5868 Chem. Rev.

2009, 109, 5868–5923

Synthesis of Conjugated Polymers for Organic Solar Cell Applications

Yen-Ju Cheng,* Sheng-Hsiung Yang, and Chain-Shu Hsu*

Department of Applied Chemistry, National Chiao Tung University, 1001 Ta Hsueh Road, Hsin-Chu 30049, Taiwan

Received May 7, 2009

Contents 7.2. Triarylamine-and Phenothiazine-Based 5912

Polymers
1. Introduction 5868 7.3. Fluorenone-Based Polymers 5912
2. Molecular Design and Engineering of Conjugated 5871 7.4. Porphyrin-Based Polymers 5914
Polymers 7.5. Platinum Metallopolyyne-Based Polymers 5914
2.1. Requirement of Band Gap and HOMO-LUMO 5871 7.6. Double-Cable Fullerene-Derivatized Polymers 5916
Energy Levels
7.7. n-Type Conjugated Polymers 5917
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2.2. Strategies for Band Gap Engineering 5871

8. Conclusions and Future Prospects 5917
2.3. Solubility Issues 5873
9. Acknowledgments 5919
2.4. General Routes for Synthesis of Conjugated 5874
10. References 5919
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Polymers
3. p-Phenylenevinylene-Based Conjugated Polymers 5874
3.1. Poly(p-phenylenevinylene) and Its Derivatives 5874 1. Introduction
3.2. Cyano-Containing Poly(p-phenylenevinylene)s 5876 Harvesting energy directly from sunlight using photovol-
3.3. Cyano- and Thiophene-Containing 5877 taic technology is considered as being one of the most
Poly(p-phenylenevinylene)s important ways to address growing global energy needs using
3.4. Acetylene-Containing Poly(p-phenylenevinylene)s 5879 a renewable resource. Polymeric solar cells (PSCs) are a
4. Fluorene-Based Conjugated Polymers 5879 promising alternative for producing clean and renewable
4.1. Fluorene-Based Copolymers Containing 5880 energy due to the fact that there is the potential to fabricate
Electron-Rich Moieties them onto large areas of lightweight flexible substrates by
4.2. Fluorene-Based Copolymers Containing 5881 solution processing at a low cost.1,2 Organic photovoltaic cells
Electron-Deficient Moieties with a single-component active layer sandwiched between
4.3. Fluorene-Based Copolymers Containing 5884 two electrodes with different work functions only led to very
Phosphorescent Complexes low power conversion efficiency due to poor charge carrier
5. Carbazole-Based Conjugated Polymers 5885 generation and unbalanced charge transport.3
5.1. Poly(2,7-carbazole)-Based Polymers 5885 A bilayer heterojunction configuration containing a p-type
5.2. Indolo[3,2-b]carbazole-Based Polymers 5888 layer for hole transport and an n-type layer for electron
6. Thiophene-Based Conjugated Polymers 5889 transport has been implemented by Tang to improve the
6.1. Poly(3-alkylthiophene) and Its Derivatives 5889 photocurrent of the solar cell device.4 As shown in Figure
6.2. Poly(3-hexylselenophene) 5892 1, the general working principle in such solar cells first
6.3. Polythiophenes with Conjugated Side Chains 5893 involves the photoexcitation of the donor material by the
6.4. Isothianaphthene-Based Polymers 5895 absorption of light energy to generate excitons. This Coulomb-
correlated electron-hole pair, the exciton, diffuses to the
6.5. Cyclopenta[2,1-b:3,4-b′]dithiophene-Based 5895
Polymers donor-acceptor (D-A) interface where exciton dissociation
occurs via an electron-transfer process. The fully separated
6.6. Silafluorene- and Dithieno[3,2-b:2′,3′-d]silole- 5897
Based Polymers free charge carriers transport to the respective electrodes in
the opposite direction with the aid of the internal electric
6.7. Dithieno[3,2-b:2′,3′-d]pyrrole-Based Polymers 5899
field, which in turn generates the photocurrent and photo-
6.8. Benzo[1,2-b:4,5-b′]dithiophene-Based Polymers 5901 voltage. Due to the fact that their limited lifetimes only allow
6.9. Thieno[3,4-b]thiophene-Based Polymers 5902 excitons to diffuse a short distance, between 5 and 14 nm,5-9
6.10. Thieno[3,2-b]thiophene-Based Polymers 5903 donor excitons created far away from the heterojunction
6.11. Other Fused Thiophene-Based Conjugated 5904 interface decay to the ground state without the chance to
Polymers reach the acceptor. This leads to the loss of absorbed photons
6.12. Pyrrole-Containing Polymers 5905 and quantum efficiency. Consequently, the performance of
6.13. Other Donor-Acceptor Conjugated Polymers 5905 bilayer heterojunction devices is greatly limited by the small
6.14. Poly(thienylvinylene)s (PTVs) 5910 area of charge-generating interface between the donor and
7. Miscellaneous Conjugated Polymers 5911 acceptor.
7.1. Poly(aryleneethynylene)s 5911 To overcome this difficulty, the concept of a bulk
heterojunction (BHJ) was introduced by the pioneering work
* To whom correspondence should be addressed. Phone: +886-3513-1523.
Fax: +886-3513-1523. E-mail: [email protected] (Y.-J.C.); of Yu et al.10 By blending donor and acceptor materials
[email protected] (C.-S.H.). together, an interpenetrating network with a large D-A
10.1021/cr900182s CCC: $71.50  2009 American Chemical Society
Published on Web 09/28/2009
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5869

Yen-Ju Cheng received his Ph.D. degree in chemistry from the National Chain-Shu Hsu received his Ph.D. degree from Case Western Reserve
Taiwan University (NTU) in 2004 under the supervision of Professor Tien- University in 1987 and conducted his postdoctoral work at the National
Yau Luh. After spending another year as a postdoctoral assistant with Tsing Hua University in Taiwan. He joined the Department of Applied
Prof. Luh at NTU, he joined Prof. Alex K.-Y. Jen’s group as a postdoctoral Chemistry of the National Chiao Tung University, Taiwan, in 1988 as an
researcher at the University of Washington in 2005. In the summer of associate professor and was promoted to full professor in 1991. Currently
2008, he joined the Department of Applied Chemistry, National Chiao he is serving as a vice president and chair professor of the National
Tung University, in Taiwan as an assistant professor. His current research Chiao Tung University. His research interests include liquid crystalline
interest is focused on the design, synthesis, and characterization of organic polymers and conjugated polymers, polymer light-emitting diodes, and
and polymeric functional materials for optoelectronic and photovoltaic organic photovoltaics. He has published more than 160 research papers
applications. and 18 patents. He is currently on the international advisory board of
Polymer and editorial boards of the Journal of Polymer Science, Polymer
Chemistry, and the Journal of Polymer Research. He received the Excellent
Research Award of the National Science Council, Taiwan, in 1994, the
Franco-Taiwan Scientific Award for nanomaterials in 2006, Teco and Hou
Chin Tui Awards in 2007, and an Academic Award of the Ministry of
Education, Taiwan, in 2008.
electron transfer in conjugated polymer-fullerene composites
as reported by Sariciftci and co-workers.11 Buckminster-
fullerene (C60) has proven to be an ideal n-type material due
to its various intrinsic advantages. First, it possesses a
relatively low-lying lowest unoccupied molecular orbital
(LUMO) energy level which is thermodynamically favorable
to accepting electrons from an excited p-type material.12
Second, the triply degenerate C60 LUMO enables it to be
reduced by up to six electrons, which reflects its unique
Sheng-Hsiung Yang received his B.S. degree from the Department of stabilization of negative charges. Third, kinetically, photo-
Applied Chemistry in 1998 from National Chiao Tung University, Taiwan. induced electron transfer from a conjugated polymer to a
He obtained his Ph.D. degree in material science from the University of C60 derivative can occur on a time scale of 45 fs, which is
Nantes, France, in 2004. His research interests include liquid crystalline
polymers, organic light-emitting diodes, and self-assembly of conjugated several orders of magnitude faster than the radiative decay
materials. Currently he is a postdoctoral researcher on light-emitting of photoexcitation or back electron transfer. As a result, the
polymers in Prof. Chain-Shu Hsu’s laboratory. quantum efficiency of charge separation is approaching
unity.13 Through this ultrafast electron transfer which im-
interfacial area can be achieved through controlling the phase mediately quenches the highly reactive excited state of p-type
separation between the two components in bulk. In this way, materials, any possible photooxidation associated with
any absorbing site in the composite is within a few oxygen can be reduced, thus dramatically improving the
nanometers of the donor-acceptor interface, leading to much photostability of the conjugated polymers.14,15 Finally, C60
enhanced quantum efficiency of charge separation. The derivatives also exhibit very high electron mobility in field-
formation of a bicontinuous network creates two channels effect transistors (FETs).16 However, the tendency to crystal-
to transport holes in the donor domain and electrons in the lize and the poor solubility of C60 in organic solvents hinder
acceptor domain, resulting in efficient charge collection. direct applications in inexpensive solution-based processing
Because the BHJ configuration only requires a single techniques unless the bare C60 structure is functionalized with
active layer to create an internal D-A heterojunction, the solubilizing moieties.17-21 To date, one particular solublizing
fabrication of the device can be greatly simplified by derivative synthesized by Wudl and Hummelen in 1995,
employing solution processing techniques without having to namely, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM),
deal with the interfacial erosion problems always encountered is the most ubiquitously used acceptor for current BHJ solar
in making the bilayer configuration. Figure 2 illustrates the cell research (Chart 1).21 One apparent drawback of PCBM
standard BHJ solar cell architecture where an active layer comes from its insufficient absorption in the visible region
of the BHJ composite is sandwiched between two electrodes. due to its structural symmetry which forbids low-energy
The current-voltage (I-V) characteristics under illumination transitions. The efficiency of BHJ devices can be further
and the essential parameters are shown in Figure 3. improved by replacing acceptor C60 PCBM with its higher
The major breakthrough and rapid development of BHJ fullerene analogue C70 PCBM (PC71BM),22,23 which has
solar cells arose from the discovery of efficient photoinduced lower symmetry and allows more transitions (Chart 1).24
5870 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Figure 1. Working mechanism for donor-acceptor heterojunction solar cells. (1) Photoexitation of the donor to generate a Coulomb-
correlated electron-hole pair, an exciton. (2) Exciton diffusion to the D-A interface. A distance longer than the maximum diffusion length
(max LD) will lead to relaxation of the exciton. (3) Bound exciton dissociation at the D-A interface to form a geminate pair. (4) Free
charge transportation and collection at electrodes.
Chart 1. Chemical Structures of PCBM and PC71BM

develop ideal p-type materials. Conjugated polymers are

Figure 2. Architecture of a bulk heterojunction photovoltaic device
novel materials that combine the optical and electronic
using indium tin oxide (ITO) as the electrode and poly[3,4- properties of semiconductors with processing advantages. As
(ethylenedioxy)thiophene]-poly(styrenesulfonate) (PEDOT:PSS) as well as having contributed to a wide range of applications
the hole-conducting layer. The enlarged area shows the active layer such as in organic conductors, field-effect transistors and
consisting of a conjugated polymer-[6,6]-phenyl-C61-butyric acid electroluminescent diodes, conjugated polymers continue to
methyl ester (PCBM) composite with a bicontinuous interpenetrat- serve as the most promising p-type materials for producing
ing morphology with domain sizes between 10 and 20 nm. (The
bottom one is a TEM image, and the top one is a drawing organic solar cells with low weight, integrated flexibility,
illustration). and low cost. Through a tremendous research effort over
the past decade to create numerous novel conjugated
polymers, device performance in BHJ solar cells has been
steadily enhanced and power conversion efficiency (PCE)
higher than 2% is becoming more and more commonplace.
A most encouraging PCE of over 5% has been achieved not
only for the well-known regioregular poly(3-hexylthiophene)
but also for many newly developed low band gap conjugated
polymers. Recent theoretical calculations further predict that
a PCE for BHJ solar cells of over 10% is foreseeable if a
perfect p-type material equipped with all required properties
is available.25-27 This indicates that the development of novel
conjugated polymers will certainly play a pivotal role in
driving this research.
Figure 3. Current-voltage (I-V) characteristics and the corre- Several reviews have examined the use of conjugated
sponding power-voltage curve for a BHJ solar cell under illumina-
tion. Essential parameters determining the photovoltaic performance polymers in solar cell applications.28-32 In view of the rapid
are shown: Jsc is the short-circuit current, Voc is the open-circuit growth of this active field and the increasing number of
voltage, Jmp and Vmp are the current and voltage, respectively, at publications in recent years, this review will not only cover
which a given device’s electrical power output is the maximum, the most important and representative conjugated polymers
Pmax, the fill factor (FF) is a graphic measure of the squareness of that have had a significant impact in the field but will also
the I-V curve, and the power conversion efficiency (PCE) is defined
as the ratio of maximum power output (Pmax) to power input (Pin).
update the latest progress and development of materials with
promising performance. Particular attention will be focused
on synthetic approaches directed toward making these
Enhancement is mainly attributed to C70’s stronger light polymers as well as highlighting the useful and important
absorption in the visible region than that of C60. building blocks leading to the necessary monomers. The
Although C60 derivatives currently fill an irreplaceable principle of molecular design with band gap engineering,
need for n-type materials, there is still an urgent need to structure-property relationships, and device performances
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5871

will also be discussed although space limits any compre-

hensive or complete coverage.

2. Molecular Design and Engineering of

Conjugated Polymers
The most critical challenges in developing ideal p-type
materials are to design and synthesize a conjugated polymer
that simultaneously possesses good film-forming properties,
strong absorption ability, high hole mobility, and suitable Figure 4. Energy diagram of donor and acceptor HOMO-LUMO
HOMO-LUMO energy levels. A fundamental understanding levels showing three intercorrelated parameters. Eg is the band gap
of molecular design and the benefits of versatile polymer of the polymer, Ed is the LUMO energy difference inducing a
syntheses allow for the effective tailoring of the intrinsic downhill driving force for electron transfer, and Vb is the built-in
properties of conjugated polymers to serve the desired potential which has a linear relationship with the open-circuit
voltage.
purpose and address the application needs.
intercorrelated parameters of the donor-acceptor interface
2.1. Requirement of Band Gap and are shown in Figure 4. The donor with the lower HOMO
HOMO-LUMO Energy Levels level will better reach the theoretically attainable Voc, whereas
reduction in a polymer’s band gap to broaden the absorption
The magnitude of the band gap and the energy positions coverage by lifting up the HOMO level will inevitably result
of the HOMO and LUMO energy levels are the most in a loss of Voc. On the other hand, the LUMO level of p-type
important characteristics for determining the optical and materials has to be at least 0.3 eV higher than that level of
electrical properties of a given conjugated polymer. These the fullerene derivatives to guarantee the formation of a
in turn greatly influence the ultimate photovoltaic perfor- downhill driving force for the energetically favorable electron
mance. The first step in the photovoltaic mechanism which transfer and overcome the binding energy of the intrachain
converts light energy to electrical energy in a device involves exciton.27,37,38 Lowering the LUMO level of a conjugated
the absorption of sunlight by the photoactive materials. The polymer to achieve a narrow band gap may result in the
wavelength of the maximum photon flux density of the solar LUMO level eventually being lower than that of the
spectrum is located at approximately 700 nm, which corre- fullerene, thus hampering the efficient electron transfer. A
sponds to a low energy of 1.77 eV. To fully exploit the compromise is needed to balance the trade-off between the
endless source of solar energy, the absorption spectrum of a small band gap of the donor and the favorable energy
conjugated polymer needs to cover both the red and near- HOMO-LUMO relationship between the donor and accep-
infrared ranges to match the greater part of the terrestrial tor. As a result, the effort to find new p-type polymers for
solar spectrum and hence harvest the maximum photon flux. PSC is not solely directed to pursuing low band gaps but
It is highly desirable to develop conjugated polymers with also to controlling the band gap by modulating the
broader absorptions through narrowing their optical band gap. HOMO-LUMO levels to their optimal values.
To efficiently absorb light, high overall extinction coefficients
of the polymers are also of critical importance and should
not be sacrificed as the optical band gaps become smaller.
2.2. Strategies for Band Gap Engineering
The low band gap conjugated polymers have been intensely In terms of the formidable challenges and complex
studied for more than two decades to realize the ultimate prerequisites needed for conjugated polymers used in solar
goal of developing organic conducting metals without the cell applications, molecular engineering to carefully fine-
need of doping. Through numerous manipulations and tune the band gap is of critical importance. Before conjugated
modifications of the chemical structures of conjugated polymers are reviewed, it would be helpful to understand
polymers, band gaps as small as 0.5 eV can be achieved.33 and discuss the general design strategies used to control their
While the utility of renewable energy emerges as a global band gaps.33,39,40 The skeleton of a polyaromatic conjugated
issue to address the energy crisis, conjugated polymers with polymer such as polyphenylene, poly(phenylenevinylene),
low band gaps regain research interest due to their potential and polythiophene can be simplified and defined as “a series
application in organic solar cells. The most straightforward of consecutive carbon-carbon double bonds linked together
way to reduce the band gap is simply by either raising the by a carbon-carbon single bond”. There are two possible
HOMO or lowering the LUMO level of the polymer or by resonance structures for the ground state with nondegenerate
compressing the two levels closer together simultaneously. energy (Figure 5). The first is called the aromatic form: here
Unfortunately, the optical property associated with light each thiophene or benzene unit maintains its aromaticity with
harvesting is not the only one under consideration in confined π-electrons. Delocalization of the flowing π-elec-
designing new p-type polymers. Following photoexcitation, trons along the conjugated chain converts double bonds into
the generated exciton diffuses to the D-A interface to single bonds and synchronously transforms single bonds into
achieve charge separation. To obtain high efficiencies from double bonds, leading to a resonance structure referred to
BHJ polymer solar cells, the n-type material properties of as the quinoid form. Compared to the aromatic form, the
the fullerene derivatives employed should be taken into quinoid form is energetically less stable and hence has a
account throughout the development process. It has been smaller band gap because adopting a quinoid structure
demonstrated that the open-circuit voltage in BHJ solar cells requires destruction of the aromaticity and a loss in the
with ohmic contacts is linearly dependent on the magnitude stabilization energy. The ratio of the aromatic to quinoid
of the built-in potential, defined as the difference between population in a polyaromatic conjugated system can be
the HOMO level of a p-type polymer and the LUMO level correlated and represented by a geometrical parameter, i.e.,
of an n-type PCBM.34-36 The schematic energy profile and bond length alternation (BLA), which is defined as the
5872 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Chart 2. Chemical Structures of Poly(thieno[3,4-b]pyrazine)

P1 and Poly(thieno[3,4-b]thiophene) P2

Chart 3. Chemical Structures of Rigidified P3 and P4

Chart 4. Chemical Structures of P5 and P6 with Its

Figure 5. Aromatic and quinoid resonance forms of poly(p- Resonance Structure
phenylene), poly(p-phenylenevinylene), polythiophene, and poly-
isothianaphthene. The relative contribution of the mesomeric
structures is represented by the size of the colored circles over the
arrows.

average of the difference in length between adjacent

carbon-carbon bonds in a polyene chain. The more the
aromatic form prevails in the ground state, the larger the
BLA value obtained.41 As the quinoid contribution increases,
the carbon-carbon single bonds between two adjacent rings
adopt more double bond character and the BLA starts to
decrease. Overall, the HOMO-LUMO band gap decreases
linearly as a function of the increasing quinoid character with to surpass the rotational disorder due to steric hindrance is
concomitant decreasing BLA value. It is apparent that the to tie and rigidify two adjacent aromatic units through
BLA is highly dependent on the aromatic stabilization covalent chemical bonding. This effect has been well
resonance energy of the aromatic unit. A reduction in demonstrated in a series of excellent work by Roncali and
aromaticity of the aromatic units in the conjugated main chain co-workers. For example, P3, where the bithiophene repeat-
allows a greater tendency to adopt the quinoid form through ing unit is rigidified and bridged by the sp3 carbon of a ketal
π-electron delocalization. Benzene rings with a high degree group, exhibits a remarkably low band gap of 1.2 eV.47,48
of aromaticity cause polyphenylene to have a high band Extension of the bridged system from bithiophene to ter-
gap of ca. 3.2 eV. By inserting a double bond to dilute the thiophene for P4 further decreases the band gap to 1.1 eV
effect of the benzene rings and reduce the aromaticity, the (Chart 3).49
band gap of poly(phenylenevinylene) is reduced to ca. 2.4 In general, the energy difference between the HOMO and
eV. Furthermore, thiophene has an even lower aromaticity LUMO decreases as the length of conjugation increases.
than benzene, so polythiophene is even more likely to adopt However, when the number of monomer units exceeds a
a quinoid form, and consequently, it has a lower band gap certain value at which the effective conjugation length is
of 2.0 eV. The most creative way to effectively increase the saturated, the band gap starts to level off. Therefore,
quinoid character of polythiophene is represented by poly- unlimited extension of the conjugation length results only
isothianaphthene (PITN).42 Again, this is because benzene in a limited reduction of the band gap.
has a larger aromatic resonance energy than thiophene (1.56 Incorporation of electron-donating or electron-withdrawing
vs 1.26 eV, respectively). The main chain of PITN tends to substituents directly onto the aromatic unit in the main chain
favor the quinoid form to selectively maintain the benzene represents another effective way of perturbing the molecular
aromaticity, making PITN the first well-known conjugated orbitals through either inductive or mesomeric effects. In
polymer with a narrow band gap as low as 1 eV.43,44 In a general, electron-donating groups raise the HOMO energy,
similar approach of quinoidization by aromatic exchange, while electron-withdrawing groups lower the LUMO energy,
poly(thieno[3,4-b]pyrazine) P145 or poly(thieno[3,4-b]- resulting in a decreased band gap. For example, poly[3,4-
thiophene) P246 with primary thiophene rings fused with (ethylenedioxy)thiophene] (P5) with direct attachment of
another aromatic pyrazine or thiophene ring at the β-position electron-donating alkoxy groups has a band gap of 1.5 eV,
have also been synthesized to promote quinoid population which is about 0.5 eV lower than that of the parent
and achieve low band gap conjugated polymers (Chart 2). polythiophene.50 For P6 the dual effects of electron-donating
Additionally, molecular modification used to impose steric amino groups and electron-withdrawing nitro groups on the
or electronic effects on conjugated main chains affords neighboring thiophene units results in a dramatically reduced
various useful strategies for reducing the band gap. Pla- band gap of 1.1 eV due to its high degree of zwitterionic
narization between adjacent aromatic units allows parallel and quinoid character (Chart 4).51
p-orbital interactions to extend conjugation and facilitate A more powerful strategy in designing low band gap
delocalization. This in turn leads to a decrease in the BLA conjugated polymers is to alternate a conjugated electron-
and reduction of the band gap. The most straightforward way rich donor (D) unit and a conjugated electron-deficient
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5873

Figure 6. Orbital interactions of donor and acceptor units leading

to a smaller band gap in a D-A conjugated polymer.

