.
71 S. Wen, W. Cheng, P. Li, S. Yao, B. Xu, H. Li, Y. Gao, Z.
Wang, W. Tian, J. Polym. Sci. Part A: Polym. Chem. 2012, 50,
3758–3766.
72 E. Zhou, J. Cong, K. Tajima, C. Yang, K. Hashimoto, J. Phys.
Chem. C 2012, 116, 2608–2614.
73 M.-H. Lai, J.-H. Tsai, C.-C. Chueh, C.-F. Wang, W.-C. Chen,
Macromol. Chem. Phys. 2010, 211, 2017–2025.
74 E. Zhou, J. Cong, K. Tajima, K. Hashimoto, Chem. Mater.
2010, 22, 4890–4895.
75 E. Zhou, S. Yamakawa, K. Tajima, C. Yang, K. Hashimoto,
Chem. Mater. 2009, 21, 4055–4061.
76 S. Wakim, S. Beaupre, N. Blouin, B.-R. Aich, S. Rodman, R.
Gaudiana, Y. Tao, M. Leclerc, J. Mater. Chem. 2009, 19,
5351–5358.
77 S. H. Park, A. Roy, S. Beaupre, S. Cho, N. Coates, J. S.
Moon, D. Moses, M. Leclerc, K. Lee, A. J. Heeger, Nat. Photon
2009, 3, 297–302.
78 J. Hou, M.-H. Park, S. Zhang, Y. Yao, L.-M. Chen, J.-H. Li, Y.
Yang, Macromolecules 2008, 41, 6012–6018.
79 J. Ku, Y. Lansac, Y. H. Jang, J. Phys. Chem. C 2011, 115,
21508–21516.
80 S. Albrecht, S. Janietz, W. Schindler, J. Frisch, J. Kurpiers,
J. Kniepert, S. Inal, P. Pingel, K. Fostiropoulos, N. Koch, D.
Neher, J. Am. Chem. Soc. 2012, 134, 14932–14944.
81 R. C. Coffin, J. Peet, J. Rogers, G. C. Bazan, Nat. Chem.
2009, 1, 657–661.
82 I. H. Jung, H. Kim, M.-J. Park, B. Kim, J.-H. Park, E. Jeong,
H. Y. Woo, S. Yoo, H.-K. Shim, J. Polym. Sci. Part A: Polym.
Chem. 2010, 48, 1423–1432.
83 J. C. Bijleveld, M. Shahid, J. Gilot, M. M. Wienk, R. A. J.
Janssen, Adv. Funct. Mater. 2009, 19, 3262–3270.
84 A. J. MouleÌ, A. Tsami, T. W. Ba€nnagel, M. Forster, N. M.
Kronenberg, M. Scharber, M. Koppe, M. Morana, C. J. Brabec,
K. Meerholz, U. Scherf, Chem. Mater. 2008, 20, 4045–4050.
85 X. Guo, H. Xin, F. S. Kim, A. D. T. Liyanage, S. A. Jenekhe,
M. D. Watson, Macromolecules 2011, 44, 269–277.
86 I. H. Jung, J. Yu, E. Jeong, J. Kim, S. Kwon, H. Kong, K.
Lee, H. Y. Woo, H.-K. Shim, Chem. Eur. J. 2010, 16, 3743–3752,
S3743/1–S3743/2.
87 K.-C. Li, J.-H. Huang, Y.-C. Hsu, P.-J. Huang, C.-W. Chu, J.-T.
s. Lin, K.-C. Ho, K.-H. Wei, H.-C. Lin, Macromolecules 2009, 42,
3681–3693.
88 Z. Li, J. Ding, N. Song, X. Du, J. Zhou, J. Lu, Y. Tao, Chem.
Mater. 2011, 23, 1977–1984.
89 Z. Li, J. Ding, N. Song, J. Lu, Y. Tao, J. Am. Chem. Soc.
2010, 132, 13160–13161.
