Progress in Polymer Science 38 (2013) 1832–1908

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Designing ␲-conjugated polymers for organic electronics

Xin Guo, Martin Baumgarten ∗∗ , Klaus Müllen ∗
Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Conjugated polymers have attracted an increasing amount of attention in recent years
Received 23 January 2013 for various organic electronic devices because of their potential advantages over inor-
Received in revised form
ganic and small-molecule organic semiconductors. Chemists can design and synthesize
10 September 2013
a variety of conjugated polymers with different architectures and functional moieties to
Accepted 17 September 2013
Available online 24 September 2013 meet the requirements of these organic devices. This review concentrates on five con-
jugated polymer systems with 1D and 2D topological structures, and on one polymer
Keywords: designing approach. This includes (i) conjugated polyphenylenes (polyfluorenes, polycar-
Conjugated polymers bazoles, and various stepladder polymers), (ii) other polycyclic aromatic hydrocarbons
Organic electronics (PAHs) as substructures of conjugated polymers, (iii) thiophene and fused thiophene con-
Organic light-emitting diodes (OLEDs) taining conjugated polymers, (iv) conjugated macrocycles, (v) graphene nanoribbons, and
Organic field-effect transistors (OFETs) finally (vi) a design approach, the alternating donor–acceptor (D–A) copolymers. By sum-
Organic photovoltaics (OPV) marizing the performances of the different classes of conjugated polymers in devices such as
Polymer solar cells (PSCs) organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and polymer
solar cells (PSCs), the correlation of polymer structure and device property, as well as the
remaining challenges, will be highlighted for each class separately. Finally, we summarize
the current progress for conjugated polymers and propose future research opportunities
to improve their performance in this exciting research field.
© 2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1833
2. One-dimensional (1D) conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1834
2.1. Conjugated polyphenylenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1834
2.1.1. Linear and ladder-type polyphenylenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1835
2.1.2. Stepladder polyphenylenes with bridging atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1836
2.2. Polycyclic aromatic hydrocarbons-based conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1857
2.3. Thiophene-containing conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1860
2.3.1. Polythiophenes and their derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1860
2.3.2. Thienoacene-containing conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1862
2.3.3. Bridged bithiophene-containing polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1862
2.3.4. Benzodithiophene-containing conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1865
2.3.5. Naphthodithiophene-containing conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1865
2.3.6. Other fused thiophene-containing conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1866

∗ Corresponding author. Tel.: +49 6131 379 150; fax: +49 6131 379 350.
∗∗ Corresponding author. Tel.: +49 6131 379 142.
E-mail addresses: baumgart@mpip-mainz.mpg.de (M. Baumgarten), muellen@mpip-mainz.mpg.de (K. Müllen).

0079-6700/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.progpolymsci.2013.09.005
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1833

2.4. Donor–acceptor polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1866

2.4.1. Donors and acceptors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1867
2.4.2. One-dimensional D–A polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1870
3. Two-dimensional (2D) conjugated polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1880
3.1. Conjugated macrocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1880
3.1.1. Carbazole and fluorene-based macrocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1880
3.1.2. PAHs-based macrocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1883
3.1.3. Thiophene-based macrocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1884
3.2. Graphene nanoribbons from polyphenylene precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1885
3.2.1. Solution synthesis of GNRs using polyphenylene precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1887
3.2.2. Surface-mediated synthesis of GNRs using polyphenylene precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1889
3.3. Two dimensional donor–acceptor polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1891
3.3.1. 2D mD–sA polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1891
3.3.2. Benzo[1,2-b:4,5-b ]dithiophene-containing 2D D–A polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1892
4. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1895
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1896
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1896