Chart 5. Chemical Structures of P7 and P8

Figure 7. Illustration of band gap engineering strategies of

conjugated polymers.

enable a dramatic reduction of the band gap. A highly

stereoregular structure with an extended coplanar conju-
gated conformation is a prerequisite to attain a closely
acceptor (A) unit in the same polymer backbone.52 Through packed and ordered crystalline domain. The general
the introduction of push-pull driving forces to facilitate strategies used to control the band gap of conjugated
electron delocalization and the formation of quinoid meso- polymers are illustrated in Figure 7.
meric structures (DsA f D+dA-) over the conjugated main After photon absorption and exciton dissociation, the most
chain, the BLA can be significantly reduced. Photoinduced critical factor regarding conjugated polymers in determining
intramolecular charge transfer (ICT) correlated with the high- the photovoltaic performance is the charge-transport mobility.
lying HOMO of the donor unit and the low-lying LUMO of The molecular engineering strategies mentioned above are
the acceptor unit can also account for the reduced optical also closely related to the charge-transporting properties of
band gap. This can be elucidated in a more explicit and conjugated polymers. Physical and chemical properties such
simpler way by introducing the concept of hybridization of as facile π-electron delocalization, ordered and planar
the molecular orbital between the donor and acceptor in the intermolecular channels, and excellent electrochemical stabil-
D-A polymer.53 As shown in Figure 6, according to the ity and reversibility will all facilitate the hole-transporting
rules of perturbation theory, the HOMO of the donor segment mobility.56-58
will interact with the HOMO of the acceptor segment to yield
two new HOMOs for the D-A polymer. Similarly, the
LUMO of the donor will interact with that of the acceptor 2.3. Solubility Issues
to produce two new LUMOs of the D-A polymer. After The targeted polymers should possess reasonable solubili-
the electrons redistribute themselves from their original ties in organic solvents to ensure their solution-processability.
noninteracting orbitals to the new hybridized orbitals of the It is rather frustrating if a new conjugated polymer made by
polymer, a higher lying HOMO and a lower lying LUMO tremendous synthetic efforts turns out to be insoluble and
are formed. This leads to a narrowing of the optical band hence unprocessable. The degree of solubility of a given
gap. One evident experimental characteristic of an ICT polymer is governed by several structural factors, including
absorption band is its sensitivity to solvent polarity. In the degree of polymerization, the chain length of the aliphatic
general, the energy required for absorption decreases as the groups, the polarity of the attached substituents, backbone
solvent polarity increases. rigidity, polymer regioregularity, and intermolecular interac-
The copolymer P7 with alternating electron-rich thiophene tions. In addition to the processability, the solubility issue
and electron-deficient quinoxaline moieties exhibits a band can directly influence many other important polymer physical
gap of 1.7 eV (Chart 5).54 The degree of band gap reduction parameters such as crystallinity, phase behavior, microscopic
is strongly dependent on the strength of donor and acceptor morphology, and contact between different active compo-
segments embedded in the conjugated polymer. A judicial nents, which ultimately determine the device performance
choice of the donor-acceptor combination allows for tuning of the final PVCs. Strong interchain π-π stacking interac-
the band gap to the desired magnitude. tions are known to be the major contributing reason that most
With a stronger donor of pyrrole and a stronger acceptor polyaromatic conjugated polymers are rendered insoluble.
of benzothiadiazole, copolymer P8 shows a very low band Introducing aliphatic side chains which are covalently
gap of 1.1 eV in comparison with P7. Such a low band gap attached to the conjugated main chain is an inevitable design
was also attributed to the presence of intramolecular hydro- for improving the solubility. Branched alkyl chains are more
gen bonding, which results in conformational planarization effective than their straight-chain counterparts for inducing
assisted by supramolecular interaction.55 Apart from the solubility. It should be stressed that increasing the content
intrinsic properties of a conjugated polymer in the solution of insulating alkyl chains relative to the hole-conductor
state, intermolecular interactions induced by secondary forces portion in the polymer may result in deterioration in the
in the solid state promote interchain delocalization and charge mobility function. As a result, depending on the nature
5874 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Chart 6. Catalytic Cycle of Transition-Metal-Catalyzed Scheme 1. Synthesis of PPV (P9) via the Wessling Route
Reactions

synthesis of vinylene-containing conjugated polymers via the

carbon-carbon double bond formation between two respec-
tive monomers.
In the following section, we will review those conjugated
polymers which are mainly classified according to the
structures of the representative electron-rich fragments along
of the conjugated backbone, judicious choice of a suitable the main chain.
solubilizing group at an appropriate location is of crucial
importance for fine-tuning the structure-property relationship. 3. p-Phenylenevinylene-Based Conjugated
Polymers
2.4. General Routes for Synthesis of Conjugated
Polymers 3.1. Poly(p-phenylenevinylene) and Its Derivatives
The construction of conjugated polymers lies essentially Conjugated poly(p-phenylenevinylene)s (PPVs) have at-
in the efficient carbon-carbon single bond formation be- tracted a great deal of attention due to their conducting and
tween two unsaturated carbons in the aromatic units. In photoluminescent properties. PPV is the first polymer
addition to electrochemical59-61 or chemical62 oxidative reported for light-emitting diode applications.70 Its derivatives
polymerizations, transition-metal-catalyzed cross-coupling remain the most popular conjugated polymers for this
reactions provide a particularly powerful arsenal for application and continue to generate considerable interest and
Csp2-Csp2 and Csp-Csp2 bond formation.63 The reaction, much research for photovoltaic applications. Pure poly(p-
in general, involves a transition-metal-catalyzed oxidative phenylenevinylene) is insoluble and infusible and therefore
addition reaction across the CsX bond of an electrophile difficult to process into the solid state. Initial attempts using
and then transmetalation with a main group organometallic a traditional Wittig reaction of p-xylylenebis(triphenylphos-
nucleophile, followed by a reductive elimination step leading phonium chloride) and terephthalaldehyde to construct the
to the carbonscarbon bond formation. Concomitantly the double bonds only led to insoluble PPV with very low
active catalyst is regenerated (Chart 6). The most commonly molecular weight.71 A general methodology to circumvent
employed transition-metal catalysts are nickel- or palladium- this problem is to develop a synthetic route that involves a
based complexes, although other metals have also been used. solution-processable polymer precursor. The synthesis of
The organometallic nucleophiles can be Grignard reagents high-quality PPV films with high molecular weights was first
(Kumada-Corriu),64 stannyl (Stille),65 boron reagents developed by Wessling (Scheme 1).72,73 Treatment of the
(Suzuki-Miyaura),66 or copper (Sonogashira).67 Thus, con- bis(sulfonium halide) salt of p-xylene (2) with 1 equiv of
jugation lengths can be extended through consecutive base induces a 1,6-elimination to generate the quinodimethane-
transformations in the catalytic cycle. When the electrophilic like intermediate 3, which subsequently undergoes 1,6-
and nucleophilic centers of the monomeric substrates are polymerization to produce the sulfonium precursor polymer
readily accessible, regioregularity of the polymers can be 4. This water-soluble precursor can then be spin-cast into a
easily achieved. Another advantage is that these reaction thin film and converted in situ into conjugated PPV (P9)
conditions are generally mild and can tolerate many func- after thermal treatment in a vacuum to trigger a 1,2-
tional groups. This is particularly important for synthesizing elimination. The Wessling sulfonium precursor route has also
advanced functional conjugated polymers. Stille and Suzuki been utilized to prepare a wide range of other PPV
coupling reactions using two distinct monomers are the most derivatives.74,75 In a similar manner, various modified
efficient and widely used methods for preparing alternating Wessling procedures using sulfur-based leaving groups such
copolymers. It is noteworthy that stannyl groups substituted as sulfinyl, sulfonyl, and xanthate have all been reported for
on the benzene ring of the monomer substrate always give the synthesis of a range of PPV derivatives.76-78
poor reactivity with aryl halides under Stille coupling Some of the drawbacks of this precursor approach include
conditions.68 Therefore, Stille coupling is more suitable for the generation of toxic side products during the solid-state
thiophene-containing polymers using monomers with stannyl elimination process, structural defects arising from incom-
groups on the thiophene ring, whereas Suzuki coupling is plete thermal conversion or oxidation, and undefined mo-
more widely used for preparing benzene-containing polymers lecular weights and distribution.79 By incorporating long alkyl
with boronic groups on the benzene ring of the monomer. or alkoxy chains into the phenylene ring before polymeri-
On the other hand, nickel-mediated Yamamoto dehaloge- zation to ensure the solubility, a one-step approach can be
nation coupling reactions also provide an alternative pathway applied to make processable PPV derivatives which can then
for carrying out self-polymerizaiton of single monomers.69 be cast into thin films directly without conversion for device
Traditional reactions such as the Wittig-Horner reaction or fabrication.80 Up until now, the most widely used method
Knoevenagel condensation are particularly useful in the for the preparation of PPV derivatives is the Gilch route.
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5875

Scheme 2. Synthesis of MEH-PPV (P10) via the Gilch Route Scheme 3. Illustration of Defect Formation during the Gilch
Route

Chart 7. Chemical Structure of MDMO-PPV (P11)

This involves the reaction of R,R′-dihalo-p-xylene 6 with 2

equiv of base to obtain conjugated PPV through a one-pot
straightforward elimination-polymerization-elimination three-
step procedure.81-83 Because of the smaller size of the halide Chart 8. Chemical Structure of Polymer BBL P14
relative to sulfur-based leaving groups, this route allows PPV
to introduce more bulky groups into the phenylene ring
without affecting the reaction. A typical Gilch route to the
synthesis of a representative solution-processable poly(2-
methoxy-5-((2′-ethylhexyl)oxy)-1,4-phenylenevinylene) (MEH-
PPV, P10) is depicted in Scheme 2.83 By following the same
synthetic route, poly(2-methoxy-5-((3′,7′-dimethyloctyl)oxy)- The substituent on the phenylene ring of PPV allows for
1,4-phenylenevinylene) (MDMO-PPV, P11) can also be the tuning of the band gap. The HOMO and LUMO levels
synthesized (Chart 7). This route involves mild polymeri- of unsubstituted PPV are reported to be ca. -5.1 and -2.7
zation conditions, and the molecular weights of the polymers eV, respectively, with a band gap around 2.4 eV.95 Introduc-
obtained are generally high. ing two alkoxy groups into the phenylene ring to perturb
the molecular orbitals lowers the LUMO to -2.9 eV with
In some cases gelation or precipitation of the polymeric
an essentially unchanged HOMO level. Hence, the band gap
products may occur during polymerization. Ferraris et al.
is reduced to 2.2 eV.95 Consequently, PPV emits a green-
developed a modified Gilch method for carrying out anionic
yellow light, while MEH-PPV exhibits a yellow-orange
polymerizations by the addition of monomer to the base
emission. Because PPV derivatives are the earliest conjugated
solution along with using 4-methoxyphenol as the initiator
polymers developed for organic electronics application, they
to control the molecular weight.83 The mechanism of the
were also frequently used as the active materials in bilayer
synthetic route to PPV via a quinodimethane intermediate
heterojunction solar cells before the concept of bulk hetero-
has been a debatable subject: a radical vs an anionic pathway.
junction configuration was widely accepted. For bilayer
The presence of radical trapping reagents during the reaction
photovoltaic cells, PPV and MEH-PPV serve as the electron
significantly reduces the molecular weight of PPV, implying
donor in conjunction with a poly(benzimidazobenzophenan-
a radical mechanism.84,85 On the other hand, in the presence
throline ladder) (BBL, P14) as the electron acceptor (Chart
of an additive nucleophile as the initiator, an anionic
8).96 The bilayer device with the configuration ITO/PPV/
polymerization pathway has been proposed.86-88
P14/Al showed a Jsc of 2.3 mA/cm2, a Voc of 1.06 V, an FF
It has been shown that formation of structural defects in of 47%, and a PCE value of 1.4%. While using MEH-PPV
PPV will give rise to deteriorated emission efficiency. as the electron donor, the device achieved a PCE of 0.8%
Regioregular, head-to-tail coupling of the asymmetric quin- under the same conditions.96 The better photovoltaic perfor-
odimethane halide 8 results in 100% vinylene formation in mance of PPV over MEH-PPV can be ascribed to the greater
P12 between the neighboring phenylene units after elimina- crystallinity and structural order of the PPV main chain
tion of 9. However, it is known that the resulting polymer compared to alkylated MEH-PPV. In addition, the fact that
P13 contains 1.5-2.2% structural defects due to head-to- the complementary optical absorption of PPV/P14 covers
head or tail-to-tail couplings in 10. This leads to the the 300-720 nm spectral range, whereas MEH-PPV/P14
sequential formation of corresponding acetylene and ethylene lacks absorption in the 350-460 nm range, also contributes.
moieties which in turn attenuate the desired electronic and Soluble MEH-PPV was also combined with PCBM for
optical properties of PPV (Scheme 3).89 By manipulating the photovoltaic applications. The bilayer photovoltaic device
substituents on the phenylene ring, the number of defects with the configuration ITO/PEDOT:PSS/MEH-PPV/PCBM/
can be reduced to obtain high-performance polymers.90,91 Al showed a Jsc of 2.1 mA/cm2, a Voc of 0.75 V, an FF of
Besides the elimination approach via a quinodimethane 23%, and a PCE value of 0.46%.97 A bulk heterojunction
intermediate, other traditional Wittig-type92 and Knoevena- photovoltaic cell using MEH-PPV/PCBM as the active layer
gel-type93 polycondensations or palladium-catalyzed Heck has also been characterized. It showed better PCE values in
coupling reactions have all been employed to prepare PPV the range 1.1-1.3% than bilayer devices.98 Furthermore, by
derivatives.94 stacking two independent single photovoltaic cells together
5876 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Chart 9. Chemical Structures of C60 Derivatives 11 and 12 bulk heterojunction active layer system: photooxidation,107
stacked cells,108 active layer thickness,109 NMR morphology
studies,110 and insertion of a hole-transporting layer between
PEDOT and the active layer.111 Apart from the PCBM
organic acceptor, inorganic electron acceptors112-115 such as
metal oxides or quantum dots are also under active develop-
ment and have been combined with conjugated MDMO-PPV
to form hybrid organic-inorganic bulk heterojunction solar
cells. Optimized photovoltaic devices using blends of MDMO-
PPV:ZnO113 or MDMO-PPV:cadmium selenide115 exhibited
moderate PCE values of 1.6% and 1.8%, respectively.
In addition to PPV homopolymer derivatives, two R,R′-
dihalo-p-xylene monomers with different side chains can also
be randomly copolymerized by the Gilch route to afford a
variety of interesting PPV derivatives. The feeding ratio of
two monomers can be varied to fine-tune the steric and
with the help of the transparent cathode LiF/Al/Au, the PCE electronic properties of the resultant polymer. Scheme 5
of the multiple-device stacked structure can be dramatically shows the synthesis of two different dendron-containing
improved 2-fold to 2.6%.98 The cells can be stacked together MEH-PPV derivatives. P17 has 3,5-dialkoxybenzyl pen-
and connected either in parallel or in series, resulting in dents,116 while P18 possesses electron-deficient oxadiazole
doubled Jsc or Voc, respectively, compared to those of a single segments as the side chain.117 A solar cell device based on
cell. P18:PCBM (1:4, w/w) displayed a Jsc of 4.93 mA/cm2, a
Two alternative soluble methanofullerene derivatives 11 Voc of 0.81 V, an FF of 40%, and a PCE value of 1.6%. On
and 12 have been developed to serve as electron acceptors the other hand, a device fabricated using a P17:PCBM (1:3,
and blended with MEH-PPV to fabricate photovoltaic w/w) blend showed a Jsc of 3.37 mA/cm2, a Voc of 0.81 V,
devices. The chemical structures of the C60 derivatives are an FF of 42%, and a PCE value of 1.41%, which is slightly
shown in Chart 9. Due to a better compatibility of 11 with better than the corresponding MEH-PPV-based device with
MEH-PPV, the MEH-PPV/11 system shows a better device a PCE of 1.32% under the same condition.
PCE of 0.49% than the MEH-PPV/12 system, which has a A new PPV derivative (P19) with two triphenylamine
PCE of 0.22%.99 In addition to C60 derivatives, different types groups attached directly to the 2,5-positions of the phenylene
of titanium oxide (TiO2) were combined with MEH-PPV for moieties was synthesized by the Wittig-Horner reaction of
photovoltaic applications.100-104 However, their device per- 22 and 23 to improve its hole-transporting properties and
formances were generally low, with PCE values lower than balance of charge transport in the active layer (Scheme 6).118
0.5%. Compared to P20 with a band gap of 2.3 eV, P19 exhibits
MDMO-PPV is the most widely used PPV derivative to a lower band gap of 2.0 eV and broader absorption spectrum
serve as the electron donor in combination with C60 electron due to the electronic band of the triphenylamino group at
acceptor derivatives in organic BHJ photovoltaic cells. shorter wavelengths and a more red-shifted band at longer
Devices based on blended MDMO-PPV:PCBM (1:4, w/w) wavelengths arising from the 3-dimensional π-π stacking.
were fabricated and reported by Shaheen and co-workers.105 The bulk heterojunction polymer solar cells based on P19/
It was found that when chlorobenzene was used as the casting PCBM (1:1, w/w) showed a PCE of 0.45%, which is much
solvent instead of toluene to deposit the active layer, an higher than that of the device based on P20 (0.09%) without
optimal morphology with suppressed phase segregation and the triphenylamino side chains.
enhanced microstructure was obtained, resulting in increased
charge carrier mobility for both holes and electrons in the 3.2. Cyano-Containing Poly(p-phenylenevinylene)s
active layer. Consequently, the device achieved a Jsc of 5.23
mA/cm2, a Voc of 0.82 V, and a high PCE of 2.5%.105 In addition to introducing functional groups on the
Regioregularity in MDMO-PPV also plays an important phenylene ring, the molecular orbital energy levels of PPV
role in determining the device performance. As shown in derivatives can also be tuned by incorporating electronic
Scheme 4, Tajima and co-workers synthesized a fully substituents into the conjugated vinylene bridges. By means
regioregular MDMO-PPV (P15) by the Wittig-Hornor of a facile Knoevenagel polycondensation between tereph-
reaction of a single monomer (15) comprised of aldehyde thaldehyde 24 and 1,4-bis(cyanomethyl)benzene 25 in the
and phosphonate functionalities.106 Regiorandom MDMO- presence of the base t-BuOK, the CN-PPV derivatives
PPV (P16), from dialdehyde 16 and diphosphnate monomers containing a cyano group on each double bond are easily
17, was also prepared for comparison. A PCE of 3.1%, a Jsc accessible (Scheme 7). Careful control of the reaction
of 6.2 mA/cm2, a Voc of 0.71 V, and an FF of 70% were conditions is required to avoid a Michael addition which may
achieved with regioregular MDMO-PPV (P15). This is the lead to defected polymers. Alkoxy chains are introduced onto
highest efficiency reported for the PPV:PCBM system so the aromatic rings to improve the solubility of the resulting
far. In contrast, the device based on regiorandom MDMO- polymers.
PPV (P16)/PCBM only achieved a PCE of 1.7%. It is Compared to MEH-PPV, the replacement of vinylene
concluded that higher crystallinity of the polymer for higher linkages with cyanovinylene linkages in MEH-CN-PPV
hole mobility and better mixing morphology between the lowers both the LUMO and HOMO levels by ∼0.5 eV, with
polymer and PCBM contribute to the improvement of little effect on the magnitude of the band gap. It should also
photovoltaic performance with regioregular MDMO-PPV. be noted that, with additional cyano groups on the double
Various physics and engineering aspects have been bond, the conjugated backbone may twist as a result of steric
investigated for devices based on the MDMO-PPV/PCBM hindrance. Additionally, CN-PPV displays high electron
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5877

Scheme 4. Synthesis of Regioregular and Regiorandom MDMO-PPVs

Scheme 5. Synthesis of PPV Copolymers P17 and P18

affinities and electron-transport properties as a result of the P23.120 The chemical structures of P22 and P23 are shown
electron-withdrawing effect of the cyano side group and a in Chart 10. It is also noteworthy that CN-PPV derivatives
low-lying LUMO level so that it can function as a suitable with increased oxidation potential also improve the stability
electron acceptor in photovoltaic devices in either a bilayer of PPV against singlet oxygen photooxidation.122
or bulk heterojunction configuration.119-121 For example, a
bilayer device consisting of P21 as the n-type layer and 3.3. Cyano- and Thiophene-Containing
polythiophene P22 as the p-type layer, was constructed by Poly(p-phenylenevinylene)s
a lamination technique followed by thermal annealing,
achieving an overall PCE of 1.9%.119 Alternatively, MEH- To effectively reduce the band gap of CN-PPV below 2
PPV has also been blended with P23 as the electron eV, electron-rich thiophene units with lower aromaticities
donor-acceptor pair in a single-layer device, showing much have been incorporated into the main chain to form a D-A
better photovoltaic performance compared to similar devices arrangement. Vanderzande et al. reported a series of copoly-
with single components of either MEH-PPV or CN-PPV mers based on the bis(1-cyano-2-thienylvinylene)phenylene
5878 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 6. Synthesis of TPA-Containing P19 and Chemical Structure of P20

Scheme 7. Synthesis of CN-PPV Copolymer P21 via a Knoevenagel Polycondensation

Chart 10. Chemical Structures of P22 and P23 responding repeating unit monomer. The optical band gaps
were determined to be 1.77, 1.72, 1.59, and 1.72 eV for P24,
P25, P26, and P27, respectively. The decreasing trend in
the band gap observed in P24-P26 is attributed to the
increasingly raised HOMO level due to the enhancement of
the electron-donating effect from octyl to ethylenedioxy
groups on the thiophene units. Moreover, such substitution
effects have little influence on the LUMO level, which is
mainly dominated by the presence of the cyanovinylene
linkages. However, with additional bulky tetradecyl groups
Chart 11. Chemical Structures of P24-P27 Synthesized by attached at the ethylenedioxy group, steric effects come into
Oxidative Polymerization of 31-34 play. P27 exhibited a higher band gap of 1.72 eV. This can
be rationalized by the decrease in π stacking interactions in
the solid state as a result of the steric hindrance. The electron-
rich nature of thiophene units in these polymers makes them
good candidates to serve as electron donors in BHJ devices.
Both P25/PCBM- and P26/PCBM-based photovoltaic de-
vices achieved a PCE of around 0.14%. Optimization of the
P26/PCBM device by thermal annealing showed a slight
increase of PCE to 0.19%. The unsatisfactory results are
related to the low hole mobility observed in the pure polymer
films.
In a very similar manner, Reynold et al. also reported
synthesizing a range of CN-PPV derivatives (P28-P31)
structure with different alkyl or alkoxy side chains on the containing dioxythiophene moieties in the main chain (Chart
thiophene rings (Chart 11).123 The monomers were all 12).124,125 These donor-acceptor conjugated polymers pos-
prepared by Knoevenagel condensations to construct cy- sess narrow band gaps of about 1.5-1.8 eV and good
anovinylene linkages (Scheme 8). Each polymer was directly solubilities in common organic solvents. The best photovol-
synthesized by FeCl3 oxidative polymerization of the cor- taic device based on P29/PCBM (1:4, w/w) showed a PCE
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5879

Scheme 8. Synthesis of Monomers 31-34 via Knoevenagel Condensations

Chart 12. Chemical Structures of P28-P31 phosphonate) 36 monomers in the presence of t-BuOK as
the base.126 Having coplanar electron-rich anthracene units
and triple bond bridges, P32 exhibits broader absorption, a
lower HOMO level, and a smaller optical band gap of 1.9
eV, compared to MDMO-PPV. A device with the configu-
ration of ITO/PEDOT/P32:PCBM (1:2, w/w)/LiF/Al, yielded
a PCE value of up to 2% with a high Voc of 0.81 V. Chart
13 shows the chemical structures of a series of acetylene-
containing PPV derivatives synthesized by similar proce-
dures. For polymers P35 and P36,127 the introduction of a
thiophene ring into the polymer backbone showed an
improvement in the PCE ranging from 1.2% to 1.7%. This
is higher than those for P33 and P34,128 based on the same
device configuration of ITO/PEDOT/polymer:PCBM (1:3,
wt %)/LiF/Al.