90 M. Helgesen, F. C. Krebs, Macromolecules 2010, 43,
1253–1260.
91 D. Mühlbacher, M. Scharber, M. Morana, Z. Zhu, D. Waller,
R. Gaudiana, C. Brabec, Adv. Mater. 2006, 18, 2884–2889.
92 H.-Y. Chen, J. Hou, S. Zhang, Y. Liang, G. Yang, Y. Yang, L.
Yu, Y. Wu, G. Li, Nat. Photon 2009, 3, 649–653.
WWW.MATERIALSVIEWS.COM
HIGHLIGHT
93 Y. Liang, D. Feng, Y. Wu, S.-T. Tsai, G. Li, C. Ray, L. Yu, J.
Am. Chem. Soc. 2009, 131, 7792–7799.
94 F. Babudri, G. M. Farinola, F. Naso, R. Ragni, Chem. Com-
mun. 2007, 1003–1022.
95 H. J. Son, W. Wang, T. Xu, Y. Liang, Y. Wu, G. Li, L. Yu, J.
Am. Chem. Soc. 2011, 133, 1885–1894.
96 J.-H. Huang, C.-M. Teng, Y.-S. Hsiao, F.-W. Yen, P. Chen,
F.-C. Chang, C.-W. Chu, J. Phys. Chem. C 2011, 115, 2398–2405.
97 J. S. Kim, Z. Fei, D. T. James, M. Heeney, J.-S. Kim, J.
Mater. Chem. 2012, 22, 9975–9982.
98 L. Huo, H.-Y. Chen, J. Hou, T. L. Chen, Y. Yang, Chem. Com-
mun. 2009, 5570–5572.
99 M. Zhang, H. Fan, X. Guo, Y. He, Z. Zhang, J. Min, J. Zhang,
G. Zhao, X. Zhan, Y. Li, Macromolecules 2010, 43, 5706–5712.
100 M. Zhang, X. Guo, Y. Li, Adv. Mater. 2011, 1, 557–560.
101 Z.-G. Zhang, J. Min, S. Zhang, J. Zhang, M. Zhang, Y. Li,
Chem. Commun. 2011, 47, 9474–9476.
102 S. Subramaniyan, H. Xin, F. S. Kim, S. Shoaee, J. R. Dur-
rant, S. A. Jenekhe, Adv. Energy Mater. 2011, 1, 854–860.
103 E. Ahmed, S. Subramaniyan, F. S. Kim, H. Xin, S. A.
Jenekhe, Macromolecules 2011, 44, 7207–7219.
104 M. Zhang, X. Guo, Z.-G. Zhang, Y. Li, Polymer 2011, 52,
5464–5470.
105 C. Cui, X. Fan, M. Zhang, J. Zhang, J. Min, Y. Li, Chem.
Commun. 2011, 47, 11345–11347.
106 J. Min, Z.-G. Zhang, S. Zhang, M. Zhang, J. Zhang, Y. Li,
Macromolecules 2011, 44, 7632–7638.
107 L. Liao, L. Dai, A. Smith, M. Durstock, J. Lu, J. Ding, Y.
Tao, Macromolecules 2007, 40, 9406–9412.
108 H.-Y. Chen, J. Hou, A. E. Hayden, H. Yang, K. N. Houk, Y.
Yang, Adv. Mater. 2010, 22, 371–375.
109 S. Zhang, Y. Guo, H. Fan, Y. Liu, H.-Y. Chen, G. Yang, X.
Zhan, Y. Liu, Y. Li, Y. Yang, J. Polym. Sci. Part A: Polym.
Chem. 2009, 47, 5498–5508.
110 S. Barlow, S. A. Odom, K. Lancaster, Y. A. Getmanenko, R.
Mason, V. Coropceanu, J.-L. Bre das, S. R. Marder, J. Phys.
Chem. B 2010, 114, 14397–14407.
111 W. Yue, Y. Zhao, S. Shao, H. Tian, Z. Xie, Y. Geng, F.
Wang, J. Mater. Chem. 2009, 19, 2199–2206.