1. Introduction processibility, (2) high molecular weights, (3) band gap and
absorption behavior, (4) HOMO and LUMO energy levels,
Conjugated polymers as semiconducting materials have and (5) suited morphology with low barriers. These factors
attracted broad academic and industrial interest for vari- are dependent on each other and must be comprehensively
ous optoelectronic devices. In particular, their applications considered for specific applications. For instance, side
in polymer light-emitting diodes (PLEDs), polymer solar chains play a significant role for improving the solubility
cells (PSCs), and organic field-effect transistors (OFETs) and the obtainable molecular weight of conjugated poly-
offer opportunities for the resolution of energy issues mers, but also influence their intermolecular interactions
as well as the development of display and information through changes in morphology and thereby the charge
technologies [1]. In comparison with inorganic materials carrier mobility. Tuning the energy band gap for obtaining
and small-molecule organic semiconductors, conjugated the desired absorptions will usually change the HOMO and
polymers provide several advantages including low cost, LUMO energy levels, and thus change the emitting color
light weight, and good flexibility. More importantly, sol- in an OLED or influence the open-circuit voltage (Voc ) in
uble polymer semiconducting materials can be readily a PSC. Therefore it is necessary to fully account for these
processed and easily printed, removing the conventional designing principles and balance the guiding concepts in
photolithography for patterning, which is a critical issue pursuit of ideal polymers for specific applications.
for the realization of large-scale roll-to-roll processing of The extension of dimensionality strongly affects the
printed electronics [2]. optoelectronic properties of conjugated polymers as
Since poly(p-phenylenevinylene) (PPV)-based PLEDs well. Most polymer systems usually possess conven-
were reported in 1990 [3], a large library of polymer tional one-dimensional (1D) structures with continuous
semiconductors have been synthesized and investigated. ␲-conjugations along the polymer backbone. Extending
Organic chemist have developed tremendous amounts of the conjugation in the lateral direction of polymer back-
building blocks, such as fluorene, carbazole, thiophene and bones can lead to different supramolecular structures in
its fused derivatives, benzothiadiazole and its derivatives, the solid state and to multidirectional charge transport
rylene diimides, and diketopyrrolopyrrole (see structures [10]. In particular, graphene, which is considered as an
in Scheme 1.1), which have been employed to design vari- ultimately sized two-dimensional (2D) polymer, possesses
ous polymers according to individual demands for specific extraordinary electronic, thermal, and mechanical proper-
applications. One particular approach was the application ties making it a promising candidate for many practical
of alternating donor (D) and acceptor (A) units to steer applications [11]. Other 2D polymers containing D–A struc-
the HOMO and LUMO levels, as well as the band gap of ture also exhibited promising performances in the PSCs
the resulting copolymers (so-called D–A polymers), which [12].
is an efficient strategy for tailoring the properties of con- In this review, we try to summarize the broad scope
jugated polymers for applications in OFETs and PSCs [4]. of publications that have reported on various 1D and 2D
Based on this strategy, current p-type and n-type mobi- conjugated polymers exhibiting high performances, or at
lities have reached 8.2 and 3.0 cm2 /V s [5,6], respectively, least desirable potentials in PLEDs, PSCs, and OFETs from a
and power conversion efficiencies (PCEs) of around 9% have viewpoint of material oriented chemists. The operational
been achieved for PSCs [7,8]. A world record for a tandem mechanisms of these organic electronic devices have been
bulk hetero junction (BHJ) organic solar cell reached 12% outlined many times before, and the synthetic details of
very recently [9]. all described polymers, as well as device fabrication, can
To design conjugated polymers for different applica- be found in the original publications, not needed to be
tions several general principles should be kept in mind, described here in detail. This review is organized into two
including (1) side chains to enhance the solubility and sections, namely, 1D conjugated polymers (Section 2) and