Scheme 9. Synthesis of Acetylene-Containing P32 via a

4. Fluorene-Based Conjugated Polymers
Wittig-Horner Reaction Fluorene-containing molecules represent an important class
of aromatic systems that have received considerable attention
due to their unique photophysical properties and potential
for chemical modification. Fluorene and its derivatives are
rigid, planar molecules that are usually associated with
relatively large band gaps and low HOMO energy levels,
rendering them highly stable toward photodegradation and
thermal oxidation during device operation. Easy dialkylation
at the 9-position and selective bromination at the 2,7-
positions of fluorene allow versatile molecular manipulation
to enhance solubility and extend conjugation easily by means
of a transition-metal cross-coupling reaction. Due to their
high fluorescence quantum yield, excellent hole-transporting
properties, good film-forming properties, and exceptional
chemical stability, polyfluorene-based (PF) conjugated poly-
mers have been extensively studied and utilized specifically
of 0.2%, which is very consistent with the results reported in the field of light-emitting diodes.129,130 It is envisioned
by Vanderzande et al.123 that the fluorene unit can emerge as a highly promising
building block for the design of new p-type materials for
3.4. Acetylene-Containing Poly(p-phenylenevinylene)s photovoltaic applications. This is due to the fact that the low-
lying HOMO levels and high hole mobility character of
A number of PPV derivatives containing alternating fluorene derivatives are expected to achieve higher open-
arylene-ethynylene units were synthesized to evaluate their circuit voltages and short-circuit currents, respectively.
photovoltaic properties. The coplanar and rigid nature of the However, the optical band gap of poly(9,9-dialkylfluorene)
acetylene moiety in the polymer chain may have the potential is ca. 3.0 eV, which is too high for efficient sunlight
to obtain a higher degree of packing and thus improve the harvesting where the maximum photon flux is around 1.7
photovoltaic performance of such devices. Scheme 9 shows eV. This problem can be solved by incorporating an electron-
the synthesis of the polymer P32 via the Horner-Emmons accepting unit into the main polyfluorene chain to form a
reaction of the dialdehyde 35 and p-xylylenebis(diethyl donor-acceptor alternating arrangement and hence narrow-
5880 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Chart 13. Chemical Structures of Acetylene-Containing PPV Derivatives P33-P36

Scheme 10. General Suzuki Coupling Reaction for the Synthesis of PF Copolymers

Chart 14. Chemical Structure of Bithiophene-Containing Chart 15. Chemical Structure of Thieno[3,2-b]thiophene-
PF Copolymer P37 Containing PF Copolymer P38

ing the band gap of the resulting copolymers for optimal

sunlight collection.
To prepare PF-based copolymers, Suzuki coupling reac- of P37 and well-defined nanophase segregation morphology.
tions are the most widely utilized. As far as the synthetic This makes it a promising high-energy-absorbing polymer
feasibility and reactivity are concerned, the 2,7-positions of for use in tandem bulk heterojunction solar cells.
the 9,9-dialkylfluorene unit are always functionalized with Chart 15 depicts the chemical structure of alternating
two boronic esters, whereas the dibromo functionality is copolymers containing 9,9-dihexylfluorene and unsubstituted
placed at another coupling aromatic unit. In a typical Suzuki or alkylated thieno[3,2-b]thiophene units via Suzuki coupling.
coupling reaction, a palladium complex such as Pd(PPh3)4 Compared with bithiophene-based P37 (454 nm), P38a
is used as the catalyst to carry out the polymerization in the shows a blue-shifted absorption maximum at 430 nm in
presence of K2CO3 and a phase-transfer catalyst, Aliquat 336, chloroform due to its shorter effective conjugation length.
in a solvent mixture (toluene/degassed water). During the When a pentyl group is introduced into the β-position of
polymerization process, the fluorenylboronic ester and the thieno[3,2-b]thiophene in P38b, the absorption maximum is
aromatic dibromide react with each other to give well-defined further blue-shifted to 388 nm as a result of steric-hindrance-
alternating PF copolymers. The molecular weights of the PF induced main chain distortion. Photovoltaic cells with the
derivatives obtained are moderate (Mn ) 10000-50000) with configuration of ITO/PEDOT/P38:PCBM (1:1, w/w)/Ca/Ag
low PDI values. A general Suzuki coupling reaction is shown were fabricated and characterized. The incident photon to
in Scheme 10. current conversion efficiency (IPCE) value was found to be
low, around 2%, leading to a limited PCE value, which might
4.1. Fluorene-Based Copolymers Containing be due to the poor device fill factor and narrow absorption
Electron-Rich Moieties range of the polymers.132
Linearly fused arene- and heteroarene-based organic
A conjugated polymer (P37) consisting of alternating semiconductors have been intensively investigated for OFET
fluorene and electron-rich bithiophene units was synthesized and OLED applications.133 Due to the extended and planar
by Suzuki coupling and is shown in Chart 14.131 The HOMO π-conjugated system, pentacene and its derivatives not only
and LUMO levels of P37 were estimated to be -5.41 and possess relatively low band gaps of 1.7 eV but also have
-2.52 eV, respectively. Through extended conjugation achieved high thin-film transistor mobility. In terms of high
between the fluorene and thiophene units, the optical band charge mobility and an intrinsic low band gap, it is of great
gap of P37 is reduced to 2.41 eV. Despite the fact that the interest that incorporation of a pentacene unit into a
P37:PCBM (1:4, w/w) blend film only absorbs light between conjugated polymer will generate a new class of promising
300 and 500 nm, a high Voc of 1.03 V and a moderate PCE p-type materials for photovoltaic applications.134 In addition
value of 2.7% were obtained due to the high hole mobility to pentacene, anthradithiophene, with two thiophenes on each
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5881

Scheme 11. Synthesis of Pentacene- and Anthradithiophene-Containing PF Copolymers P39 and P40

end of anthracene, is more stable than pentacene and can PCBM:P41 (1.0:0.6:1.4, wt %) showed a higher PCE value
form a more coplanar structure with other conjugated units.135 of 1.94% than that of the binary blend P3HT:PCBM (1:2,
Two alternating high molecular weight polyfluorene-based wt %) solar cell having the same donor-acceptor composi-
polymers containing pentacene (P39) or anthradithiophene tion due to the additional light-harvesting effect of P41.
(P40) units were successfully synthesized by Suzuki coupling The charge-carrier-transporting properties of P41 can be
(Scheme 11).136 The synthetic routes to (triisopropylsilyl)- further modulated by copolymerizing fluorene with the 4,7-
ethynyl-substituted pentacene and anthradithiophene have bis(3-hexylthiopen-5-yl)-2,1,3-benzothiadiazole unit to yield
been previously reported.134,137 P39 and P40 show more red- the polymer P42.144 With two additional electron-rich
shifted absorption spectra than their corresponding monomers thiophene rings attached to both sides of the benzothiadiazole
37 and 38 and have optical band gaps of 1.78 and 1.98 eV, unit, the hole mobility of P42 is expected to be improved
respectively. Bulk heterojunction solar cells were fabricated compared to that of P41. Therefore, P42 shows an ambipolar
using polymer P40:PCBM (1:3, w/w) as the active layer, nature and is capable of functioning as an efficient electron
giving a Jsc of 2.35 mA/cm2, a Voc of 0.75 V, and a PCE acceptor in blends with donor P3HT as well as an efficient
value of 0.68%. However, the device performance based on electron donor in blends with acceptor PCBM. A polymer/
polymer P39 was poor. A relatively low absorption coef- polymer blend device based on P3HT:P42 showed an
ficient at longer wavelengths may account for the poor enhanced PCE value from 0.14% to 1.2% after thermal
performance. annealing.
On the other hand, P43, which is structurally analogous
4.2. Fluorene-Based Copolymers Containing to P42, serves as a promising electron donor in a photovoltaic
Electron-Deficient Moieties device in combination with PCBM as the electron acceptor
Electron-deficient 2,1,3-benzothiadiazole units have been due to its higher hole mobility. The device with the
widely incorporated into PF-based copolymers to alter the configuration ITO/PEDOT/P43:PCBM (1:4, w/w)/LiF/Al
energy levels and fine-tune the emitting color over the entire showed a Jsc of 4.66 mA/cm2, a Voc of 1.04 V, an FF of
visible region.138 Chart 16 shows a series of 2,1,3-benzothia- 46%, and a PCE value of 2.2%.145 The result is superior over
diazole-containing PF derivatives (P41-P49) synthesized via the MDMO-PPV-based photovoltaic device due to P43’s ca.
Suzuki coupling reactions. 50 nm red-shifted spectral coverage and much greater Voc
In spite of the high hole mobility and weak electron- value. The polymer P44 contains 9,9-dioctylfluorene (DOF)
transport nature of polyfluorene, alternating poly(9,9-dio- and 4,7-di-2-thienyl-2,1,3-benzothiadiazole (DTBT) with
ctylfluorene-co-benzothiadiazole) (P41) exhibits a reduced different feeding ratios.146 Two obvious absorption bands
LUMO level and thereby enhanced electron mobility (10-3 with maxima at 383 and 540 nm were observed. The shorter
cm2/(V s)). This is a result of the high content of electron- wavelength absorbance comes from the higher energy of the
deficient benzothiadiazole units and results in it being fluorene unit, whereas the lower energy band is attributed
categorized as an electron-transport material.139 When com- to intramolecular charge transfer from the electron-rich unit
bined with the triarylamine-based polyfluorene P50 (Chart to the benzothiadiazole segment so that its intensity increases
17) as the electron donor with a high hole mobility of 10-4 with increasing DTBT content. When the ratio of DOF to
cm2/(V s), P41 serves as an electron acceptor in polymer/ DTBT was 65:35 in P44, the best photovoltaic performance
polymer bulk heterojunction photovoltaic devices.140-142 They based on P44:PCBM (1:2, w/w) was obtained, showing a
were fabricated by depositing the polymer blend P41/P50 Jsc of 5.18 mA/cm2, a Voc of 0.95 V, and a PCE value of
(1:1, w/w) as the active layer between ITO and Al electrodes, 2.24%. As shown in Scheme 12, P44 with a comonomer
resulting in a low external quantum efficiency (EQE) value ratio of 65:35 was synthesized by a Suzuki copolymerization
of 4% at an excitation energy of 3.2 eV.140 The electron of 40-42.147
acceptor P41 can also be added into a binary P3HT/PCBM By mixing chloroform/chlorobenzene as the cosolvent, a
system to act as the third component.143 The photovoltaic finer and more uniform domain of the P45a:PCBM (1:3,
performance of the ternary blend solar cell based on P3HT: w/w) thin layer was formed. The resulting photovoltaic
5882 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Chart 16. Chemical Structures of 2,1,3-Benzothiadiazole-Containing PF Copolymers P41-P49

Chart 17. Chemical Structures of Triarylamine-Based PF P50 It has been shown that selenium-containing heterocycles
such as selenophene and benzoselenadiazole have stronger
abilities to lower the band gaps of conjugated polymers than
their sulfur analogues thiophene and benzothiadiazole.153
Diselenophene-ylbenzothiadiazole and diselenophene-ylben-
zoselenadiazole units have both been incorporated into the
polyfluorene main chain to furnish P48 and P49, respec-
tively.154 The optical band gaps deduced from the onset
absorption are about 1.85 eV for P48 and 1.77 eV for P49.
device had a Jsc of 6.3 mA/cm2, a Voc of 1.01 V, an FF of
Both of them have a relatively low-lying HOMO level of
44%, and a high-energy conversion record of 2.84%.148 Apart
-5.5 eV. The best photovoltaic performance for a device
from PCBM, CdSe nanoparticles were also used as the
electron acceptor. A photovoltaic device based on P45a:CdSe based on P49/PCBM (1:4, w/w) reached a Jsc of 2.53 mA/
showed a spectral response extending to 650 nm and gave a cm2 and a very high Voc of 1.0 V and PCE of 1%. However,
PCE value of 2.4%.149 Furthermore, when the dioctyl chains a device based on P48/PCBM (1:4, w/w) showed only 0.1%
in P45a were replaced by didecyl chains in the fluorene unit under the same conditions. This result can be attributed to
of P45b, a device based on P45b/PCBM showing the highest the fact that P49 has a weaker CT absorption band in the
PCE value of 4.2% with a Voc of 0.99 V, a Jsc of 7.7 mA/ longer wavelength than P48. The syntheses of P48 and P49
cm2, and an FF of 0.54 was reported.150 are similar to that of P44.
The long alkoxy group can be introduced to the β-positon Donor-acceptor polyfluorene-based polymers containing
of the thiophene unit in the polymer P46 to strengthen its dithiophene-ylbenzothiadiazole units have shown larger Voc
electron-donating ability.151 P46 exhibited a significantly red- values (about 0.8-1.0 V) than P3HT (0.6-0.7 V) and
shifted absorption maximum of 581 nm and smaller band broader absorption coverage (300-650 nm) than MDMO-
gap of 1.78 eV relative to its alkyl counterpart P47152 with PPV derivatives (425-575 nm), achieving moderate to good
525 nm and 2.06 eV due to the stronger donating strength power conversion efficiency in the average range of 2-3%
of thiophene and thus more efficient intramolecular charge in BHJ devices. In terms of chemical feasibility and
transfer. The solar cell based on a P46/PCBM (1:4, w/w) tunability, considerable effort has been directed to the design
blend reached a Jsc of 4.31 mA/cm2, a Voc of 0.76, an FF of and synthesis of new polyfluorene-based polymers integrating
0.48, and a PCE of 1.6%. The efficiency can be further a series of alternative electron-accepting aromatic units.
improved to 2.4% by using PC71BM as the acceptor to Scheme 13 shows the synthesis of alternating PF derivatives
strengthen the light-harvesting ability.23 containing electron-accepting thieno[3,4-b]pyrazine units.
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5883

Scheme 12. Synthesis of Copolymer P44

Scheme 13. Synthesis of Thieno[3,4-b]pyrazine-Containing PF Copolymer P51

Scheme 14. Synthesis of Alkoxylated Thieno[3,4-b]pyrazine-Containing PF Copolymer P52

Imine formation of the diamino 43 with the 1,2-diketone 44 obtained through a series of steps: bromination of the
led to the cyclization product 45 containing the thieno[3,4- thiophene ring in 47 and reduction of the nitro groups in 48
b]pyrazine unit. N-Bromosuccimide (NBS) bromination of followed by imine formation of 49 with 1,2-diketone 50,
45 yielded the monomer 46, which was allowed to polymer- finally leading to P52 through a Suzuki coupling (Scheme
ize with 40 to give P51.155,156 The HOMO and LUMO levels 14).157 Photovoltaic devices with the configuration ITO/
of P51 were estimated to be -5.6 and -3.6 eV, respectively, PEDOT/P52:PCBM (1:3, w/w)/LiF/Al were fabricated,
determining an electrochemical band gap of 2.0 eV. The showing a Jsc of 8.88 mA/cm2, a Voc of 0.59 V, an FF of
absorption spectrum of P51 covers a broad range from 300 42%, and a highest PCE value of 2.2%. Compared to
to 850 nm. A device with the configuration of ITO/PEDOT/ polymer P51, the introduction of two alkoxy side chains into
P51:PCBM (1:6, w/w)/LiF/Al was fabricated to measure its P52 not only increased the solubility to produce a higher
photovoltaic performance. When the ratio of P51 to PCBM molecular weight (Mn ) 40000) but also shifted the HOMO/
was increased to 1:6, the resulting device showed a photo- LUMO energy levels to -5.0/-3.4 eV, respectively, with
current extended to 850 nm, achieved a Jsc of 3.0 mA/cm2 subsequent lowering of the electrochemical band gap to 1.6
and a Voc of 0.78 V, and had the highest PCE value of 0.96%. eV. The high molecular weight of P52 leads to a higher FET
The polymer P52 has a conjugated backbone similar to hole mobility of the P52/PCBM blend by 2 orders of
that of P51, with two additional (2-ethylhexyl)oxy substit- magnitude compared to that of P51/PCBM (8 × 10-4 vs 8
uents on the pendent phenyl rings of the thieno[3,4- × 10-6 cm2/(V s)). In addition, the higher LUMO also
b]pyrazine unit. The synthesis of the monomer 51 was facilitates the electron transfer from P52 to PCBM, which
5884 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 15. Synthesis of [1,2,5]Thiadiazolo[3,4-g]quinoxaline-Containing PF Copolymer P53

Chart 18. Chemical Structure of Fullerene Derivative (1:3, w/w)/LiF/Al showed a Jsc of 4.8 mA/cm2, a Voc of 0.82
BTPF V, and FF of 41%, and a PCE value of 1.7%. To intensify
P54’s absorption valley around 500 nm, PC71BM was used
to replace PCBM as the electron acceptor capable of
collecting photons in that region, resulting in 33% enhance-
ment of Jsc (6.5 mA/cm2) and thereby a higher PCE value
of 2.3%.