112 X. Zhang, T. T. Steckler, R. R. Dasari, S. Ohira, W. J. Pots-
cavage, S. P. Tiwari, S. Coppee, S. Ellinger, S. Barlow, J.-L.
Bredas, B. Kippelen, J. R. Reynolds, S. R. Marder, J. Mater.
Chem. 2010, 20, 123–134.
113 E. Zhou, M. Nakamura, T. Nishizawa, Y. Zhang, Q. Wei, K.
Tajima, C. Yang, K. Hashimoto, Macromolecules 2008, 41,
8302–8305.
114 P. Sista, H. Nguyen, J. W. Murphy, J. Hao, D. K. Dei, K.
Palaniappan, J. Servello, R. S. Kularatne, B. E. Gnade, B. Xue,
P. C. Dastoor, M. C. Biewer, M. C. Stefan, Macromolecules
2010, 43, 8063–8070.
115 P. Sista, J. Hao, S. Elkassih, E. E. Sheina, M. C. Biewer, B.
G. Janesko, M. C. Stefan, J. Polym. Sci. Part A: Polym. Chem.
2011, 49, 4172–4179.
116 P. Sista, B. Xue, M. Wilson, N. Holmes, R. S. Kularatne, H.
Nguyen, P. C. Dastoor, W. Belcher, K. Poole, B. G. Janesko, M.
C. Biewer, M. C. Stefan, Macromolecules 2011, 45, 772–780.
117 Y. Liang, Y. Wu, D. Feng, S.-T. Tsai, H.-J. Son, G. Li, L. Yu,
J. Am. Chem. Soc. 2009, 131, 56–57.
118 J. Hou, H.-Y. Chen, S. Zhang, R. I. Chen, Y. Yang, Y. Wu,
G. Li, J. Am. Chem. Soc. 2009, 131, 15586–15587.
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 743–768 767

HIGHLIGHT WWW.POLYMERCHEMISTRY.ORG
119 W. Nie, C. M. MacNeill, Y. Li, R. E. Noftle, D. L. Carroll, R.
C. Coffin, Macromol. Rapid Commun. 2011, 32, 1163–1168.
120 J. Hou, H.-Y. Chen, S. Zhang, Y. Yang, J. Phys. Chem. C
2009, 113, 21202–21207.
121 P. Ding, C. Zhong, Y. Zou, C. Pan, H. Wu, Y. Cao, J. Phys.
Chem. C 2011, 115, 16211–16219.
122 P. Ding, C.-C. Chu, B. Liu, B. Peng, Y. Zou, Y. He, K. Zhou,
C.-S. Hsu, Macromol. Chem. Phys. 2010, 211, 2555–2561.
123 Y. Li, Y. Chen, X. Liu, Z. Wang, X. Yang, Y. Tu, X. Zhu,
Macromolecules 2011, 44, 6370–6381.
124 S. C. Price, A. C. Stuart, W. You, Macromolecules 2010,
43, 4609–4612.
125 H. Zhou, L. Yang, S. C. Price, K. J. Knight, W. You, Angew.
Chem. Int. Ed. 2010, 49, 7992–7995, S7992/1–S7992/11.
126 Y. Lin, H. Fan, Y. Li, X. Zhan, Adv. Mater. 2012, 24,
3087–3106.
127 Q. Shi, H. Fan, Y. Liu, J. Chen, L. Ma, W. Hu, Z. Shuai, Y.
Li, X. Zhan, Macromolecules 2011, 44, 4230–4240.
128 H. Fan, M. Zhang, X. Guo, Y. Li, X. Zhan, ACS Appl. Mater.
Interfaces 2011, 3, 3646–3653.
129 M. Zhang, H. Fan, X. Guo, Y. He, Z.-G. Zhang, J. Min, J.
Zhang, G. Zhao, X. Zhan, Y. Li, Macromolecules 2010, 43,
8714–8717.