1834 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 1.1. Typical building blocks as fluorene, carbazole, thiophene and its fused derivatives, benzothiadiazole, diketopyrrolopyrrole, and rylene diimides.
2D conjugated polymers (Section 3). In this vein four sorts
of 1D conjugated polymers, specifically, (i) conjugated
polyphenylenes (Section 2.1), (ii) conjugated polymers
from polycyclic aromatic hydrocarbons (PAHs) (Section
2.2), (iii) thiophene and fused thiophene containing conju-
gated polymers (Section 2.3), and (iv) 1D D–A conjugated
polymers (Section 2.4) will be discussed in Section 2,
respectively. Particularly, fluorene- and carbazole-based
(Sections 2.1.2.1 and 2.1.2.3) conjugated polymers and
their derivatives have become vitally significant for appli-
cations in organic electronics in the past decade, while
D–A polymers (including 1D and 2D cases (Sections 2.4
and 3.3)) have achieved extremely high performances
in both PSCs and OFETs applications in recent years, and
represent a popular research topic. Section 3 includes
three parts, namely, (i) conjugated macrocycles (Section
3.1), (ii) graphene nanoribbons (Section 3.2), and (iii) 2D
D–A conjugated polymers (Section 3.3). Among them,
graphene nanoribbons will be especially highlighted
because currently their synthesis and applications are one
of the most intriguing research areas. Finally, Section 4
will present a brief summary and outlook on conjugated
polymers to conclude. We hope that after reading this
review researchers will have a clear grasp of the advance-
ments of conjugated polymers, past and present, to gain
inspirations toward designing new conjugated polymers
for applications in organic electronics.
2. One-dimensional (1D) conjugated polymers
Most conjugated polymers possess 1D ␲-conjugated
backbones. Early research focused on poly-para-
phenylenes (PPPs) and polyphenylenevinylenes (PPVs),
and then extended to various polyphenylene deriva-
tives such as ladder-type poly-para-phenylenes (LPPP)
and shorter bridged so-called stepladder polymers, like
polyfluorenes (PFs), polycarbazoles (PCz), and polyinde-
nofluorenes (PIFs). Among these polymers, PFs and PCz
have attracted the highest attentions and have been widely
studied as active materials in PLEDs and PSCs. A variety of
PAHs have also been used as repeating units of conjugated
polymers and tested as blue emitters. Thiophenes are
another important class of building blocks, which were
used to make conjugated polymers for OFETs and PSCs. All
these building blocks can be used as donor units combined
with electron-deficient acceptor units for the construction
of alternating D–A copolymers, resulting in the rapid
evolution of high-performance charge transporting and
photovoltaic polymer materials.
This section is divided into four parts to describe the four
classes of 1D conjugated polymers mentioned above. The
D–A polymers containing fluorene, carbazole, indenofluo-
rene and some other PAHs as donor units will be discussed
in Section 2.1 (conjugated polyphenylenes) and Section 2.2
(PAHs-based conjugated polymers) rather than in Section
2.4 (D–A polymers).
2.1. Conjugated polyphenylenes
In the last two decades, conjugated polyphenylenes
have formed one of the most extensively studied classes
of conducting polymers and have been used in vari-
ous organic electronic devices [13]. Poly-para-phenylene
(PPP, 1 Scheme 2.1.1), the simplest but most impor-
tant conjugated polymer, and their derivatives have been
developed as early as in the 1960s and used for many sig-
nificant applications [14,15]. Unfortunately, unsubstituted
PPP is insoluble and intractable, limiting its characteriza-
tion, reproducibility, and thereby its proper applications.
Introducing solubilizing substituents onto the main chain
can improve the solubility of the PPP, which, however,
leads to increasing torsion between neighboring repeating
units and thereby interrupts conjugation to quite an extent
[16,17].
In order to increase the conjugation and bathochromi-
cally shift the fluorescence into the visible region, several
methods were applied including the use of phenylen-
vinylenes in the polymer backbone and the fully or partially
planarized neighboring phenylene units via carbon or het-
eroatoms (such as Si and N) bridges. This resulted in
the tremendous development of linear polyphenylenes
derivatives such as PPVs, LPPPs, stepladder polyphenylenes
and their heteroatoms bridged analogs (see structures in
Schemes 2.1.1 and 2.1.2). These methods can restrict the
rotation between the repeating units, improve the solubil-
ity and the stability of the polymers, and adjust the optical
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1835