4.3. Fluorene-Based Copolymers Containing

Phosphorescent Complexes
Considering the limited diffusion length of singlet excitons
generated by the photoexcitation of donor materials, the bulk
is evidenced by complete PL quenching in the film of the heterojunction strategy dominates over a bilayer heterojunc-
P52/PCBM blend. The P52 absorption range covers 500-800 tion device because the exciton can travel a shorter distance
nm and absorbs more solar simulated light. The maximum to meet the electron acceptors before recombination occurs.
EQE value of about 40% at 650 nm for the P52 device also The diffusion length of an exciton is highly dependent on
helps explain its better photovoltaic performance compared
its mobility and lifetime. One of the most promising ways
to the P51 device (with a maximum EQE value of 15% at
to improve the efficiency of charge generation is to utilize
600 nm).
The polymer P53, which contains [1,2,5]thiadiazolo[3,4- triplet excitons which possess an inherently longer lifetime,
g]quinoxaline units in the main chain was synthesized by a which strengthens the diffusion ability of the exciton to reach
synthetic route similar to that of P51, as shown in Scheme the donor-acceptor interface. Holdcroft and co-workers
15.156 It was observed that no photoluminescence quenching reported a poly(fluorene-co-phenylpyridine)-based polymer
could be detected for the P53:PCBM blended film compared (P55) containing an iridium complex tethered to the main
with a film of pristine P53. This indicates that the strong chain.161 The polymer was synthesized using Suzuki coupling
electron-accepting ability of the thiadiazoloquinoxaline unit as shown in Scheme 17. The corresponding non-Ir polymer
leads to stronger electron affinity and a lower LUMO level P56 was also prepared for comparison (Scheme 18). Upon
in P53 and in turn prohibits favorable electron transfer from excitation, P56 only shows a fluorescence λmax at 422 nm,
P53 to PCBM. Indeed, the P53 LUMO level is determined whereas in P55 energy transfer takes place from the main
to be -4.0 eV, which is even lower than the -3.8 eV chain to the iridium complex. This produces a peak of
reported for PCBM. However, a partial photoluminescence phosphorescence at 596 nm with a triplet lifetime of 0.26
quenching was observed on mixing P53 with another C60 µs. The phosphorescence can be completely quenched by
derivative (BTPF)158 which has a lower LUMO level at ca. blending with PCBM, which is indicative of efficient electron
-4.1 eV that can facilitate electron transfer (Chart 18). A
transfer from the triplet exiciton of the polymer to PCBM.
device with the configuration ITO/PEDOT/P53:BTPF (1:4,
Both polymers, blended with PCBM (1:4, w/w), were made
w/w)/LiF/Al was fabricated and evaluated. It showed an onset
photocurrent at 1000 nm and a maximum EQE value of 9.7% into photovoltaic devices. P55 showed a 10 times higher
at 840 nm with a Jsc of 2.1 mA/cm2 and a Voc of 0.5 V.159 maximum EQE at 350 nm than its non-Ir counterpart (10.3%
Polymer P54, the acceptor part of which consists of the vs 1.1%), as well as a higher PCE of 0.07% compared to
pyrazino[2,3-g]quinoxaline unit, was also prepared by a 0.002%. This clearly demonstrates the benefits of the longer
similar procedure, as shown in Scheme 16.160 The HOMO triplet exciton diffusion length. It is expected that the device
and LUMO levels were estimated to be -5.7 and -3.9 eV, performance can be further improved by choosing a polymer
respectively, with an electrochemical band gap of 1.8 eV. having a lower band gap main chain to harvest more solar
A device with the configuration ITO/PEDOT/P54:PCBM energy.
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5885

Scheme 16. Synthesis of Pyrazino[2,3-g]quinoxaline-Containing PF Copolymer P54

Scheme 17. Synthesis of PF Copolymer P55 with a Pendent Ir Complex

Scheme 18. Synthesis of PF Copolymer P56 without a Pendent Ir Complex

5. Carbazole-Based Conjugated Polymers and electron-blocking material.163 In addition, it serves as a

large band gap host in polymer light-emitting devices.164
Carbazole, also known as 9-azafluorene, is one of the most
Alternatively, conjugated poly(carbazole) derivatives have
attractive heterocyclic units for electronic applications in the
been successfully applied in organic field-effect transistors.165
field of conjugated polymers. Despite being structurally
analogous to fluorene, the central fused pyrrole ring, with These properties make the carbazole unit a promising
its donating nitrogen, makes tricyclic carbazole fully aromatic candidate for incorporation into low band gap polymers for
and electron-rich. The replacement of carbon by nitrogen in solar cell applications.166
the fluorene skeleton avoids the susceptibility to oxidation
of the 9-position toward ketone formation leading to 5.1. Poly(2,7-carbazole)-Based Polymers
undesired electronic and optical properties. The availability
of nitrogen in carbazole to functionalization with an alkyl In general, the carbazole unit can be connected and
chain also ensures sufficient solubility. As a result, carbazole extended in a symmetrical manner through either the 3,6-
derivatives have been widely used as p-type semiconductors positions or 2,7-positions to yield linear conjugated polymers.
due to their ability to form stable radical cations, as well as Connecting carbazole via the 3,6-positions results in a meta-
their excellent thermal and photochemical stabilities, rela- linkage of phenylene with limited conjugation. On the other
tively high charge mobility, and easy availability. For hand, the 2,7-positions lead to a para-linkage and a higher
example, poly(N-vinylcarbazole) (PVK), a nonconjugated effective conjugation length.167 It appears that 2,7-linked
linear polymer with pendent carbazole units, acts not only carbazole-based conjugated polymers for use as donor
as a superb photoconductor162 but also as a hole-transporting materials in photovoltaic devices are much more promising
5886 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 19. Synthesis of Poly(3,6-carbazole) P57

Scheme 20. Synthesis of 2,7-Dibromocarbazole (68)

Scheme 21. Synthesis of Alkylated Poly(2,7-carbazole) Homopolymer P58 and Chemical Structure of Perylene Diimide 71

in terms of better charge migration along the more conjugated Scheme 22. Synthesis of Poly(2,7-carbazole) P59 Containing
main chain. As shown in Scheme 19, bromination of 2,1,3-Benzothiadiazole Units
carbazole 63 by NBS takes place regioselectively and
quantitatively at the 3,6-positions, which are para to the
directing nitrogen, to obtain 64. After N-alkylation with an
alkyl halide under basic conditions, poly(3,6-carbazole) P57
with a high molecular weight can be synthesized using a
Yamamoto coupling.168
In contrast, the preparation of 2,7-dibromocarbazole is not
that straightforward.169 However, Mullen et al. developed a
facile route to its synthesis in two steps (Scheme 20).170
Nitration of 4,4′-dibromobiphenyl (66) by nitric acid gave
67. A Cadogan reductive cyclization of 67 using triethyl
phosphate afforded 2,7-dibromocarbazole (68).171
Due to their poor solubilities, poly(2,7-carbazole) ho-
mopolymers generally have low molecular weights, which
limits their use in thin-film devices. P58, a soluble and
processable poly(2,7-carbazole) with a branched 2-de-
cyltetradecyl substituent on the nitrogen, was designed and DTBT moieties, was synthesized by Leclerc and co-
and synthesized by a Ni(COD)2-mediated Yamamoto workers. Scheme 22 shows the synthesis of P59 via a Suzuki
coupling polymerization (Scheme 21).172 The resultant coupling reaction.173 P59 has an optical band gap of 1.88
polymer has a lower HOMO level, -5.6 versus -5.2 eV, eV from its absorption edge. The HOMO and LUMO levels
than P3HT. This implies a better environmental stability were estimated to be -5.5 and -3.6 eV, respectively. The
toward air oxidation and the ability to obtain a higher Voc. photovoltaic device based on P59:PCBM (1:4, w/w) showed
In spite of the relatively large band gap of 3.0 eV along with a Jsc of 6.92 mA/cm2, a Voc of 0.89 V, an FF of 63%, and a
limited absorption, P58 can be blended with the electron PCE value of 3.6%. The result makes poly(2,7-carbazole)
acceptor perylene diimide 71, which has a low band gap of derivatives among the best conjugated polymers reported to
2.0 eV, to form a bulk heterojunction solar cell. A simple date.
device with the configuration ITO/P58:71 (1:4, w/w)/Ag was Leclerc and co-workers further reported a series of
fabricated to evaluate its photovoltaic performance, showing poly(2,7-carbazole) derivatives (P60-P64) using different
a Jsc of 0.26 mA/cm2, a Voc of 0.71 V, an FF of 37%, and a electron-deficient moieties (Chart 19).174 P60, P62, and P59
PCE value of 0.63%. have three different symmetric electron-withdrawing units,
The band gap of poly(2,7-carbazole) can be reduced by respectively, with benzene as the core. The corresponding
incorporating an electron-accepting unit to generate a new compounds P61, P63, and P64 all have asymmetric electron-
class of D-A poly(2,7-carbazole)-based polymers. The withdrawing units with pyridine as the core. These copoly-
copolymer P59, comprised of alternating 2,7-carbazole units mers were all synthesized via a Suzuki coupling reaction in
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5887

Chart 19. Chemical Structures of Alternating Poly(2,7-carbazole) Copolymers P60-P64

Scheme 23. Synthesis of Poly(2,7-carbazolenevinylene) Derivative P65

a manner similar to that of polymer P59. Cyclic voltammetric high molecular weights, an all-trans double bond configu-
analysis shows that the HOMO levels of these polymers, ration, and low contamination, the Horner-Emmons reaction
ranging from -5.55 to -5.46 eV, are mainly determined by was employed to synthesize the polymers P65-P68 by
the carbazole unit. However, the LUMO level is dependent reacting the dialdehyde and corresponding diphosphonate
on the nature of the electron-withdrawing unit. Compared derivatives in the presence of excess amounts of t-BuOK in
to benzene-based acceptors, the corresponding pyridine-based anhydrous THF. However, polymer P69 was prepared by
ones are more electron-withdrawing, resulting in lower the Stille cross-coupling reaction of the dibromo monomer
LUMO levels by ca. 0.25 eV. It was found by X-ray analysis 86 and distannyl compound 87 in the presence of Pd2(dba)3
that polymers with symmetric benzene-based acceptors have and AsPh3 in THF. The polymers P65-P69 have optical
better structural organization in the solid state than those with band gaps of 2.3, 2.2, 2.1, 2.0, and 1.7 eV, respectively,
asymmetric acceptors. This greatly affects their photovoltaic indicating that the band gap of this polymer series decreases
performance. On the basis of the polymer/PCBM (1:4, w/w)
as the number of thiophene rings increases. The HOMO
blend in the device, P60, P62, and P59 all show higher PCE
energy level is also proportionally lowered with increasing
values, 1.8%, 2.4%, and 3.6%, respectively, than their
corresponding counterparts P61, P63, and P64, 1.1%, 0.8%, conjugation length of the backbone with the exception of
and 0.7%. It should be noted that these poly(carbazole)-based polymer P69. It should be noted that the thienyl S,S-dioxide
polymers generally deliver a higher Voc of ca. 0.8-1.0 V. unit in P69 is no longer aromatic and has two localized CdC
Schemes 23 and 24 show the synthetic routes to a series and two SdO double bonds,176 which results in greater
of poly(2,7-carbazolenevinylene) (PCV) polymers using electron affinity and a significantly lower LUMO level. Bulk
different polymerization methods.175 P65 is a PCV ho- heterojunction photovoltaic cells having the sandwiched
mopolymer with an (octyloxy)benzyl side group on the structure ITO/PEDOT/polymer:PCBM (1:4, w/w)/Al were
nitrogen of the carbazole unit. The polymers P66-P68, on fabricated. Among them, P69 showed the best photovoltaic
the other hand, are PCV copolymers incorporating different performance: a Jsc of 1.56 mA/cm2, a Voc of 0.8 V, an FF of
lengths of oligothiophenes into the main chain. To obtain 54.6%, and a PCE value of 0.8%. The other four polymers
5888 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 24. Synthesis of 2,7-Carbazolenevinylene-Based Copolymers P66-P69

showed PCE values ranging from 0.2% to 0.4% following donating indolocarbazole unit, has been synthesized by the
the same fabrication and characterization protocol. Suzuki coupling of 88 and 89 (Scheme 25).179 Both long
and branched aliphatic chains must be introduced onto the
5.2. Indolo[3,2-b]carbazole-Based Polymers nitrogen atom to ensure sufficient solubility of the polymer.
The indolocarbazole polymerization site is at the 3,9-
Indolo[3,2-b]carbazole can be regarded as two carbazoles positions so that the fully conjugated main chain of the
fused together. It is envisaged that indolo[3,2-b]carbazole-
polymer can be obtained. A strong peak located at 538 nm
based materials will have stronger donating abilities than
in the absorption spectrum in chloroform is due to the
carbazole while inheriting the advantages of carbazole such
as hole-transporting properties and enhanced photostability intramolecular charge-transfer transition. Compared to the
and thermal stability. For the indolo[3,2-b]carbazole-based solution state, the absorption edge in the solid state is
small molecule and homopolymer a very high mobility in significantly red-shifted by 100 nm, indicating very strong
FET has been achieved.177,178 There are many intrinsic interchain packing induced by planarization of the aryl rings.
advantages making indolo[3,2-b]carbazole a promising elec- According to DSC measurements, P70 has a strong tendency
tron-rich building block for the construction of a new class to crystallize, as evidenced by an exothermic crystallization
of donor-acceptor conjugated polymers. First, the penta- peak at 209 °C without showing a glass transition. The
fused heterocyclic unit of indolocarbazole provides a large HOMO level remains low at 5.17 eV, which is crucial to
coplanar π-conjugated system. Second, the low-lying HOMO obtaining a high Voc and air stability. The device based on a
feature of indolocarbazole is expected to be beneficial for blend of P70/PCBM (1:2, w/w) in the active layer exhibited
obtaining a high Voc. The arylamine-type structure of a high Voc of 0.69, a Jsc of 9.17 mA/cm2, and a high PCE of
indolocarbazole is known to be a good hole transporter. As 3.6%. The preparation of the 3,9-indolo[3,2-b]carbazole unit
a result, the copolymer P70, composed of an electron- is shown in Scheme 26. Treatment of 1,4-cyclohexadione
accepting benzothiadiazole oligothiophene and an electron- (91) with (3-bromophenyl)hydrazine (90) formed the bishy-
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5889

Scheme 25. Synthesis of Indolocarbazole-Based P70 by Suzuki Coupling

Scheme 26. Synthetic Route toward Monomer 88

drazone 92, which underwent a double Fischer indole ring now is para to the quinoxaline unit so that intramo-
cyclization and reduction under acidic conditions (H2SO4/ lecular charge transfer from the donating nitrogen to the
AcOH), resulting in the formation of 93.180 After N-alkylation acceptor unit may be facilitated and may contribute to the
of 93 to introduce an aliphatic chain, the dibromo functional- lower band gap. On the basis of a solar cell device with a
ity in 95 was then converted to diboronic ester to produce blend of polymer/PCBM (1:4, w/w), the PCE of P74 reached
the final monomer 88. 0.87% and can be further improved to 1.4% when using
Chen and co-workers also reported four alternating D-A PC71BM as the acceptor, outperforming the P72/PCBM-
copolymers (P71-P74) combining either 3,9-indolo[3,2- based device with a PCE of 0.32%.
b]carbazole or 2,8-indolo[3,2-b]carbazole as the donor unit
and 2,3-didodecylthienopyrazine or 2,3-bis(4-((2-ethylhexyl)- 6. Thiophene-Based Conjugated Polymers
oxy)phenyl)quinoxaline as the accepting unit.181 The syn-
thesis of P71-P74 is shown in Scheme 27. The absorption 6.1. Poly(3-alkylthiophene) and Its Derivatives
maxima of P71 are more red-shifted than those of P73 both
in solution (552 vs 544 nm) and in the solid state (582 vs Polythiophene represents the most important conjugated
557 nm), resulting in a lower optical band gap (1.79 vs 1.89 polymer utilized in a broad spectrum of applications such
eV). These results can be rationalized by the fact that the as conducting polymers, light-emitting diodes, field-effect
3,9-linkage of indolocarbazole can form a fully p-phenylene transistors, and plastic solar cells due to its excellent optical
conjugated main chain, whereas the 2,8-linkage generates a and electrical properties as well as exceptional thermal and
less conjugated m-phenylene relationship between indolo- chemical stability. Early synthesis of poly(3-alkylthiophene)
carbazole and thienopyrazine. Moreover, compared to P73, involved chemical oxidation or electrochemical polymeri-
P71 has a lower HOMO level, implying that the 3,9-based zation in the pursuit of soluble and processable polythio-
copolymers have better air stability than the corresponding phenes.60,182,183 However, these processes suffered from the
2,8-based copolymers. The P71/PCBM-based solar cell gross defect that the structure of the polymer is somewhat
device exhibited a better PCE of 0.66% than the P73/PCBM undirected and undefined.184 Because 3-alkylthiophene is an
one with a PCE of 0.22%. On the other hand, however, P72 asymmetrical molecule, there are three relative orientations
shows a slight blue shift of its λmax and a larger band gap available when the two thiophene rings are coupled between
than that of P74. This is just the trend opposite that observed the 2- and 5-positions. The first of these is the 2-5′ or head-
in the P71 and P73 pair. This might be attributed to the fact to-tail coupling (HT), the second is 2-2′ or head-to-head
that the quinoxaline unit causes a larger steric effect in the coupling (HH), and the third is 5-5′ or tail-to-tail coupling
3,9-linkage than in the 2,8-linkage. It is also worthy to note (TT). Containing a mixture of the possible couplings
that, in the 2,8-linkage, the nitrogen atom on the benzene mentioned above results in a regioirregular poly(3-alkyl-
5890 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 27. Synthesis of P71-P74 by Suzuki Coupling from Corresponding Monomers 96-99

Scheme 28. Synthesis of Regioregular Poly(3-alkylthiophene) Scheme 29. Synthesis of Regioregular Poly(3-alkylthiophene)
P75 by the McCullough Route P76 by the Rieke Route

thiophene) in which a large number of thiophene rings Later on, McCullough reported another method for the
twisted out of conjugation in a manner of HH coupling due synthesis of regioregular poly(3-alkylthiophene)s by Grignard
to steric repulsion between alkyl chains. Overall this reduces metathesis (GRIM).189,190 Treatment of 2,5-dibromo-3-hexy-
the electrical conductivity of the polymer. On the other hand, lthiophene (104) with a variety of alkyl Grignard reagents
coupling each thiophene unit in a consecutive head-to-tail resulted in two metalated regioisomers (105 and 106) in an
manner during the polymerization affords a regioregular 85:15 ratio via a magnesium exchange reaction (Scheme 30).
poly(3-alkylthiophene) which is capable of adopting a This ratio appears to be independent of the reaction time,
coplanar conformation, resulting in a lower energy. This temperature, and Grignard reagent employed. Introduction
arrangement produces a highly conjugated polymer having of a catalytic amount of Ni(dppp)Cl2 to this isomeric mixture
a lower band gap. afforded poly(3-hexylthiophene) (P77), which contained
The first synthesis of regioregular head-to-tail coupled greater than 95% regioregularity.
poly(3-alkylthiophene)s (P3ATs) was reported by Mc- McCullough and Yokozawa independently demonstrated
Cullough early in 1992.185,186 As shown in Scheme 28, the that the Grignard metathesis polymerization of regioregular
regioregular polymerization of 3-alkylthiophene P75 can be 3-alkylthiophene proceeds by a living chain growth mech-
controlled by selective lithiation of 2-bromo-3-alkylthiophene anism instead of the traditionally accepted step growth
100 with lithium diisopropylamide (LDA) followed by polycondensation. As a result, low polydispersities (ca.
transmetalation using magnesium bromide to yield the 1.2-1.3) and well-defined molecular weights can be con-
organomagnesium intermediate 101. The use of a Ni(dppp)Cl2 trolled by the feed ratio of monomer to the Ni catalyst.191-194
catalyst for the polymerization of this intermediate gives the Their proposed mechanism is shown in Scheme 31. First,
corresponding poly(3-alkylthiophene) P75 with over 90% head- two Grignard nucleophilic additions to a nickel catalyst
to-tail regioselectivity. generate the intermediate 109. A reductive elimination
The second synthetic approach to HT-PAT was subse- involving carbon-carbon bond formation in 109 accompa-
quently developed by Rieke.187,188 Highly reactive zinc nied by Ni migration and insertion into the terminal C-Br
undergoes a selective oxidative addition to 2,5-dibromo-3- bond keeps the living chain capable of further reacting with
alkylthiophene 102 to yield 2-(bromozincio)-3-alkyl-5-bro- compound 107. Propagation via consecutive coupling be-
mothiophene intermediate 103 in quantitative yields. In the tween the polymer with a Ni complex at the chain end and
presence of Ni(dppe)Cl2 as the catalyst this metalated compound 107 elongates the conjugated backbone. Because
intermediate undergoes regioselective polymerization to yield this reaction can be accomplished both at room temperature
the desired HT-PAT P76 product (Scheme 29). and on a large scale, the Grignard metathesis/Kumada-Corriu
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5891

Scheme 30. Synthesis of Regioregular Poly(3-hexylthiophene) P77 by Grignard Metathesis and Kumada-Corriu Coupling

Scheme 31. Mechanism of Chain Growth Polymerization Proposed by Yokozawa et al

coupling has become the most widely used method for Scheme 32. Synthesis of P78 for Lowering the
producing poly(3-alkylthiophene)s with predetermined high Regioregularity by the Incorporation of a Dihexylthiophene
molecular weights. The beneficial features of GRIM are Repeat Unit
obtaining monodispersed samples of P3ATs without resorting
to time-consuming polymer fractionation techniques and
refining the properties of P3ATs by eliminating molecular
weight distribution variations. Moreover, it is possible to keep
the polydispersity constant when trying to determine if one
polymer performs better than another.
Increasing regioregularity in poly(3-hexylthiophene) (P3HT)
through these advanced metal-catalyzed reactions leads to retains the device efficiency but also enhances the thermal
various beneficial outcomes including a red shift in absorp- stability of morphology in the solar cells.205 Polythiophene
tion in the solid state with an intensified extinction coefficient P78 with a regioregularity lower than 91% was synthesized
and an increase in the mobility of the charge carriers.195 by the copolymerization of 2-bromo-3-hexylthiophene (111)
Regioregular poly(3-hexylthiophene) possesses HOMO and with a small amount of the 2-bromo-3,4-dihexylthiophene
LUMO levels at -5.2 and -3.2 eV, respectively, with an (110) unit using a modified McCullough route (Scheme 32).
optical band gap of ca. 2.0 eV. To date, a combination of After 30 min of annealing at 150 °C, the resulting devices,
poly(3-hexylthiophene) as the electron donor and PCBM as using 96% regioregular P3HT and PCBM or P78/PCBM,
the electron acceptor in the active layer represents the most showed PCEs of 4.3% and 4.4%, respectively. However, the
efficient bulk heterojunction solar cell with power conversion PCE of P3HT/PCBM further fell to 2.6% when the annealing
efficiency approaching 5%. The success of the P3HT/PCBM time was increased to 300 min, whereas the PCE of P78/
system is largely associated with careful control and opti- PCBM remained at 3.5% under identical conditions.
mization of the active layer morphology. It has been A later more straightforward study, on the influence of
demonstrated that device performance based on P3HT/PCBM the regioregularity of P3HT on polymer-fullerene solar cell
can be dramatically improved by judicious choice of the casting performance, was carried out by systematically comparing
solvent,196 by external treatment of solvent annealing197-199 three samples of P3HT having regioregularities of 86%, 90%,
and thermal annealing,200-202 or by forming P3HT nanofibers and 96%.206 It was found that in blends with PCBM all three
prior to deposition.203 Thermal annealing of the P3HT/PCBM polymers were able to achieve solar cells with PCEs of about
composite provides an external energy to drive reorganization 4% and exhibit the same order of magnitude of charge
of the polymer chains, which ultimately leads to a nanoscale mobility (10-4 cm2/(V s)). Most importantly, the P3HT with
phase separation with a bicontinuous interpenetrating D-A the lower regioregularity possessed superior thermal stability
network.204 As a result of this higher degree of nanoscale over those with higher regioregularities. This was ascribed
P3HT crystallinity, better charge transport and maximum to the suppression of the crystallization-driven phase separa-
interfacial area for efficient charge generation are obtained. tion through introduction of a controlled amount of disorder
However, prolonged thermal annealing causes regioregular into the polymer backbone. This result is consistent with
P3HT to further crystallize and thereby tends to destroy the previous observations. Another example illustrating the effect
optimal morphology as a result of continuous phase segrega- of alkyl substitution patterns in thiophene copolymers was
tion between P3HT and PCBM to form a macroscale domain presented by the comparison of polymers P79 and P80,
larger than the exciton diffusion length. Fréchet and co- which have identical compositions and similar molecular
workers found that a slight decrease of the regioregularity weights and polydispersities.207 Polymer P79, synthesized
of P3HT to weaken the crytallization formation not only by the Stille copolymerization of distannyl monomer 114
5892 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 33. Synthesis of P79 and P80