130 Z. Li, Y. Zhang, S.-W. Tsang, X.-M. Du, J.-Y. Zhou, Y. Tao,
J.-F. Ding, J. Phys. Chem. C 2011, 115, 18002–18009.
131 Y. Zou, A. Najari, P. Berrouard, S. Beaupre, A. B. Reda, Y.
Tao, M. Leclerc, J. Am. Chem. Soc. 2010, 132, 5330–5331.
132 G. Zhang, Y. Fu, Q. Zhang, Z. Xie, Chem. Commun. 2010,
46, 4997–4999.
133 C. Piliego, T. W. Holcombe, J. D. Douglas, C. H. Woo, P.
M. Beaujuge, J. M. J. Frechet, J. Am. Chem. Soc. 2010, 132,
7595–7597.
134 A. Najari, S. Beaupre, P. Berrouard, Y. Zou, J.-R. Pouliot, C.
Lepage-Perusse, M. Leclerc, Adv. Funct. Mater. 2011, 21,
718–728.
768 JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 743–768
JOURNAL OF
POLYMER SCIENCE
135 G. Zhang, Y. Fu, Q. Zhang, Z. Xie, Macromol. Chem. Phys.
2010, 211, 2596–2601.
136 H. G. Kim, S. B. Jo, C. Shim, J. Lee, J. Shin, E. C. Cho, S.-
G. Ihn, Y. S. Choi, Y. Kim, K. Cho, J. Mater. Chem. 2012, 22,
17709–17717.
137 Q. Shi, H. Fan, Y. Liu, W. Hu, Y. Li, X. Zhan, Macromole-
cules 2011, 44, 9173–9179.
138 L. Huo, J. Hou, S. Zhang, H.-Y. Chen, Y. Yang, Angew.
Chem. Int. Ed. 2010, 49, 1500–1503.
139 Q. Peng, X. Liu, D. Su, G. Fu, J. Xu, L. Dai, Adv. Mater.
2011, 23, 4554–4558.
140 L. Huo, X. Guo, S. Zhang, Y. Li, J. Hou, Macromolecules
2011, 44, 4035–4037.
141 L. Huo, S. Zhang, X. Guo, F. Xu, Y. Li, J. Hou, Angew.
Chem. Int. Ed. 2011, 50, 9697–9702.
142 M. Wang, X. Hu, P. Liu, W. Li, X. Gong, F. Huang, Y. Cao,
J. Am. Chem. Soc. 2011, 133, 9638–9641.
143 J. Min, Z.-G. Zhang, S. Zhang, Y. Li, Chem. Mater. 2012,
24, 3247–3254.
144 R. Duan, L. Ye, X. Guo, Y. Huang, P. Wang, S. Zhang, J.
Zhang, L. Huo, J. Hou, Macromolecules 2012, 45, 3032–3038.
145 W. Li, W. S. C. Roelofs, M. M. Wienk, R. A. J. Janssen, J.
Am. Chem. Soc. 2012, 134, 13787–13795.
146 R. S. Kularatne, P. Sista, H. Q. Nguyen, M. P. Bhatt, M. C.
Biewer, M. C. Stefan, Macromolecules 2012, 33, 9–20.
147 L. Huo, Y. Huang, B. Fan, X. Guo, Y. Jing, M. Zhang, Y. Li,
J. Hou, Chem. Commun. 2012, 48, 3318–3320.
148 P. Sista, P. Huang, S. S. Gunathilake, M. P. Bhatt, R. S.
Kularatne, M. C. Stefan, M. C. Biewer, J. Polym. Sci. Part A:
Polym. Chem. 2012, 50, 4316–4324.
149 B. Liu, X. Chen, Y. Zou, L. Xiao, X. Xu, Y. He, L. Li, Y. Li,
Macromolecules 2012, 45, 6898–6905.
150 L. Huo, L. Ye, Y. Wu, Z. Li, X. Guo, M. Zhang, S. Zhang, J.
Hou, Macromolecules 2012, 45, 6923–6929.