and dibromo monomer 115, has a perfect regioregular Scheme 34. Synthesis of P81 and P82
alternating arrangement, whereas P80 made by the Mc-
Cullough route has a random sequence distribution (Scheme
33). X-ray diffraction measurements of the polymers were
performed after spin-coating and thermal annealing at 100
°C for 30 min. Due to its longer alkyl chain interdigitation
and structurally well-defined nature, P79 crystallizes into a
three-dimensional highly ordered structure208 and exhibits an
even higher degree of crystallinity than P3HT, which is
known to have disordered noninterdigitated side chains.209 mic shift of the long-wavelength maxima and a prominent
On the contrary, P80 exhibits amorphous character as a result shoulder at 600 nm in the solid-state absorption spectrum.
of its random structure. The best device PCE of P80 blended This indicates the formation of a lamellar structure and
with PCBM (30:70, w/w) was 1.84%. However, the optimal interchain aggregates, whereas the lower molecular weight
PCE of P79 blended with PCBM (25:75, w/w) only reached with a shorter conjugation length results in reduced inter-
0.54%, which is much lower than that of P3HT. These results molecular interactions with a concomitant decrease in hole
indicate that increasing the crystallinity of the polymer to mobility.
be higher than that of P3HT turns out to have a detrimental The major function of the aliphatic chain substituent is to
effect, because a higher crystallinity makes P79 unable to provide adequate solubility of polythiophenes with weak
form bicontinuous donor-acceptor networks at all and the electronic interactions with the main chain. Nevertheless,
longer alkyl chains further lower the miscibility with PCBM. alkoxy chains introduced into the 3-position of poly-
Therefore, the random, amorphous polymer with the more thiophenes not only serve as solubilizing groups but also
favorable active layer morphology outperforms its more greatly perturb the molecular orbitals involved in tuning the
highly ordered analogues by more than 3-fold. These results band gap.215 Regioregular poly(3-(decyloxy)thiophene) (P81)
clearly demonstrate that highly crystalline conjugated poly- was synthesized by a GRIM synthesis of 2,5-dibromo-3-
mers are advantageous for achieving high mobility in field- (decyloxy)thiophene (120) (Scheme 34).151 Despite the fact
effect transistors because polymers constitute the only that the resultant polymer showed a lower band gap of 1.6
component. However, the addition of another component eV, due to electron-donating effects elevating the HOMO
such as fullerene into a BHJ solar cell renders the morphol- level, the resulting poor solubility and film-forming properties
ogy, a bulk property, more important than the polymer and air instability restricted its performance in solar cell
crystallinity. devices. Therefore, the high head-to-tail regioregular co-
The length of the solubilizing group in the conjugated polymer P82 was synthesized by reacting 120 with 2,5-
thiophene unit also plays an important role in determin- dibromo-3-octylthiophene (121) via the McCullough method.
ing the balance between crystallinity and miscibility in the Compared to that of P3HT, the absorption maximum of P82
bid to achieve optimal morphology. A systematic study of a in the solid state was dramatically red-shifted to 621 nm.
series of regioregular poly(3-alkylthiophene)s, with different The electrochemical band gap of P82 was determined to be
butyl, hexyl, octyl, decyl, and dodecyl side groups, has been 1.64 eV. However, P82/PCBM (1:1, w/w) also showed very
conducted.210 It was found that chain lengths longer than poor photovoltaic performance with a PCE of 0.054%.
eight carbons facilitate diffusion rates of PCBM in the
polymer matrix during the thermal annealing. This leads to
a larger scale of phase separation, reduced interfacial area,
6.2. Poly(3-hexylselenophene)
and thereby lower device performance. Poly(3-butylth- Poly(3-hexylselenophene) (P3HS, P83) is an analogue of
iophene) lacks suitable solubility in chloroform. Ultimately, poly(3-hexylthiophene) with selenium replacing the sulfur
the hexyl group in P3HT demonstrated an optimal balance atom. It can be synthesized successfully in a regioregular
with the best device performance in the poly(3-alkylth- manner by employing a McCullough-type Ni coupling
iophene) family. Moreover, the efficiency of the BHJ device reaction of 123 made by bromination of 122 (Scheme 35).216
also greatly depends on the molecular weight211-213 and It was found by Heeney and co-workers that poly(3-
polydispersity214 of the P3HT. It has been shown that only hexylselenophene) has a smaller band gap of 1.6 eV than
P3HT with a number-average molecular weight greater than P3HT through lowering the LUMO level without elevating
10000 can achieve a power conversion efficiency over the HOMO level. These are promising properties for obtain-
2.5%.211 High molecular weight P3HT exhibits a bathochro- ing profound absorption at lower energy while maintaining
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5893

Scheme 35. Synthetic Route to Poly(3-hexylselenophene) (P83) by Grignard Metathesis and Kumada-Corriu Coupling

Scheme 36. Synthesis of P84 by a Stille Coupling Reaction

Scheme 37. Synthesis of P85 by Grignard Metathesis

an open-circuit voltage comparable to that of P3HT. As a Wei and co-workers reported a new regioregular 3-hexy-
result, P3HS shows a much greater red-shifted absorption lthiophene copolymer (P85) incorporating (octylphenanthre-
maximum at 630 nm in the solid state compared to 550 nm nyl)imidazole moieties directly conjugated with 90% thiophene
for P3HT. It was also found that P3HS is more resistant to units at the 3-position.220 This polymer was synthesized by
photooxidation than P3HT. It has been suggested that one Grignard metathesis and a Ni-catalyzed reaction of 104 with
of the photooxidation mechanisms is through electron transfer 127 (Scheme 37). The electron-accepting ability of this
from excited P3HS to oxygen, generating a superoxide anion moiety induces efficient intramolecular charge transfer from
that reacts with the conjugated backbone. The low-lying the donor thiophene main chain to the conjugated acceptor
LUMO of P3HS can reduce the electron-transfer rate and side chain: this reduces the optical band gap slightly to 1.9
therefore accounts for the better photostability of P3HS. The eV. In addition, charge separation is also facilitated through
lower LUMO can be attributed to the smaller ionization sequential transfer of electrons from the main chains to the
potential of selenium. Moreover, P3HS displays crystalline side chains and then to PCBM. Consequently, the electron-
morphology and thus has an FET charge mobility similar to transfer probability from this polymer to PCBM is twice as
that of P3HT under the same measurement conditions. The high than that from pure P3HT. Using a blending of P85/
solar cell device based on P3HS/PCBM (1:1, w/w) produced PCBM (1:1, w/w) in a solar cell device gives a high PCE of
a PCE of 2.7% after optimal thermal annealing, which is 3.45%. The synthesis of monomer 127 is shown in Scheme
comparable to that of a P3HT/PCBM device.217 38. The 1,2-diketone compound 130 was synthesized by NBS
bromination of 128 to form 129, which was then oxidized
6.3. Polythiophenes with Conjugated Side Chains by CrO3 to give 130. The phenanthrenylimidazole core in
compound 131 was generated under acidic conditions
An alternative design strategy to intensify the absorption through a cyclization reaction of 130 with aniline, ammonium
ability of p-type polymers is to introduce additional absorp- acetate, and 3-formylthiophene. The nickel-catalyzed Kumada–
tive chromophores directly and conjugatively attached to the Corriu reaction of 131 afforded compound 132 with two
main chain backbone.218,219 Li et al. designed and synthesized, attached octyl side chains. Subsequent NBS bromination
by Stille coupling, a series of polythiophene derivatives P84 yielded the final monomer 127.
having conjugated bi(thienylenevinylene) side chains (Scheme Charge mobility of conjugated polymers plays a critical
36). It has been shown that extension of a conjugated side role in high-performance polymer solar cells. In addition to
chain to the polythiophene main chain leads to strong and intramolecular charge transport along the conjugated main
broad absorption covering both the UV and visible regions chains, it is known that intermolecular hopping between
from 350 to 650 nm. In addition, the P84 HOMO level is adjacent main chains is the limiting step in the charge-
lower by 0.2 eV than that of P3HT, resulting in a higher Voc transport process. Increased molecular weight or controlled
of the PSC. The solar cell device based on a blend of P84 regioregularity of conjugated polymers has been shown to
(m/n ) 0.59) as the donor and PCBM as the acceptor (1:1, induce higher hole mobility as a result of improved conjuga-
w/w) reached a PCE of 3.18%; this is superior to that of the tion and π-π stacking interactions. A series of poly-
device based on P3HT under the same conditions. thiophenes P86, cross-linked by different amounts of con-
5894 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 38. Synthetic Route toward Monomer 127

Scheme 39. Synthesis of P86 by a Stille Coupling Reaction

Scheme 40. Synthesis of P87 by Grignard Metathesis and a

jugated vinylene-terthiophene-vinylene (VTTV) bridges Kumada-Corriu Coupling Reaction
(2% P86a, 4% P86b, 8% P86c), were synthesized by Li and
co-workers via Stille coupling (Scheme 39).221 These bridges
connected and conjugated with the polythiophene main
chains might provide an avenue to facilitate efficient charge
transport from chain to chain in the network.222-224 The hole
mobilities of these polymers, determined according to the
space-charge-limited current model, are 4.7 × 10-3, 2.58 ×
10-3, and 9.48 × 10-4 cm2/(V s) for P86a, P86b, and P86c,
respectively. The value for P86a is about 3 times higher than
that of the corresponding non-bridge-conjugated polymer.
Notably, any further increase in the bridge content is dibromo-3-hexylthiophene with a small amount of a tet-
accompanied by more steric distortion in the main chain as rafunctional branching agent, 2,5,2′,5′-tetrabromo-3,3′-
evidenced by the declining hole mobility and blue-shifted bithiophene, under McCullough-type Grignard metathesis
absorption spectra. A PCE of 1.72% for the solar cell device conditions (Scheme 40).225 It has been shown that systemati-
based on a 1:1 (w/w) blend of P86a and PCBM can be cally increasing the branching unit from 2% through 4% to
obtained. 8% in the P3HT backbone leads to improved solubility, a
In a similar approach to improving the charge mobility blue-shifted absorption, and decreased hole mobility with
between conjugated polymers, Scherf et al. synthesized a concomitant reduced solar cell power conversion efficiency.
series of modified polythiophenes P87 by polymerizing 2,5- These phenomena can certainly be attributed to the lower
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5895

Scheme 41. Synthesis of PITN (P88) by Electrochemical Polymerization and Its Mesomeric Structure

Scheme 42. Synthesis of P89 by Thermal Polymerization of Scheme 43. Synthesis of P90-P92 by FeCl3 Oxidative
Dithiophthalide Polymerization

degree of solid-state ordering and packing caused by the

severe interchain distortion of the backbone due to branching
effects. The best PCE of 2% comes from a P87a /PCBM
(1:1, w/w) BHJ solar cell, showing a moderate reduction in
efficiency as compared to a P3HT-based device having a
PCE of 3.5% under identical conditions. These results are
also in good agreement with the fact that the degree of
regioregularity impacts the backbone conformation of poly(3-
alkylthiophene).

6.4. Isothianaphthene-Based Polymers

Polyisothianaphthene (PITN, P88) is a polythiophene
derivative where all the thiophene rings are fused to a
benzene ring at the 3,4-positions of thiophene. The first PITN
was reported by Wudl et al. in 1984 and prepared by
electrochemical polymerization (Scheme 41).42 The PITN matrix in the active layer to improve the film-forming
main chain tends to favor the quinoid form to preserve the property. The PSC based on PMMA/P90/PCBM (1:2:6, w/w/
benzene aromaticity at the expense of the thiophene aroma- w) showed the highest device characteristic with a PCE of
ticity. As a consequence, PITN is the first conjugated polymer 0.31%.231
to have a band gap as low as 1 eV, which is 1 eV smaller Hillmyer and co-workers reported a new distannyl-
than that of polythiophene. The monomer precursor isothia- isothianaphthene compound (144) which was synthesized by
naphthene (ITN, 138) was prepared by dehydration of the the n-BuLi lithiation of isothianaphthene (138) in tetram-
sulfoxide 137, which was made by the NaIO4 oxidation of ethylethylenediamine (TMEDA) and THF followed by
136 (Scheme 41).226 reaction with trimethyltin chloride.232 This molecule is
PITN syntheses have been described using various elec- chemically stable under an inert atmosphere at low temper-
trochemical or oxidative polymerizations of isothianaphthene. atures and can be used as a useful building block to prepare
Straightforward chemical polymerization routes have also the alternating ITN-fluorene copolymer P93 or the ITN–
been developed to make substituted PITNs with sufficient thiophene copolymer P94 by a Stille coupling with 9,9-
solubilities and tunable band gaps. As shown in Scheme 42, dihexyl-2,7-dibromofluorene (60) or bis(bromothienyl)-
the thermal polymerization of dithiophthalide 140227,228 in isothianaphthene 145, respectively (Scheme 44). It is
the presence of catalytic amounts of toluenesulfonic acid particularly noteworthy that 145 can also be synthesized from
afforded poly(5,6-bis(octylmercapto)isothianaphthene) (P89). 144 by a Stille coupling reaction with 2-bromo-3-decylth-
Its band gap of 1.16 eV is too low to obtain sufficient iophene (146) followed by NBS bromination. This is a more
photovoltaic performance.229 facile way for making dithienylisothianaphthene derivatives
Incorporation of different aromatic units into PITN allows without using the traditional route, which requires harsh
greater structural versatility for the fine-tuning of the intrinsic conditions involved with using Lawesson’s reagent.233,234
properties. However, the use of these low band gap PITN Although when blended with PCBM (1:4, w/w) P93 has a
derivatives for solar cell device applications encountered larger band gap of 2.3 eV, it showed a higher PCE of 0.46%
difficulties such as inefficient polymerization, low molecular than P94 (band gap 1.66 eV) with a PCE of 0.23% under
weights, poor film-forming ability, and the unstable nature the same testing conditions. This could be ascribed to its
of both the isothianaphthene monomer and the polymer. better film-forming properties.
Thiophene-isothianapthene copolymers P90, P91, and P92,
synthesized by FeCl3 oxidative polymerization (Scheme 43) 6.5. Cyclopenta[2,1-b:3,4-b′]dithiophene-Based
with band gaps of 1.8, 1.5, and 1.4 eV, respectively, cannot Polymers
form homogeneous pinhole-free thin films by spin-coating
due to their low molecular weights, which is a result of an Structurally analogous to fluorene, 4H-cyclopenta[2,1-b:
inefficient oxidative coupling reaction.230,231 3,4-b′]dithiophene (CPDT) derivatives, where two thiophene
In addition to PCBM and a donor polymer, poly(methyl units are tied and rigidified by a covalent carbon, have
methacrylate) (PMMA) was required to serve as the host attracted considerable research interest.235 Due to its fully
5896 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 44. Synthesis of P93 and P94 by a Stille Coupling Reaction

Scheme 45. Synthesis of Homopolymers P95-P97 this polymer both in solution and in the solid state are
essentially identical. This suggests that self-assembly of the
interchain interactions in the solid state is not established.
To further decrease the band gap and improve the
absorption coverage, poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cy-
clopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothia-
diazole)] (PCPDTBT) (P98) containing alternating CPDT
units as the donor and benzothiadiazole units as the acceptor
was developed and synthesized by Zhu and co-workers via
a Stille coupling (Scheme 46).239 With two ethylhexyl groups,
PCPDTBT is very soluble in organic solvents and has good
miscibility with PCBM, thus facilitating its processability.
The HOMO and LUMO values, from electrochemical
measurements, were calculated to be -5.3 and -3.57 eV,
respectively. The optical band gap, from solid-state absorp-
tion, is approximately 1.4 eV, which is regarded as ideal for
polymer-fullerene BHJ solar cells. Unlike the homopolymer
of CPDT, PCPDTBT showed a much greater red shift in
the absorption spectrum of the thin film than in solution.
coplanar structure, many intrinsic properties based on This indicates more interchain interactions when benzothia-
bithiophene can be altered, leading to extended conjugation, diazole units are incorporated. When blended with PC71BM,
lower HOMO-LUMO energy band gaps, and stronger the BHJ device achieves a PCE of up to 3.5% with a Jsc of
intermolecular interactions. Furthermore, the option of func- 11.8 mA/cm2 and a Voc of 0.65 V. This is together with an
tionalization at the bridging carbon allows greater structural elevated EQE higher than 25% over the spectral range from
variations for fine-tuning both the electronic and steric 400 to 800 nm: the maximum of 38% is around 700 nm.
properties. Moreover, the photocurrent production is extended to
As reported by Ferraris and co-workers,236,237 poly(cyclo- wavelengths even longer than 900 nm.240 The high perfor-
penta[2,1-b:3,4-b′]dithiophen-4-one) (P95) or poly(4-(dicya- mance of PCPDTBT can be attributed to its broad, strong
nomethylene)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene) (P96) absorption spectrum and high mobility of charge carriers.
were electropolymerized from their parent monomers 148 The planar structure facilitates carrier transport between the
and 149, respectively (Scheme 45). Owing to the electron- polymer chains, allowing its hole mobility to reach up to 1
withdrawing effect of the ketone or dicyano groups for × 10-3 cm2/(V s). By incorporating a small amount of 1,8-
reducing the aromaticity of bithiophene and stabilizing the octanedithiols into the PCPDTBT/PC71BM solution prior to
quinoid form, the band gaps of P95 and P96 can be markedly spin coating, the solar cell efficiency was further improved
reduced to as low as 1.2 and 0.8 eV, respectively. To make to 5.5% through the formation of an optimal bulk morphol-
solution-processable polymers, 2,6-dibromo-CPDT 150 with ogy which enhances both the photoconductivity and charge
two 2-ethylhexyl side chains was homopolymerized by a Ni- carrier lifetime.241 Without the need for thermal annealing
catalyzed coupling reaction to afford P97.238 The resulting during fabrication, this approach offers easier control over
polymer showed a much lower band gap of ca. 1.7-1.8 eV tailoring the morphology and is especially applicable to the
compared to its analogous poly(3-alkylthiophene) or poly- more amorphous p-type polymers with low degrees of
fluorene. It should be noted that the absorption spectra of crystallinity where thermal annealing is less effective.242,243
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5897

Scheme 46. Synthesis of P98 by a Stille Coupling Reaction

Scheme 47. Synthesis of P99 by a Stille Coupling Reaction

Scheme 48. Synthesis of P100 by a Stille Coupling Reaction

Heeger and co-workers also reported an efficient tandem cell PCE of 0.89% was recorded with a Jsc of 5 mA/cm2 and a
with two active layers. This was aimed at maximizing the Voc of 0.52 V. The poorer performance of P103 compared
sunlight harvesting by smartly integrating a complementary to PCPDTBT is attributed to its weaker absorbance and an
pair comprised of P3HT with the wider band gap and imbalance in the hole and electron transport of the active
PCPDTBT with the smaller band gap. The result led to the layer.
realization of a record-high PCE of over 6%.244 Because A number of synthetic routes directed toward the prepara-
PCPDTBT is the first breakthrough on the way to developing tion of useful CPDT monomers require laborious multistep
efficient low band gap D-A polymers, extensive analysis synthesis and purification.251-254 Considerable interest in the
of the physical behavior of PCPDTBT/PCBM blends was preparation of the ketone 160 as a precursor for low band
carried out, namely, in terms of photoconductivity,245 electron gap polymers led to a more efficient route developed by
transfer,246 and charge transport.247 Brzezinski and Reynolds using only three steps from starting
About the same time, Müllen and co-workers reported a material 157 (Scheme 50).255 The ketone 160 is further
polymer (P99) analogous to PCPDTBT (P98) but with 4,4- reduced to 161 by a hydrazine Wolff-Kishner reduction.
dihexyldecyl substituents instead of the ethylhexyl groups The methylene proton in 161 is acidic enough to undergo a
(Scheme 47). P99 shows a markedly high hole mobility of double alkylation in the presence of potassium hydroxide in
0.17 cm2/(V s) in FET. This can be attributed to the enhanced dimethyl sulfoxide to yield 163. Lithiation of 163 by tert-
packing order as a result of the introduction of the straight butyllithium and sequential quenching using trimethyltin
side chains.248 chloride afforded the distannyl monomer 151 ready for
By decreasing the content of the acceptor 4,7-(2,1,3- polymerization.
benzothiadiazole) molecule 152 and introducing 5,5′-
[2,2′]bithiophene 154 as the donor, a series of random 6.6. Silafluorene- and Dithieno[3,2-b:2′,3′-d]silole-
copolymers P100 were also synthesized (Scheme 48).239
Based Polymers
Through adjusting the D:A ratio, the absorption character-
istics can be tuned to cover the whole visible spectrum. Initial Compared with many heterocyclic arenes such as thiophene,
cell testing on P100/PCBM has already resulted in PCE furan, or pyrrole, the silole (silacyclopentadiene) ring has
values of up to 3% being attained. the smallest HOMO-LUMO band gap and the lowest lying
Subsequently, CPDT was used as an electron-donating LUMO level due to the σ*-π* conjugation between the
building block for the construction of a series of alternating π-symmetrical σ* orbital of two σ exocyclic bonds on silicon
D-A conjugated polymers. In addition to benzothiadiazole, and the π* orbital of the butadiene moiety.256 As a result a
other electron-accepting moieties such as quinoxaline and variety of conjugated small molecules and polymers consist-
dithiophene-ylbenzothiadiazole were also copolymerized with ing of silole derivatives exhibit extraordinarily unique
CPDT to form P101 and P102, respectively (Scheme 49).249 properties such as high fluorescence efficiency and electron
By using a 19:1 (v/v) mixture of chlorobenzene and anisole affinity and excellent electron mobility.257-260 Conjugated
as the solvent to cast the P102/PCBM film, the optimal polymers containing alternating electron-rich pyrroles or
morphology was attained and the corresponding PSC device thiophenes and silole units have shown considerably smaller
reached a PCE of 2.1%. band gaps, which is indicative of the electron-accepting
4,7-Dibromo-2,1,3-benzoselenadiazole (BSe), which is ability of silole to induce intramolecular charge transfer.261-263
similar to the benzothiadiazole unit, was also coupled with It is envisioned that the silole unit can serve as a useful
CPDT by a Stille coupling to make the polymer P103.250 A building block in the molecular design of new conjugated
5898 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 49. Synthesis of P101-P103 by a Stille Coupling Reaction

Scheme 50. Synthetic Route toward Monomer 151 A facile synthesis aimed toward accessing 2,5-difunctional
silole derivatives has been described by Tamao and co-
workers (Scheme 52).265 Upon treatment with lithium naph-
thalenide, bis(phenylethynyl)dimethylsilane (167) undergoes
intramolecular reductive cyclization to form 2,5-dilithiosilole
168, which was then transformed into 2,5-dizincated silole
169. A Negishi Pd-catalyzed cross-coupling of this inter-
mediate with 2-bromothiophene (117) afforded 2,5-bis(2′-
thienyl)silole 170, which was further brominated by NBS
to furnish 164.
The fluorene-containing D-A conjugated polymer P44
and its derivatives have all been shown to have good
photovoltaic properties as well as to deliver high PCEs over
the 2-3% range. When the carbon atom on the 9-position
of the fluorene unit is replaced with a silicon atom, a new
type of building block, namely, silafluorene evolves. By
fusing a silole ring between two phenyl rings, the silafluorene
Scheme 51. Synthesis of P104 by a Suzuki Coupling
Reaction
is expected to combine the advantages of both the silole and
fluorene intrinsic properties. The tetravalence of the silicon
atom in the silole ring opens up two additional substitution
sides for the introduction of solubilizing groups. Cao and
co-workers made the copolymer P105, which was synthe-
sized by the Suzuki coupling266 of 2,7-silafluorene 171 and
dithienylbenzothiadiazole unit 42 (Scheme 53).
The solar cells made from a P105:PCBM (1:2, w/w) blend
achieved a Voc of 0.9 V, a Jsc of 9.5 mA/cm2, an FF of 50.7%,
and a PCE of up to 5.4%. The high Voc can be attributed to
the low-lying HOMO of P105, which is -5.39 eV. From
FET measurements, P105 showed a hole mobility of 1 ×
10-3 cm2/(V s), which is much higher than that of the PFO-
DBT polymer (3 × 10-4 cm2/(V s)). In addition, P105
exhibits a lower optical band gap and a greater red-shifted
polymers for use in organic solar cell applications. An absorption maximum compared to PFO-DBT P45a (1.82 vs
alternating copolymer P104, derived from 9,9-dihexylfluo- 1.92 eV and 565 vs 544 nm, respectively). These enhanced
rene and the 1,1-dimethyl-3,4-diphenyl-2,5-bis(2′-thienyl)- properties contribute to improved hole transport and broader
silole unit, was synthesized by a Suzuki coupling (Scheme absorption, leading to a higher Jsc and an acceptable FF.
51).264 The HOMO and LUMO levels and the optical band Around the same time, a parallel study using the same
gap of P104 were determined to be -5.71, -3.6, and 2.08 polymer was reported by Leclerc et al.267
eV, respectively. Blended with PCBM in the active layer of The synthetic route for monomer 171 was developed by
a bulk heterojunction device, P104 achieved a promising Holmes and co-workers (Scheme 54).268 An Ullmann cou-
PCE of 2.01%. pling of compound 172 gave the dimerization product 173.
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5899

Scheme 52. Synthetic Route toward Monomer 165

Scheme 53. Synthesis of P105 by a Suzuki Coupling Reaction

Scheme 54. Synthetic Route toward Monomer 171

Reduction of the nitro groups in 173 yielded the amino PCPDTBT, the substitution of the silicon atom significantly
compound 174. This was followed by iodination via a improved the hole-transport properties. The hole mobility
diazonium pathway to generate 175. Selective lithiation of of P108 (3 × 10-3 cm2/(V s)), determined by a field-effect
the iodo groups of 175 by tert-butyllithium to react with transistor, is 3 times higher than that for PCPDTBT. The
dioctyldichlorosilane led to the formation of the central silole photovoltaic device with an active layer of P108/PC71BM
ring of 176. Finally, the bromo groups in 176 can be easily (1:1, w/w) exhibited a Voc of 0.68 V, a Jsc of 12.7 mA/cm2,
transformed to the bis(boronic ester) 171. and a very impressive PCE of 5.1%. Notably, the EQE as a
In view of the beneficial molecular design on going from function of the wavelength showed a broad response ranging
fluorene to silafluorene, the exceptional cyclopentadithiophene from 350 to 800 nm.
system is further modified by substituting the carbon atom The synthesis of the distannyldithienosilole 179 is
with a silicon bridge to generate a dithienosilole having a shown in Scheme 56. By a selective lithium-bromide
silole ring embedded in the center of dithiophene. A exchange followed by nucleophilic substitution, the tri-
dithienosilole homopolymer (P106) and an alternating methylsilyl group was introduced into the 5,5′-positions
dithienosilole and dithienylbenzothiadiazole copolymer of the bithiophene compound 181 to act as a protecting
(P107) were reported and synthesized by Stille coupling group. As a consequence, the subsequent lithiation in
reactions (Scheme 55).269 Due to the incorporation of compound 181 only occurred at the 3,3′-positions of the
electron-accepting units, the copolymer P107 has both a bithiophene, which then underwent cyclization through
lower HOMO level, -5.13 eV, and a smaller band gap, 1.4 double addition to dialkyldichlorosilane and gave 182.
eV, than the homopolymer P106 (-4.85 and 1.9 eV, NBS bromination via electrophilic aromatic substitution
respectively). The best photovoltaic performance after ther- to replace the trimethylsilyl moiety resulted in the
mal annealing at 140 °C was based on P107/PCBM (1:1, formation of compound 183, which was then converted
w/w) and showed a Voc of 0.44 V, a Jsc of 1.32 mA/cm2, to the distannyl compound 179 by lithiation and final
and a PCE of 0.18%. quenching with trimethyltin chloride.
Recently, Yang and co-workers reported another dithienos-
ilole-containing copolymer (P108). Here benzothiadiazole
is the acceptor and 2-ethylhexyls are the solublizing groups,
6.7. Dithieno[3,2-b:2′,3′-d]pyrrole-Based Polymers
which makes it structurally similar to PCPDTBT (Scheme After the tricyclic cyclopentadithiophene and dithienos-
55).270 The HOMO and LUMO of the polymer were ilole rings were shown to serve as excellent donor
estimated to be -5.05 and -3.27 eV, respectively. Although components with various acceptor units in low band gap
the optical band gap of 1.45 eV is very close to the polymer polymers, dithieno[3,2-b:2′,3′-d]pyrrole attracted attention
5900 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 55. Synthesis of P106-P108 by a Stille Coupling Reaction

Scheme 56. Synthetic Route toward Monomer 179

Scheme 57. Synthesis of P109 by FeCl3 Oxidative Polymerization and P110 by a Stille Coupling Reaction

as another appealing fused bithiopene member with a 57).272 P110 showed a greater red-shifted absorption maxi-
bridged nitrogen having strong electron-donating ability. mum at 697 nm in a film than in solution at 671 nm. This
As reported by Rasmussen and synthesized by the oxida- indicates strong interchain interactions due to its coplanar
tion polymerization of 184, the homopolymer poly- structure. Compared with the homopolymer dithienopyrrole,
(dithieno[3,2-b:2′,3′-d]pyrrole) P109 showed a reduced P110 also exhibited a more bathochromic shift in the
band gap of ca. 1.7 eV and a high red-emitting quantum absorption spectrum and a smaller optical band gap of 1.46
efficiency.271 Hashimoto and co-workers reported another eV. Again this demonstrates efficient charge transfer between
D-A conjugated copolymer (P110) constituted of alternating the donating dithienopyrrole and accepting benzothiadiazole
dithienopyrrole and dithienylbenzothiadiazole units and units. The PSC based on P110 as the donor and blended
synthesized by a Stille cross-coupling reaction (Scheme with PCBM (1:1, w:w) exhibited a PCE of 2.18%.
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5901

Scheme 58. Synthetic Route toward Monomers 185 and 191

Scheme 59. Dibromo and Distannyl Monomers for the Synthesis of Polymers P111-P117 by a Stille Coupling Using Pd(PPh3)4
as the Catalyst

The dithieno[3,2-b:2′,3′-d]pyrrole ring of 188 was built Yang and co-workers reported a series of BDT-based
up by a one-step cyclization through a double Pd-catalyzed polymers, P111-P117, with different alternating units. They
amination of 3,3′-dibromobithiophene (187) with the primary systematically investigated their structure-property relation-
amine 186 having a long aliphatic side chain (Scheme 58). ships for PSC applications.275 Using a Stille cross-coupling
Another efficient way to synthesize the dithieno[3,2-b:2′,3′- of the relevant monomers, 4,8-bisalkoxy-BDT was copoly-
d]pyrrole ring involves the Pd-catalyzed amination of 3-bro- merized with two types of electron-donating units, including
mothiophene (157) with a variety of primary amines to form thiophene and (ethylenedioxy)thiophene (EDOT), and four
189. This is followed by a one-pot NBS bromination and electron-deficient units, including thieno[3,4-b]pyrazine (TPZ),
Cu cyclization to yield 191(Scheme 58).273 benzoselenadiazole (BSe), 2,3-diphenylquinoxaline (DPQ),
and benzothiadiazole (BT) (Scheme 59). The absorption
6.8. Benzo[1,2-b:4,5-b′]dithiophene-Based spectrum of the homopolymer P111 showed a maximum
Polymers wavelength at 495 nm. As the donating strength of the
The benzo[1,2-b:4,5-b′]dithiophene (BDT) unit has emerged incorporated unit increases from thiophene in P112 to EDOT
as an attractive building block for making conjugated in P113, the maximum absorption shifts to 511 and 532 nm,
polymers due to its large planar conjugated structure ideal respectively. However, it was found that the electron-
for efficient π-π packing. Alternating BDT and bithiophene donating power of EDOT in P113 also resulted in an
copolymers exhibiting a high field-effect transistor mobility increased HOMO level and a subsequent decrease in Voc.
of 0.25 cm2/(V s) and enhanced stability has been reported.274 On the other hand, the ability of the four electron-deficient
5902 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 60. Synthetic Route toward Monomer 192

Scheme 61. Synthesis of P118 by a Stille Coupling Reaction

units to lower the band gap of the corresponding polymer is by good electrochemical stability.277-279 However, such a low
in the order TPZ (P117) > BSe (P115) > DPQ (P116) > BT band gap polymer is not ideal for solar cell applications.
(P114). This also reflects their electron-accepting strength To dilute the thieno[3,4-b]thiophene content in the main
as well as their capability to adopt the quinoid structure in chain with a view to adjusting the band gap, a series of
the polymer. As a result, P117 containing TPZ showed a copolymers P118 consisting of thieno[3,4-b]thiophene and
very low band gap of 1.05 eV, which matchs the solar thiophene units were synthesized by Stille coupling reactions
spectrum well. However, because of the fact that the HOMO (Scheme 61).280 By changing the ratio between thiophene
level lies somewhat too high, the Voc of P117 is only 0.21 and thieno[3,4-b]thiophene to fine-tune the degree of quinoid
V. One interesting observation is that, unlike the BSe formation, the band gap and energy levels of the polymer
analogue, the BT unit in the BDT-based polymer P114 can could be controlled to optimal values. As expected, the band
narrow the band gap by depressing the LUMO level without gap of the polymer decreases as the thieno[3,4-b]thiophene
elevating its HOMO level when compared to the standard increases by compressing the HOMO and LUMO levels
homopolymer P111. This is reflected in an improved Voc of closer to each other. Importantly, P118a with the highest
0.68 V. When blended with PCBM (1:1, w/w), P112 showed content of thieno[3,4-b]thiophene exhibits the greatest hole
the highest PCE, 1.6%, with a Voc of 0.75 V, a Jsc of 3.78 mobility, very comparable to that of P3HT, suggesting that
mA/cm2, and an FF of 0.56. the more the TT units induce the quinoid form the greater
The synthesis of the monomer 1,8-bis(dodecyloxy)-BDT the planarity along the aromatic backbone to facilitate charge
192 is shown in Scheme 60. Lithiation of N,N-diethylth- transport. In addition, when the TT ratio decreases in the
iophene-3-carboxamide (199) with butyllithium, followed by copolymers, the 3-hexylthiophene units are irregularly at-
nucleophilic addition to the amide group, afforded the tached to the backbone, which causes a twisting of the main
cyclized dimerization product 200. The central benzoquinone chain and leads to decreased hole mobility. P118d with an
of 200 was reduced to a hydroquinone-type intermediate by m:n ratio of 1:3.7 has a more ideal optical band gap of 1.45
treatment with zinc dust followed by O-alkylation to produce eV and more optimal HOMO/LUMO levels relative to the
201 in a one-pot reaction.276 The resulting 201 can be directly PCBM acceptor, achieving a highest Jsc of 8.66 mA/cm2 and
lithiated by butyllithium and then quenched with trimethyltin a PCE of 1.93% among these polymers using the composite
chloride to obtain 192 without having to go through a of polymer/PCBM (1:1, w/w) in BHJ solar cells. Although
bromination step. P118a showed only a PCE of 0.73% due to its band gap as
low as 1.2 eV, which limits its application for the solar cell,
its derivative with a different alkyl chain has been success-
6.9. Thieno[3,4-b]thiophene-Based Polymers fully used in a plastic near-infrared photodetector.281
The low band gap strategy involving PITN derivatives led A regioregular 3-hexylthiophene-conjugated oligomer
to interest in other fused ring systems as potential building (203) and its polymer analogue P119 containing small
blocks for p-type conjugated polymers. Like ITN with its amounts of thieno[3,4-b]thiophene were also synthesized
thiophene-fused benzene ring, thieno[3,4-b]thiophene (TT) (Scheme 62).282 The perfluorohexyl substituent is used to
is thiophene fused with another thiophene ring at the 3,3′- stabilize the electron-rich thieno[3,4-b]thiophene and renders
thiophene positions. Polythieno[3,4-b]thiophene (PTT) is it more chemically stable. The optical band gap of 203 and
capable of stabilizing the quinoid form of the main chain, P119 determined to be ca. 1.6 eV is much lower than that
resulting in a very low band gap of 0.84 eV accompanied of P3HT (1.9 eV) due to the effect of the introduced
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5903

Scheme 62. Synthesis of P119 by a Stille Coupling Reaction and Chemical Structure of Oligomer 203

Scheme 63. Synthesis of P120 by a Stille Coupling Reaction

Scheme 64. Synthetic Route toward Monomer 206

thienothiophene units. Although 203 and P119 exhibited 4.5 × 10-4 cm2/V s as measured by the space charge limited
similar optical properties and HOMO energies due to the current method. The synthesis of monomer 206 is shown in
similarity of structure, P119 having higher molecular weight Scheme 64. Chloromethylation of 207 by using chloromethyl
showed better hole mobility due to the extension of the methyl ether with zinc chloride as a catalyst afforded the
electron delocalization length in the polymer and better bis(chloromethyl) product 208, which was cyclized by
miscibility with PCBM to yield an optimal morphology of reacting with sodium sulfide to give compound 209. After
an interpenetrating nanofiber with a diameter ranging from hydrolysis of 209 to give the carboxylic acid 210, the sulfide
15 to 20 nm. In contrast, 30-40 nm fibers were found in was oxidized to the sulfoxide 211 by sodium metaperio-
the 203/PCBM blend because of the more favorable phase date.284 Reacting with acetic anhydride followed by base-
separation. Therefore, the P119-based solar cell devices induced elimination, compound 211 was reduced to form a
achieved a PCE of 2.38% and outperformed the 0.46% thiophene ring in compound 212. Bromination followed by
obtained from the oligomer 203. etherification led to the formation of the final product 206.
To take advantage of the BDT and thieno[3,4-b]thiophene
units together, Yu and co-workers designed and synthesized 6.10. Thieno[3,2-b]thiophene-Based Polymers
the copolymer P120. Stille coupling produced a product
comprised of alternating BDT and thieno[3,4-b]thiophene Another attractive example of the fused thiophene family
units (Scheme 63).283 The ester-substituted thieno[3,4- is thieno[3,2-b]thiophene. The incorporation of linearly
b]thiophene in this polymer makes it both soluble and symmetrical and coplanar thieno[3,2-b]thiophene units in the
oxidatively stable. The optical band gap derived from the conjugated polymer is predicted to facilitate the adoption of
onset of the film absorption is 1.6 eV. The HOMO and a low-energy backbone conformation, leading to strong
LUMO were determined to be -4.9 and -3.2 eV, respec- interchain interactions for ordered packing. Unfortunately,
tively. The BHJ solar cells were fabricated using a P120/ polythieno[3,2-b]thiophene has very poor solubility, which
PCBM composite (1:1, w/w), giving a Voc of 0.58 V, a Jsc limits its characterization and processability.285,286 The
of 12.5 mA/cm2, and a high power conversion efficiency of introduction of alkyl chains into the β-position of the
4.76%. An improved conversion efficiency of up to 5.3% thieno[3,2-b]thiophene unit can improve the solubility, but
was achieved when the polymer was blended with PC71BM. the down side is that it also imposes a negative effect on the
The thienothiophene unit tends to stabilize the quinoid effective conjugation due to severe steric-hindrance-induced
structure in the polymer chain and thus enhances the planarity twisting between the neighboring units.287,288 To reduce steric
along the polymer backbone. The high power conversion interactions and thereby restore planarity and conjugation,
efficiency can be attributed to the rigidity and planarity of vinylene units serving as spacers were incorporated and
the polymer backbone, leading to a high hole mobility of copolymerized with either a 3-hexylthiophene or a thieno[3,2-
5904 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 65. Synthesis of P121 and P122 by Stille Coupling of P123 were estimated to be -5.1 and -3.1 eV, which are
Reactions very close to those of P3HT. The PSCs fabricated from the
active layer of P123/PC71BM (1:4, w/w) achieved the
maximum PCE of 2.3% with a Voc of 0.58 V, a Jsc of 12.5
mA/cm2, and an FF of 0.48. The synthesis of 216 is outlined
in Scheme 67.296 Deprotonation of 3-bromothiophene with
lithium diisopropylamide (LDA) followed by quenching with
N-formylpiperidine afforded 218. The Michael addition of
ethylmercaptoacetate to the 3-position of 218 followed by
elimination of bromide and an Aldol condensation yielded
219. This was then hydrolyzed to the corresponding car-
boxylic acid 220. Decarboxylation by copper and quinoline
led to the formation of thieno[3,2-b]thiophene 221. Lithiation
of 221 and quenching with trimethyltin chloride led to 2,5-
bis-trimethylstannyl-thieno[3,2-b]thiophene 216.

6.11. Other Fused Thiophene-Based Conjugated

Polymers
Three bithiophene-based compounds planarized by bridg-
ing benzo, naphtho, and quinoxalino units were polymerized
b]thiophene unit to prepare the copolymers P121 and P122, with the CDPT moiety 225 by Suzuki coupling to yield the
respectively (Scheme 65).289 corresponding polymers P124, P125, and P126, respectively
It was observed that the absorption maximum of P122 in (Scheme 68).297 These fused five-six-five tricyclic conju-
solution is at 538 nm, which is 18 nm hypsochromically gated segments are designed to enhance molecular planarity
shifted as compared with that of P121, implying that hexyl and π-electron delocalization. The optical band gap was
groups in the thienothiophene unit still cause distortion of estimated to be 2.00, 1.91, and 1.94 eV for P124, P125, and
the polymer backbone. It is noteworthy that, whereas no P126, respectively, very comparable to that of P3HT and
emission was observed for P121, P122 exhibits strong larger than that of the CPDT homopolymer with a band gap
photoluminescence in the wavelength range from 500 to 750 of 1.7-1.8 eV. This result indicated that, although incorpora-
nm. From field-effect transistor studies, P122 showed a hole tion of a benzene ring fused into two thiophenes enhances
mobility of 4.64 × 10-4 cm2/(V s). After thermal annealing the coplanarity, the formation of a 14-π-electron system with
at 180 °C for 30 min, the hole mobility dramatically a higher degree of aromaticity may also reduce the quinoid
increased to 0.019 cm2/(V s). The morphology investigated formation in the polymer chain, resulting in a higher band
by AFM indicated that, after annealing, crystalline domains gap. With additional benzene rings or pyrazine rings fused
were induced in the P122 film from its original amorphous with this system, the delocalization decreases the aromaticity
phase, leading to markedly improved mobility. On the so that the band gap can be reduced to some extent. It is
contrary, the P121 films exhibited only characteristic amor- expected that lower polymer band gaps can be obtained if
phous morphologies both with and without annealing. As a 221-224 are copolymerized with an electron-withdrawing
result, P121 showed relatively low mobility on the order of acceptor instead of the electron-rich CPDT. Due to the
10-4 cm2/(V s). Due to the higher mobility resulting from presence of an electron-deficient pyrazine ring, -5.15 eV
the thieno[3,2-b]thiophene units, the PCE of the PSCs based was the lowest HOMO for P126. BHJ photovoltaic devices
on P122 reached 0.28%, which is superior to the 0.19% for made from P126/PCBM (1:1.6, w/w) exhibited an overall
the P121 device. PCE of 1.14%.
Poly(2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2- The synthesis of the monomers 222-224 is depicted in
b]thiophene (P123) containing no substituents on the thieno[3,2- Schemes 69-71. The Pd-catalyzed coupling reaction of 3,3′-
b]thiophene units but with two long tetradecyl chains on the diiodo-2,2′-bithiophene (226) and 9-octadecyne gave the
bithiophene unit was reported by McCulloch and co-workers cyclization product 227, which was brominated to obtain the
(Scheme 66).290 Two symmetrical monomers coupled by a monomer 222 (Scheme 69).298 The Suzuki coupling reaction
Pd-catalyzed Stille reaction offer a regioregular arrangement of 228 with 3-thiopheneboronic acid gave the product 229.
of the polymer under formation. The tail-to-tail arrangement Oxidative photocyclization of 229 by UV irradiation in the
of the alkyl chains on the bithiophene units also minimizes presence of a catalytic amount of iodine resulted in the
the steric interactions between neighboring units, leading to formation of compound 230, which was then brominated to
coplanarity of the backbone and hence promoting self- obtain the final monomer 223 (Scheme 70). The condensation
organization. It was found that the hairy rigid-rod P123 of the 1,2-diamine 231 with 1,2-diketone 232 directly
exhibits a liquid-crystalline phase and self-assembles into a furnished the dehydrogenated product 233, which after NBS
highly crystalline domain with lamellar and π-stacked bromination gave the final monomer 224 (Scheme 71).
polymer chains.291,292 The side chain attachment density in 4,9-Dihydro-s-indaceno[1,2-b:5,6-b′]dithiophene-4,9-di-
P123 is sufficiently low to allow interdigitation, which one derivatives are pentacyclic systems consisting of a
provides a three-dimensional ordering.293 Due to this en- thiophene-1,4-phenylene-thiophene skeleton with two fused
hanced structural order, a remarkably high field-effect hole cyclopentadienone rings in between. This new conjugated
mobility of 0.2-0.6 cm2/(V s) was realized. This is even diketone system has been shown to have unique optical and
greater than that obtained in regioregular P3HT (0.1-0.2 redox properties.299 This pentacyclic component was copo-
cm2/(V s)).290 Its potential application in BHJ solar cells was lymerized with different ratios of thiophene units to afford
therefore investigated.294,295 The HOMO and LUMO levels two new conjugated polymers (P127a (m:n ) 1:5) and
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5905

Scheme 66. Synthesis of P123 by a Stille Coupling Reaction

Scheme 67. Synthetic Route toward Monomer 216 layer (1:3, w/w) gave the highest performance and delivered
a PCE of 4.4%, a Voc of 0.8 V, a Jsc of 10.1 mA/cm2, and an
FF of 0.53. The PCE is better than that of a cell based on
P3HT (PCE ) 3.9%) under the same conditions. 241 was
prepared by following the procedure developed by Wong et
al. (Scheme 75).304 A double nucleophilic addition of (4-
hexylphenyl)magnesium bromide (243) to the ester groups
of 242 led to the formation of the benzylic alcohol 244, which
P127b (m:n ) 1:2.5)) using a Stille cross-coupling reaction was then subjected to intramolecular annulation through acid-
(Scheme 72).300 When the diketone content is higher than mediated Friedel-Crafts reaction to furnish 245. The NBS
that of P127b, the resulting polymer becomes insoluble. P128 bromination of 245 yielded the final monomer 241.
with a pure polythiophene main chain was also prepared for
comparison. Besides the absorption at 300-600 nm which 6.12. Pyrrole-Containing Polymers
is observed in P128, P127a and P127b exhibited an
additional broad absorption peak at 600-800 nm which is A pyrrole-containing polymer (P131) has been synthesized
assigned to the π-π transition of the diketone unit. However, by the Stille coupling of 2,5-bis(5-(trimethylstannyl)-2-
both in solution and in the solid state, the absorption thienyl)-N-dodecylpyrrole (246) and 4,7-dibromo-2,1,3-ben-
coefficient of the lower energy absorption band is much zothiadiazole (152) using Pd(PPh3)2Cl2 as the catalyst
weaker than those in the 300-600 nm region. This prevents (Scheme 76).305,306 During the polycondensation, extensive
efficient light harvesting at longer wavelengths. As the destannylation of the distannyl monomer 246 occurred. This
diketone unit content increases, the oxidation potential of resulted in a low molecular weight polymer terminated with
P127b becomes higher than those of P128 and P127a due bromobenzothiadiazole end groups. Polymers with higher
to the electron-withdrawing effect of the diketone units. molecular weights can be obtained by adding excessive
These three polymers have very similar band gaps at ca. 2.3 amounts of the distannyl monomer 246. As a result of
eV as determined by cyclic voltammetry. The PCE values alternating electron-rich and electron-deficient units along
of solar cells using blends of these polymers with PCBM the conjugated chain, this polymer shows a low band gap of
(1:3, w/w) were measured and found to be 0.33% for P127a 1.6 eV. Efficient photoinduced electron transfer from the
and 0.26% for P127b, better than that of P128, which is donor P131 to the acceptor PCBM, in the blending com-
0.11%. posite, has been demonstrated by photoinduced absorption
The synthesis of the monomer 234 is shown in Scheme and photoluminescence quenching of P131. The solar cell
73.299 Due to its decreasing solubility as a result of chain device based on P131/PCBM (1:1, w/w) showed a Voc of
elongation, hexyl groups were introduced in each of the 0.67 V, a Jsc of 0.8 mA/cm2, an FF of 0.35, and a PCE of
terminal thienyl units in 236. Desilylation of the protecting 0.34%. The efficiency has been further improved by up to
trimethylsilyl groups in 236 with trifluoroacetic acid resulted 1% with a P131:PCBM ratio of 1:3. Despite the band gap
in the formation of 237. Saponification of the diesters 237 of P131 being significantly lower than that of MDMO-PPV,
yielded the terephthalic acid 238, which is readily converted the Voc is decreased by only 0.1 V. Alternatively, P131 can
into the corresponding acid dichloride 239. A Lewis acid- be utilized as an efficient near-infrared-emitting material in
promoted intramolecular Friedel-Crafts cyclization of 239 light-emitting diode applications since it shows an emission
furnished the diketone 240, which was easily brominated at peak at 800 nm with a turn-on voltage below 4 V.37
the terminal thiophenes by NBS to give 234.
Two new low band gap polymers based on the thiophene– 6.13. Other Donor-Acceptor Conjugated
phenylene–thiophene moiety (TPT) have been reported by Polymers
Ko and co-workers.301,302 As shown in Scheme 74, the
synthesis involved a Pd-catalyzed Stille coupling under Diketopyrrolopyrrole-based (DPP) chromophores have
microwave-assisted conditions.303 TPT and benzothiadiazole been widely used as organic pigments in various applications
units were copolymerized with bithiophene or thiophene units such as paints and color inks.307 In terms of planar conjugated
to generate P129 or P130, respectively. Two outer thiophenes bicyclic structures and the electron-withdrawing nature of
are rigidified and held together using a central phenyl ring, the polar amide group, the diketopyrrolopyrrole unit can be
which provides a coplanar conjugated backbone of penta- exploited as a promising acceptor for p-type conjugated
cyclic fused aromatic rings. This planar structure provides polymers. A semiconductor of a conjugated polymer con-
effective conjugation and facilitates strong intermolecular taining the diketopyrrolopyrrole unit has shown ambipolar
interactions, leading to a low band gap of 1.76 eV for P129 high electron and hole mobility both close to 0.1 cm2/(V s)
and 1.70 eV for P130 and a high absorption coefficient for in an FET device.308 Very recently, Janssen and co-workers
efficient light harvesting. Furthermore, a high hole mobility reported a new conjugated polymer (P132) based on alternat-
of 3.4 × 10-3 cm2/(V s) for P130 was obtained in a field- ing electron-rich quaterthiophene and electron-deficient dike-
effect transistor, allowing efficient charge extraction and a topyrrolopyrrole units.309 The polymer synthesized by the
high fill factor. Blending P130 with PC71BM in the active Yamamoto coupling of 247 exhibits an ideal band gap of
5906 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 68. Synthesis of P124-P126 by Stille Coupling Reactions

Scheme 69. Synthetic Route toward Monomer 222

Scheme 70. Synthetic Route toward Monomer 223

Scheme 71. Synthetic Route toward Monomer 224

1.4 eV (Scheme 77). The absorption spectrum of P132 in only exhibited a very low EQE of 0.13 at 680 nm. It was
chloroform shows a λmax at 650 nm and an onset at 720 nm. found that by using a chloroform/ODCB mixture (4:1) to
However, an onset significantly red-shifted to 860 nm and process the active layer, a large degree of semicrystallinity
vibronic fine structure were observed when P132 was could be formed. On the basis of these optimal processing
dissolved in o-dichlorobenzene (ODCB), which is indicative conditions, the best device using P132/PCBM (1:2, w/w)
of strong intermolecular-interaction-induced semicrystalline gave a PCE of 3.2%. By utilizing PC71BM as the acceptor,
aggregation. The film spin-cast from a chloroform solution the photovoltaic performance was further improved and
of P132/PCBM showed amorphous polymer morphology due showed a high PCE of 4.0%, an FF of 0.58, a Voc of 0.61 V,
to the fast evaporation of the chloroform, which does not and a Jsc of 11.3 mA/cm2.
allow for the development of crystallinity. Therefore, the cell The synthesis of monomer 247 is shown in Scheme 78.
in which the active layer was processed from chloroform Reaction of 2-thiophenecarbonitrile (248) with 0.5 equiv of
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5907

Scheme 72. Synthesis of P127 and P128 by Stille Coupling Reactions

Scheme 73. Synthetic Route toward Monomer 234

Scheme 74. Synthesis of P129 and P130 by Stille Coupling Reactions

di-n-butyl succinate ester in tert-amyl alcohol under basic were synthesized from the corresponding dibromo monomers
conditions afforded an insoluble dimerization product (249) 254-257 via a Yamamoto reductive reaction using
which was allowed to undergo N-alkylation with 162 to give Ni(COD)2 as the dehalogenating reagent (Scheme 79). The
compound 250. Bromination of 250 by NBS, followed by a advantage of Yamamoto coupling is that only a single
Stille coupling and sequential bromination, produced the final component of monomer can self-polymerize to afford the
monomer 247. alternating D-A polymer with moderate to high molecular
Janssen and co-workers310,311 reported a series of side chain weight. These polymers are very soluble in common organic
substituted conjugated polymers (P133, P134, and P135) that solvents with the help of the branched (2-ethylhexyl)oxy side
consist of alternating electron-rich bithiophene and electron- chains. The absorption edges of P133, P134, and P135 in
deficient units including benzothiadiazole, thienopyrazine, solution are located at 720, 915, and 960 nm, respectively.
and thiadiazoloquinoxaline, respectively. These polymers In the solid state, the band edges are further red-shifted to
5908 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 75. Synthetic Route toward Monomer 241

Scheme 76. Synthesis of P131 by a Stille Coupling Reaction

Scheme 77. Synthesis of P132 by a Yamamoto Coupling Reaction

Scheme 78. Synthetic Route toward Monomer 247

800, 965, and 1034 nm corresponding to optical band gaps donating (2-ethylhexyl)oxy side chains attached to the P134
of 1.55, 1.28, and 1.20 eV for P133, P134, and P135, backbone decrease the oxidation potential by 0.18 V
respectively. Again, the thienopyrazine unit is more capable compared to that of P135. The PSC device based on P134/
of forming quinoid main chains than benzothiadiazole, PCBM (1:4, w/w) gave a Voc of 0.39 V, a Jsc of 1.5 mA/
leading to a much lower band gap. The slightly red-shifted cm2, and a PCE of 0.29%. A similar device based on P135
absorption and lower optical band gap of P135 compared to showed much improved performance with a Voc of 0.56 V,
P134 indicate improved conjugation caused by a more a Jsc of 3.1 mA/cm2, and a PCE of 1.1%. This is attributed
coplanar structure of the main chain in P135 due to the to its lower HOMO and improved miscibility with PCBM
absence of bulky substituents, although P134 has stronger compared to those of P134. On the other hand, a P133-based
donating alkoxythiophene and P135 has a stronger acceptor device reached a higher Voc of 0.77 V with a PCE of 0.9%.
due to the inductive effect of the alkoxy group in the meta- The electron-accepting strength of benzothiadiazole can be
position of the phenyl ring. Therefore, in the present case, further enhanced by fusing another pyrazine ring into the
steric effects dominate over electronic effects. The electron- vacant sites of the phenyl ring to form thiadiazoloquinoxa-
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5909

Scheme 79. Synthesis of P133-P136 by Yamamoto Coupling Reactions from 254-257

line. By arranging thiadiazoloquinoxaline and bithiophene Chart 20. Resonance Structure of Benzobis(thiadiazole)
in an alternating fashion, the polymer P136 exhibits a strong (258)
absorption in the near-infrared region along with an ultras-
mall band gap of 0.94 eV in solution.312 The onsets of the
oxidation and reduction waves of P136 are at -0.09 and
-1.06 eV vs Fc/Fc+, respectively, and provide an electro-
chemical band gap of 0.97 eV. However, the high electron
affinity of thiadiazoloquinoxaline also significantly lowers
the LUMO, resulting in negligible offset between P136 and
PCBM and thus inefficient photoinduced electron transfer. 20).314,315 A polymer (P137) containing quaterthiophene
PC84BM with an electron affinity larger by 0.35 V than as the donor and benzobis(thiadiazole) as the acceptor was
PCBM was therefore used to increase the LUMO offset synthesized by Stille coupling (Scheme 80).316 An analogous
between donor and acceptor.313 The device based on P136/ polymer (P138) using benzothiadiazole as the acceptor was
PC84BM (1:4, w/w) showed a photoresponse up to about also prepared for comparison. From the absorption spectra,
1300 nm, which is one of furthest red shifts reported for a P137 shows an extremely low band gap of 0.67 eV, which
polymer BHJ solar cell. However, the overall device ef- is 1 eV lower than 1.65 eV for P138 and even lower than
ficiency still remains low. that of polyisothianaphthene (1 eV). This result further
Benzobis(thiadiazole), derived from benzothiadiazole fused demonstrates the exceptional electron-accepting power of the
with another thiadiazole ring, is an extremely electron- benzobis(thiadiazole) subunit. Solar cell devices with a large
deficient unit due to its high tendency for the formation of area (3 cm2) based on a P138/PCBM (1:2, w/w) blend gave
quinoid structures and the hypervalent sulfur atom (Chart a photovoltaic response with a PCE of 0.62%.317 However,
5910 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 80. Synthesis of Benzobis(thiadiazole)-Containing P137 and P138 by a Stille Coupling Reaction

Scheme 81. Synthesis of PYM-Containing P139 and P140 by Voc values was observed on going from P139c to P139b to
Stille Coupling Reactions P139a in accordance with the HOMO levels. The solar cells
using a polymer/PCBM (1:1, w/w) blend achieved PCEs of
0.08%, 0.2%, and 0.6% for P139a, P139b, and P139c,
respectively. Because the thiophene unit and PYM are
connected through the meta-position of a phenyl ring, the
effective conjugation of the main chain is disrupted. There-
fore, increasing the content of thiophene units leads to
enhanced charge transport and hence improved Jsc values
and PCEs. When the phenyl group attached at the PYM
moiety was replaced by a thiophene ring, P140 showed an
enhanced absorption and a higher PCE of 0.9%.

6.14. Poly(thienylvinylene)s (PTVs)

Poly(thienylvinylene)s are another class of polythiophene-
based conjugated polymers. These polymers display high
nonlinear optical responses, moderate charge mobilities, and
good electroluminescent properties. By inserting a vinylene
unit between every thiophene unit to planarize the main chain
and reduce aromaticity, PTVs exhibit more effective con-
jugation and lower band gaps than polythiophenes. Much
attention and effort has been paid to evaluate their potential
for organic solar cell applications. Like the synthesis of PPV,
there are two synthetic approaches used in the preparation
of PTVs. One approach involves a straightforward polym-
erization reaction in a single step using the appropriate
monomers to generate the conjugated polymer. Two typical
transition-metal-catalyzed reactions can be used to synthesize
PTV directly. A Stille coupling of 2,5-dibromo-3-dodecylth-
the devices produced with P137 showed very low Voc and iophene (263) and 1,2-bis(tributylstannyl)ethylene (214) is
Jsc values, which is ascribed to the mismatch of LUMO expected to yield regiorandom PTV (Scheme 82). However,
energy levels between P137 and PCBM. This result again the resulting polymer with a regioregularity greater than 90%
emphasizes the importance of controlling the band gap and was found.321 This is because the oxidative addition of the
corresponding energy levels of the polymer with respect to palladium catalyst takes place selectively at the less sterically
PCBM when the band gap starts to decrease. hindered 5-position of thiophene, leading to the formation
2-Pyran-4-ylidenemalononitrile (PYM) is known to have of the intermediate compound 264, which continues to
strong electron-withdrawing abilities and has been intensively polymerize to afford regioregular P141.
used as the electron acceptor part of red-emitting and Interestingly, the Heck reaction of the monomer 265
nonlinear optical materials.318,319 A series of copolymers designed to prepare regioregular PTV turned out to form the
utilizing the PYM unit as the electron acceptor were reported regioirregular polymer P142 due to 15% R-arylation occur-
by Dai and co-workers.320 Different amounts of PYM units ring during the reaction (Scheme 82). The regioregular P141
were copolymerized with thiophene units to yield the D-A- made by Stille coupling has a lower optical band gap, 1.6
type copolymers P139 and P140 (Scheme 81). It was found eV, than regiorandom P142 made by the Heck coupling
that the properties of the polymer can be controlled by where the band gap is 1.8 eV. When P141 was blended with
varying the PYM content ratio and the thiophene units. PCBM, an external quantum efficiency with a maximum
Increasing the thiophenes from P139a through P139b to response at 580 nm was detected. This is approximately 100
P139c results in red-shifted absorption spectra, gradually nm red-shifted compared to that of the device made from
reduced band gaps (2.33, 2.21, and 1.99 eV), higher HOMO the MDMO-PPV/PCBM blend. The PSC device based on
levels (-5.17, -5.10, and -5.01 eV), and relatively un- regioregular P141/PCBM (1:10, w/w) showed a moderate
changed LUMO levels. As expected, the increasing trend in PCE of 0.24%.322
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5911

Scheme 82. Synthesis of Regioregular P141 by a Stille Coupling Reaction and P142 with Defects by a Heck Coupling Reaction

Scheme 83. Synthesis of P143 with a Conjugated Side Chain by a Stille Coupling Reaction

Scheme 84. Synthesis of Poly(thienylenevinylene) P144

Scheme 85. Synthesis of Poly(thienylenevinylene) P145

The strategy of using branched side chains conjugated to polymer precursor 269, which can readily undergo thermal
the main chain of polythiophene has also been applied to elimination of the sulfinyl group to produce the 3,4-dihalo-
poly(thienylenevinylene)s. 2,5-Dibromothiophene 266 with substituted P144 with a high molecular weight of >50000.
a bis(thienylenevinylene) side chain was copolymerized with Its optical band gap was estimated to be ca. 1.55 eV. The
2,5-dibromo-3-hexylthiophene (104) and 1,2-bis(tributyl- active layer of a solar cell device was made by spin-casting
stannyl)ethylene (214) by a Stille coupling to form the the polymer precursor 269/PCBM (1:4, w/w) solution on top
bis(thienylenevinylene)-branched poly(thienylenevinylene) of the PEDOT substrate followed by thermally induced
P143 (Scheme 83).323 With an m/n ratio of 0.35, this polymer conversion at 70 °C to obtain the P144 and PCBM
shows a narrower band gap (1.57 eV) than poly((3-hexy- composite. After postproduction thermal annealing, the
lthienylene)vinylene) (P3HTV) (1.62 eV) and a strong broad device based on poly((3,4-dichlorothienylene)vinylene) gave
absorption band covering the whole visible region from a PCE of 0.18%. Following a similar mechanism, dithio-
380 to 780 nm. The PCE of the PSC based on P143/PCBM carbamate thiophene derivative 270 has also been developed
(1:1, w/w) reached 0.32%, which is higher than 0.21% for to serve as a facile precursor for the synthesis of poly((3,4-
P3HTV. diphenyl-2,5-thienylene)vinylene) (P145), which has en-
Another method is to prepare nonconjugated polymer hanced thermal stability and a lower band gap of 1.7-1.8
precursors, which produce conjugated polymers in situ upon eV (Scheme 85).325,326
thermal or chemical treatment. This indirect approach is
commonly applied to the synthesis of unsubstituted PTV to 7. Miscellaneous Conjugated Polymers
overcome the problematic processing resulting from the poor
solubility of PTV. The sulfinyl route was developed by 7.1. Poly(aryleneethynylene)s
Vanderzande and co-workers to prepare the 3,4-dichloro- and
3,4-dibromo-PTV derivatives P144 (Scheme 84).324 In the Poly(aryleneethynylene)s are a class of conjugated poly-
presence of sodium tert-butoxide as the base, the sulfinyl mers where aromatic or heteroaromatic groups are linked
monomer 267 was polymerized via the thiophene analogues by acetylene units. The internal triplet bonds in the polymer
of the p-quinodimethane intermediate 268 to obtain the main chain provide extended conjugation and rigidified
5912 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 86. Synthesis of P146 and P147 by a Sonogashira This can be rationalized by the fact that P150 is a fully
Coupling Reaction conjugated polymer whereas the conjugated length of P149
is disrupted by the amino groups. In spite of a shorter
conjugation length, P149 still has a relatively low band gap
due to efficient intramolecular charge transfer. The hole
mobility, measured by a hole-only device based on the space
charge limited current (SCLC), is determined to be 3.07 ×
10-5 and 4.58 × 10-5 cm2/(V s) for P150 and P149,
respectively. This indicates that incorporation of the triary-
lamine groups indeed improves the hole mobility. The high
mobility for P149 is translated to a higher Jsc of 2.85 mA/
cm2 and a higher PCE of 0.52% compared to those of P150
with a Jsc of 2.16 mA/cm2 and a PCE of 0.26%. It is also
noteworthy that the nonplanar 3-dimensional structure of the
triarylamine moiety makes the polymer more amorphous,
which may exert a detrimental influence on the interchain
charge carrier transport.
backbones for pronounced interchain interactions. To design Scheme 89 depicts the Suzuki coupling synthesis of
low band gap polymers for solar cell applications, donor and P151 containing tricyclic phenothiazine units from 40 and
acceptor moieties can be regioregularly separated by con- 286.330 The phenothiazine moiety with its electron-rich sulfur
jugated ethyne bridges. Scheme 86 shows the synthesis of and a nitrogen heteroatom incorporated into the polyfluorene
two poly(heteroaryleneethynylene) derivatives containing skeleton can potentially serve as the donor segment in
thieno[3,4-b]pyrazine as the acceptor and thiophene (P146) conjugated polymers and improve their hole-transporting
or dialkoxyphenylene (P147) as the donor, respectively, via abilities. In addition, attachment of two (phenylcyano)vinyl
the palladium-catalyzed Sonogashira coupling reaction.327 groups to the phenothiazine exerts an electron-withdrawing
Both materials have wide absorption ranges from 390 to 800 influence which reduces the band gap. The HOMO and
nm and low optical band gaps of ca. 1.57 eV due to LUMO of the resulting polymer P151 are -5.26 and -3.12
donor-acceptor push-pull effects through the conjugated eV, respectively. The band gap is 2.14 eV. This polymer’s
triple bonds. A device based on P146:PCBM (1:1, w/w) red-emitting luminescence in a thin film can be completely
showed a Jsc of 10.72 mA/cm2, a Voc of 0.67 V, and a PCE quenched in the presence of PCBM, implying efficient
value of 2.37%. When using P147:PCBM (1:2, w/w) as the exciton dissociation. The best photovoltaic performance was
active layer, the device exhibited a Jsc of 4.45 mA/cm2, a obtained from a device which used P151:PCBM (1:3 in wt%)
Voc of 0.7 V, and a PCE value of 1.36%. as the active layer; it showed a Jsc of 2.38 mA/cm2, a Voc of
Scheme 87 shows the synthesis of a new poly(aryle- 0.78 V, and a PCE value of 0.53%.
neethynylene) copolymer (P148) grafted with tetrathi- Two other phenothiazine-based copolymers, comprising
afulvalene (TTF) units via a Sonogashira coupling reaction bithiophene (P152) and thieno[3,2-b]thiophene (P153) moi-
between 278 and 279.328 This polymer has a conjugated eties, were also synthesized by Suzuki coupling reactions
main chain serving as the electron-deficient acceptor with (Scheme 90).331 The optical band gaps were calculated as
an electron-rich TTF side chain as the electron donor, 2.47 eV for P152 and 2.54 eV for P153. A device based on
inducing intramolecular charge transfer between the TTF side P152/PCBM (1:1, w/w) demonstrated the best PCE of
chains and the benzothiadiazole-containing main chain. X-ray 0.24%. This is in contrast to the P153/PCBM device, which
diffraction analysis suggests that strong self-assemby by π-π only showed a PCE of 0.1% albeit with a high Voc of 0.82
stacking through interdigitation due to the coplanarity of the V. Because the absorption of these polymers only covers
backbone leads to an optical band gap of 1.78 eV from its the 300-500 nm range, the relatively low device efficiencies
absorption edge. A polymer BHJ solar cell with the photo- are mainly due to the lack of sufficient absorption in the red
active layer of P148:C60 (2:1, w/w) showed a Jsc of 2.47 and near-infrared regions.
mA/cm2, a Voc of 0.42 V, an FF of 24.2%, and a PCE value
of 0.25%. 7.3. Fluorenone-Based Polymers
7.2. Triarylamine-and Phenothiazine-Based Fluorenone-containing conjugated polymers have also
attracted much interest for solar cell applications. It has
Polymers been shown that the incorporation of rigid and planar
Triarylamine-based small molecules or polymers have fluorenone subunits into the conjugated polymer not only
been extensively utilized as hole-transporting materials for enhances the intermolecular self-organized packing, but
light-emitting diode applications due to their high hole also effectively prevents chain folding. The latter is one
mobility. It is envisaged that the introduction of electron- of the most likely limiting factors for efficient charge
donating triarylamine segments into the polymer main chain transport.332 Furthermore, due to the electron-withdrawing
in conjunction with an electron-deficient unit would form effects of the ketone group, the fluorenone moiety exhibits
an alternating donor-acceptor arrangement. This should a wider absorption band covering a large part of the visible
potentially afford a polymer with a lower band gap and spectrum. This effect can be more pronounced when fluo-
improved intrinsic hole mobility. With this in mind, P149, renone units are conjugated with electron-rich units in the
which contains a triarylamine moiety in the main chain, and polymer. Two regioregular copolymers (P154333 and P155334)
its PPV derivative P150 were synthesized by a Heck coupling were synthesized by oxidative polymerization from the
reaction (Scheme 88).329 The optical band gap of P150 is monomers 290 and 291, respectively (Scheme 91). P154
1.76 eV, which is lower than that of P149 with 1.86 eV. contains alternating fluorenone and tetrathienylenedivinylene
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5913

Scheme 87. Synthesis of Poly(aryleneethynylene) Copolymer P148

Scheme 88. Synthesis of Triphenylamine-Containing Copolymer P149 and Its PPV Analogue P150

Scheme 89. Synthetic Route toward Phenothiazine-Containing Copolymer P151

Scheme 90. Synthetic Route toward Phenothiazine-Containing P152 and P153

units, while P155 consists of alternating fluorenone and served for both P154 and P155 in the solid state. This is
tetrathiophene units. Compared to the solution state, signifi- attributed to ordered interchain aggregation. The optical band
cant bathochromic shifts and broadened spectra were ob- gaps for P154 and P155 are 1.52 and 2.0 eV, respectively.
5914 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 91. Synthetic Route toward Fluorenone-Containing P154 and P155

Scheme 92. Synthesis of Porphyrin-Containing P156 by a Sonogashira Coupling Reaction

The best photovoltaic performance showed a PCE of 1.1% Scheme 93. Synthesis of P157
and 1.45% for the P154/PCBM- and P155/PCBM-based
devices, respectively.

7.4. Porphyrin-Based Polymers

7.5. Platinum Metallopolyyne-Based Polymers
Porphyrin derivatives have attracted considerable attention
as useful materials for organic photonic and electronic In addition to general strategies using organic donor and
applications due to their large π-conjugation systems as well acceptor segments in the main chain, platinum alkyne
as their good photochemical and thermal stabilities. The organometallic units have attracted a great deal of interest.
involvement of porphyrin derivatives in many biological They can be incorporated into the conjugated polymers as a
processes such as light harvesting and photoinduced electron result of the fact that the d-orbital of the Pt can overlap with
transfer in the photosynthesis of plants strongly suggests that the p-orbital of the alkyne unit, leading to an enhancement
porphyrin molecules could serve as potential photosensitizers in π-electron conjugation and delocalization along the
in dye-sensitized solar cells335,336 as well as electron donors polymer chain.339 Moreover, due to strong spin-orbital
in BHJ solar cell application. Although organic solar cells coupling, efficient intersystem crossing in such organome-
utilizing porphyrin-containing polymers as active layers have tallic species facilitates the formation of triplet excited states
been reported, only low power conversion efficiencies were which have longer lifetimes and thus allow extended exciton
obtained. This is presumably due to the limited light diffusion lengths. Electron transfer from this triplet-spin
absorption of porphyrins insofar that the absorption spectra donor to the acceptor produces a geminate ion-radical pair
of porphyrin units exhibit narrow, strong Soret bands which also retains the triplet character, so that charge
(410-430 nm) and weak Q-bands (530-540 nm) with recombination is spin-forbidden and the probability of
nothing in between.337 A soluble porphyrin-dithienothiophene efficient charge separation is enhanced compared with those
copolymer (P156) was synthesized by a Sonogashira cou- of the system involving only singlet exciton electron transfer.
pling reaction of 292 and 293 (Scheme 92).338 Introduction On the basis of these considerations, Schanze and Reynolds
of diethynyldithienothiophene into the porphyrin main chain reported a polymer (P157) containing alternate platinum
is expected to reduce steric hindrance, extend conjugation, acetylide and thiophene units.340 The trimethylsilyl protecting
enhance absorption, and improve the charge-transport prop- groups in 294 were in situ cleaved by tetrabutylammonium
erty. However, to ensure sufficient solubility of the porphy- fluoride, and the intermediate was coupled with Pt(PBu3)2Cl2
rin-containing polymer for solution processing, a large (295) in the presence of CuI to yield P157 (Scheme 93).341
aliphatic chain insulating portion must be incorporated into The phosphorescence of this polymer has a maximum at 609
the porphyrin unit, and this may have a negative effect on nm and was quenched upon the addition of PCBM. This is
the charge transport. Although a rather small PCE of 0.3% indicative of efficient electron transfer via the triplet excited
was obtained for the PSC using P156/PCBM (1:3, w/w) as state of the organometallic polymer. A photovoltaic device
the active layer, this value is among the highest obtained so made from the 1:4 (w/w) blend of P157 and PCBM gave a
far for devices based on porphyrin-containing polymers. PCE of 0.27% with a Voc of 0.6-0.7 V. Due to the high
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5915

Scheme 94. Synthesis of P158-P161

Scheme 95. Synthesis of P162

Chart 21. Chemical Structures of P163-P166

band gap of P157, the low efficiency is mainly due to its based on a 1:4 (w/w) blend of polymer/PCBM in the active
low coverage of the solar spectrum. layer. One noteworthy feature is that such a high performance
A series of platinum diacetylene-based polymers was obtained without thermal annealing, which is needed to
(P158-P161) containing electron-accepting bithiazole rings achieve a high efficiency for the P3HT-fullerene composite.
with different numbers of electron-donating thiophene units Right after this report, Janssen et al. commented on the
have been synthesized (Scheme 94) from their corresponding occurrence of such a high efficiency for P162 as reported
monomers 296-299.342 As the number of thiophene units by Wong et al. and created a controversy.344 It was argued
increases, the band gap of the polymer decreases from 2.4 that, on the basis of the optical data and the 70 nm film
to 2.0 eV, due to the extended π-electron delocalization thickness of the active layer as reported in the paper, the
through D-A intramolecular charge transfer. It was also highest PCE should not exceed 2.2%.
found from emission lifetime measurements that when the The potential of metalated conjugated polymers for use
content of the heteroaryl units increases to dilute the in PSCs continues to generate research where various
organometallic influence, these low band gap polymers only platinum polyyne-based conjugated polymers with different
exhibit singlet emission instead of triplet-excited-state phos- donor-acceptor arrangements are used.345-348 Very recently,
phorescence. As a result, unlike Pt-monothiophene P157 Jenekhe and co-workers further synthesized a series of
blends where charge separation occurs via the triplet state platinum diethylene-containing polymers in combination with
of the polymer, it is a charge-transfer excited state which is different electron-accepting units. These included pyrido[3,4-
responsible for the photoinduced charge separation. The b]pyrazine and thieno[3,4-b]pyrazine units (Chart 21).345 In
photovoltaic performance based on a polymer/PCBM (1:4, addition, a polymer exactly the same as P162 using ben-
w/w) showed an increasing trend for PCE values from 0.21% zothiadiazole as the acceptor was also prepared. The device
to 0.76% to 2.14% to 2.5% for P158 to P161, respectively. based on P162 reached a PCE of 1.4% when blended with
This is due to the increasing optical absorbance and hole PCBM and a PCE of 2.41% when blended with PC71BM.
mobility. This value is more consistent with the calculated 2.2% than
Wong and co-workers reported a thermally stable and air- with the prior experimental data. Moreover, BHJ solar cells
stable compound (P162) which contains a platinum metal- based on other polymers blended with PC71BM (1:4, w/w)
lopolyyne as the donor and BT units as the acceptor to afford gave lower PCE values, 0.68%, 0.36%, and 0.32% for P163,
a narrow band gap of 1.85 eV (Scheme 95).343 In a similar P164, and P165, respectively.
fashion, the polymer P162 was synthesized simply by Using a similar strategy, Jen et al. made a Pt-metalated
reacting a platinum dichloride (295) with a diacetylene conjugated polymer (P166) using thieno[3,2-b]thiophene-
moiety (300) under Sonogashira-type dehydrohalogenation connected benzothiadiazole as the core (Chart 21).348 Despite
conditions in the presence of a catalytic amount of copper this polymer being highly amorphous, a high hole mobility
iodide. Due to its lower HOMO level of -5.37 eV, the Voc of 1× 10-2 cm2/(V s) (in the field-effect transistor) was
obtained for the best cell was 0.82 eV with a very high Jsc achieved due to the more rigid structure enhancing the
of 15.43 mA/cm2. This resulted in a high PCE of 4.93% electron coupling between the donor and acceptor units along
5916 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 96. Synthesis of a P167-Derivatized Double-Cable Fullerene Using a Sonogashira Coupling Reaction

Scheme 97. Synthesis of a P169-Derivatized Double-Cable Fullerene by Postfunctionalization

the polymer backbone. The best performance of solar cell main chain and electron hopping between neighboring
devices based on P166 and PC71BM (1:4, w/w) resulted in attached fullerenes. The first double-cable polymer (P167)
a high PCE of 4.3% without the need of post thermal used in PSCs was reported by Janssen et al. and synthesized
annealing. by a Sonogashira reaction of diiodobenzene 301 having a
pendent methanofullerene and oligo(p-phenylenevinylene)-
7.6. Double-Cable Fullerene-Derivatized Polymers diacetylene 302 (Scheme 96).352 Photoluminescence quench-
ing was observed in a thin film of P167, which indicates
The most critical challenge in bulk heterojunction solar
efficient photoinduced electron transfer. Further evidence of
cells is that tremendous work is required to fine-tune the
efficient electron transfer is found in the photoinduced
complicated physical interactions between electron donor–
donor, acceptor-acceptor, and donor-acceptor units to absorption spectra, which show a characteristic band at 1.2
obtain an optimal morphology with a well-defined nano- eV due to the methanofullerene radical anion and two
structure. Different combinations of polymer-fullerene distinctive bands at 0.62 and 1.53 eV assigned to cation
blends led to completely different optimal conditions. Exces- radicals of the conjugated polymer. A PSC based on a
sive thermal annealing can eventually lead to undesirable double-cable polymer as the single component in the active
severe phase segregation. One promising way to solve this layer (no additional fullerene derivative blended) exhibited
problem is to covalently attach fullerene to a conjugated a Jsc of 0.42 mA/cm2, a Voc of 0.83 V, and an FF of 0.29.
polymer to form a so-called “double-cable fullerene-deriva- The low efficiency of the device based on this double-cable
tized polymer”, which can be regarded as a molecular polymer possibly results from the low content of fullerene
heterojunction.349-353 Such polymer structures ensure that relative to conjugated polymer, which limits the electron
donor and acceptor units are held in intimate proximity to transportation. P169, another double-cable polymer, was
facilitate exciton dissociation and furnish homogeneous synthesized by postfunctionalization of a thiophene-based
distribution to prevent potential phase separation. After conjugated polymer (P168) with C60 (Scheme 97).353 The
photoinduced electron transfer, the double cable creates two phenylenevinylene side chain is used to increase the conju-
ideal channels for both hole transportation in the conjugated gation of the polymer. The role of the long aliphatic spacer
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5917

Scheme 98. Synthesis of n-Type Copolymer P170 by Stille Coupling Reactions

Scheme 99. Synthetic Route toward Monomers 293 and 304

linking the backbone and C60 is to improve solubility and intramolecular charge transfer, which leads to an increased
simultaneously prevent donor-acceptor interaction in the coverage of the solar spectrum. Electron mobility of this
ground state. The surface morphology as studied by AFM polymer measured by FET reached as high as 1.3 × 10-2
showed that the P169 film is very smooth with an rms cm2/(V s) thanks to the high electron affinity and mobility
roughness of 1.4 nm, whereas the blend film of PCBM and of the PDI units as well as the planar structure of the fused
reference polymer P168 without the attached pendent C60 terthiophene. An all-polymer PSC was fabricated by blending
showed a roughness of 3.2 nm. These results indicate that P170 as the electron acceptor with P84 as the donor in the
the interpenetrating network in P169 is possibly improved active layer (1:1, w/w). The average PCE was found to be
as a result of the larger interfacial donor-acceptor area at over 1%, which so far is among the highest reported in all-
the molecular level. The maximum power conversion ef- polymer blend PSCs.
ficiency of the PSC based on this polymer reached 0.52%, The synthesis of dithieno[3,2-b:2′,2′-d]thiophene devel-
which is the best value for a double-cable polymer ever oped by Holmes and Frey is outlined in Scheme 99.355 The
reported. The fast recombination and inefficient hopping dilithiation of tetrabromothiophene (305) followed by quench-
electron transport probably accounts for the poorer results ing with 1-formylpiperidine afforded compound 306. In the
of double-cable polymers compared to blended BHJ solar presence of base in DMF, cyclization between the dialdehyde
cells. 306 and ethyl mercaptoacetate gave compound 307 via a
thiolate addition, bromo elimination, and sequential Aldol
7.7. n-Type Conjugated Polymers condensation to form the two outer thiophene rings. Hy-
drolysis of compound 307 gave the dicarboxylic acid 308,
While considerable efforts have been devoted to the design which underwent decaboxylation with copper in quinoline
and synthesis of new conjugated polymers with ideal p-type to yield 309.
semiconducting properties for BHJ solar cells, n-type materi- Alternatively, another n-type conjugated polymer (P171)
als are still dominated by the fullerene family because of containing alternating PDI units and CPDT units was
their outstanding electron-accepting and -transporting proper- synthesized by the Stille coupling of 310 and 151 (Scheme
ties, in particular a soluble member known as PCBM. 100).356 The HOMO and LUMO levels of P171 were
However, the major drawback of fullerene derivatives is their determined to be -4.02 and -5.52 eV. Having such a low-
weak absorption in the visible and near-infrared regions. The lying LUMO makes it a good candidate of n-type material.
employment of another complementary conjugated polymer Moreover, P171 showed reversible n-doping/dedoping and
in a polymer/polymer bulk heterojunction is an effective p-doping/dedoping in electrochemical processes. A PSC
approach for enhancing the light absorption ability of n-type device using P171 as the electron acceptor and P108 as the
materials. However, the search for an n-type conjugated electron donor in the active layer was fabricated and showed
polymer with improved light absorption and n-type properties a PCE of 0.43% with a Voc of 0.68 V and a Jsc of 1.4 mA/
comparable to those of PCBM is far more challenging cm.2
because the phase separation between two different conju-
gated polymers is more severe. Marder and co-workers 8. Conclusions and Future Prospects
reported a new conjugated polymer (P170) bearing alternat-
ing electron-rich dithienothiophene and electron-deficient With extensive research and accumulated practical experi-
perylenediimine (PDI) units (Scheme 98).354 The donor– ence that we have outlined in this review, the guidelines to
acceptor arrangement of the main chain induces a strong pursuing and developing p-type conjugated polymers be-
5918 Chemical Reviews, 2009, Vol. 109, No. 11 Cheng et al.

Scheme 100. Synthesis of n-Type Copolymer P171 by a Stille Coupling Reaction

comes evident. The requirements of specific intrinsic proper- outside this category is certainly desirable to fulfill the goal
ties necessary for an ideal donor material include (1) of creating the next generation of electron acceptors with
sufficient solubility to guarantee solution-processability as prominent electronic and stereochemical properties. Although
well as miscibility with n-type materials, (2) a low optical absorption abilities have been substantially enhanced as a
band gap for a strong and broad absorption spectrum to result of the benefits of band gap engineering, a large number
capture more solar energy, and 3) high hole mobility for of newly produced low band gap polymers with suitable
accelerating charge transport, which in turn allows a thicker energy levels still exhibited inferior device performance
active layer required for increased light harvesting as well compared to that of P3HT. Bulk morphological factors which
as reduced charge recombination and series resistance. In are closely related to charge dissociation and transport are
combination with a fixed electron acceptor, specific charac- mainly responsible for this discrepancy. With more complex
teristics between a D-A pair are required: these include (1) D-A conjugated polymer structures, the degree of stereo-
appropriate HOMO and LUMO energies to ensure a large regularity is decreased to some extent. Furthermore, branched
Voc and a downhill energy offset for exciton dissociation and solubilizing groups introduced into the polymers to ensure
(2) formation of an interpenetrating network with the solubility sometimes turn out to be able to attenuate
optimum morphology for creating two distinct bicontinuous intermolecular interactions in the solid state. As a result, the
highways for transporting free charge carriers. In addition polymers generally have more amorphous character, which
to the choice of viable molecular designs already in the usually results in poorer charge-transporting properties.
“toolbox” such as chemical planarization, quinoidiation, and Without optimal control of the morphology on the nanoscale,
D-A arrangement, a new influx of molecular designs and it becomes difficult to translate the microscopic intrinsic
synthetic endeavors has led to a range of novel p-type properties of the conjugated polymer into macroscopic device
conjugated polymers. These advances have ensured an important performance. The development of amorphous-oriented con-
step toward a better understanding of structure-property jugated polymers exhibiting high hole mobility might be an
relationships. Structural analysis of the current successful alternative way to overcome this problem and potentially
low band gap conjugated polymers reveals that an alternating eliminate the need of post-treatment to induce polymer
D-A arrangement is essential and must be combined with crystallinity.
the necessary newly designed donor segments composed of Beyond external treatments such as thermal or solvent
multicyclic aromatic rings with enforced planarity. In ac- annealing, bulk morphological engineering involving the
cordance with these guidelines, the further development of tailoring of interactions between D and D, A and A, and D
promising donors might be fortuitously directed toward and A at the molecular level may emerge as an attractive
hybridizing different electron-rich aromatic units into mutu- solution and initiate a new explorative direction. The
ally fused structures in the anticipation of benefiting from utilization of auxiliary supramolecular self-assembly between
the individual intrinsic advantages. This will require more conjugated polymers and fullerene derivatives provides a
elegant designs and challenging synthesis. With respect to broad window of interaction for the control of charge
the development of acceptor units, the electron-withdrawing separation and transport within a well-defined morphology.357
ability of an acceptor in a conjugated polymer needs to be The formation of self-organized double-cable conjugated
carefully tweaked to ensure both efficient ICT transition and polymers can be realized by careful controlled molecular
electron transfer. A too strong electron affinity will cause manipulation. Such a self-assembly-assisted arrangement can
the formation of electron traps with deep-lying LUMO levels, be permanently locked by smartly controlled lattice hardening
resulting in poor electron transfer to the n-type material and to improve the long-term thermal stability of the morphology.
hence low hole mobility. Among the wide range of acceptor Reactions triggered by light or heat for cross-linking the
units containing heteroaromatic rings with different electron molecular system would be an ideal strategy.358
affinities and resonance structures, the benzothiadiazole unit It is well-known that functional block copolymers are
appears to be the most promising acceptor with the potential capable of forming nanoscale phase separations with cylin-
of achieving superior results. This reflects its more balanced drical, lamellar, spherical, and bicontinuous morphologies.359
electronic properties and simple planar structure. A general It is of great interest that p-type- and n-type-containing block
feature of the existing acceptor units is that the additional copolymers have the potential to be used to precisely control
fused rings are extended in the axis perpendicular to the the nanostructure of the bulk heterojunction for improving
conjugated main chain. A range of more diversified structures the charge-separation at the p-n interface.
Conjugated Polymers for Solar Cell Applications Chemical Reviews, 2009, Vol. 109, No. 11 5919

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