Scheme 2.1.1. Linear and ladder-type polyphenylenes and polyphenylenevinylenes.

and electrochemical properties of polyphenylenes. In this
part, the development of these conjugated polyphenylenes
will be reviewed and their optoelectronic properties will
be described. In particular, emphasis will be put on PFs and
PCz, both of which have become vitally important conju-
gated polymers for applications in organic electronics in
the past decade.
2.1.1. Linear and ladder-type polyphenylenes
PPP 1 has good thermal stability and large band gap of
about 3.5 eV and therefore can be used as active compo-
nent of blue PLEDs [18]. Nevertheless, it is undefined and
not solution processable. As mentioned above, side chains
can be easily introduced into the phenylenes (2) to improve
solubility, however, emissions shift into the UV region. To
obtain visible emitting color, the neighboring phenylene
units in PPP could be planarized via a methine bridge while
still carrying solubilizing side chains. In this vein, fully lad-
derized poly-para-phenylenes (3) (LPPPs) were developed
as demonstrated in Scheme 2.1.1 [19,20]. It turned out that
this fully planar alignment of polymer backbone led to a
strong enhancement of the conjugation, which was indi-
cated by bathochromically shifted optical absorptions. The
photoluminescence of 3 was obviously red-shifted com-
pared to that of non-bridged PPP, with maximum emission
at 450 nm in diluted toluene, but both photoluminesce-
nce in the solid state and electroluminescence shifted to
600 nm [21], partially explained by excimer formation and
ketone-defects [22]. To overcome the yellow-green emis-
sions, a stepladder copolymer with dialkylated phenylenes
incorporated into LPPP main chains was synthesized, which
suppressed the excimer formation and displayed blue
1836 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.2. General formulas of stepladder polyphenylenes with methine bridges.
emission in the PL and EL spectra owing to the distorted
structure of the copolymer [21,23]. Another LPPP deriva-
tive 4 containing spiro-fluorene at bridged carbons was also
developed, where no low energy emission was observed in
PL spectra of thin films even after annealing at 110 ◦ C for
24 h in air [24].
Quite a different class of linear conjugated poly-
mers derived from phenylenes is polyphenylenevinylenes
(PPVs), which are very renowned semiconducting poly-
mers and widely applied in PLED and PSCs. Unsubstituted
PPV 5 (Scheme 2.1.1) was initially prepared by way of a
solution-processable precursor and first used as an electro-
luminescent polymer in a large-area LED with an emission
in the green-yellow region in 1990 [3]. Later on, the stud-
ies on PPV were focused on improving the solubility by
introducing side chains into the backbone (typically via a
Gilch method [25]), which made PPV-based polymers able
not only to be solution-processable but also to tune the
light-emitting color covering the whole visible region.
The most important soluble PPV is poly[2-methoxy-5-
(2 -ethylhexyloxy)-1,4-phenylene vinylene] 6 (MEH-PPV).
The development of the PSCs was propelled in 1992 by
photophysical studies on a bilayer of 6 with C60, which
revealed an ultrafast, reversible, metastable photo-induced
electron transfer from 6 to C60 in solid films [26]. More-
over, it was also the first conjugated polymer applied to
fabricate a flexible “plastic” LED emitting orange light with
an external quantum efficiency of about 1% [27].
Most PPV derivatives have low electron affinities and
are commonly used as donor materials in PSC devices.
By introducing electron-withdrawing cyano groups on the
vinylenes, polymer 7 (CN-PPV) exhibited a larger electron
affinity and narrower band gap leading to red emission and
utilization of high work-function aluminum as a cathode of
LEDs. High internal efficiencies of up to 4% were achieved
based on such devices with 7 as the emitting layer [28].
This polymer was used for the first time as a polymer elec-
tron acceptor in a two-layer PSC fabricated by a lamination
device processing technique, providing an IPCEmax of 29%
and a PCE of 1.9% [29].
2.1.2. Stepladder polyphenylenes with bridging atoms
There was a strong need for stable and pure blue-light
emitting polymers being solution-processable in order
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
to prepare large-area LEDs. The linear polyphenylenes
discussed above regardless of PPP, LPPP, or PPV, could
not match such requirements. Thereby, further research
interests were raised to design and develop so-called
stepladder polymers, namely, partially ladderized PPPs,
where two or more adjacent phenylene units in the poly-
mer backbone were planarized by additional methine
bridges (Scheme 2.1.2) or other bridgehead atoms such as
N, Si, and P (Schemes 2.1.17–2.1.20).
Among them, carbon bridged stepladder
polyphenylenes have attracted substantial research
interest because of their relative easy of synthesis,
fewer defects, and excellent photophysical properties
as comparison with the fully ladderized polymers. More
importantly, the absorption and fluorescence properties
of these stepladder polyphenylenes can be well tuned by
varying the size of the bridged unit. For examples, the
emission maximum of polyfluorenes (8, PFs, Scheme 2.1.2)
is around 420 nm, while those for polyindenofluorenes (9,
PIFs), ladderized polytetraphenylenes (10), and ladderized
polypentaphenylenes (11) are gradually red-shifted from
430 nm to around 440–445 nm, as shown in Fig. 1 [13,30].
Before considering the important exchange of the
methine bridges by other heteroatoms we will first discuss
PFs, a most widely studied class of conjugated polymers.
2.1.2.1. Polyfluorenes (PFs). Polyfluorenes are the most
shining star in conjugated polymers because of their use
in various polymer optoelectronic devices, such as LEDs,
OPVs, FETs, chemical and biosensors, lasers, memories, and
light-emitting electrochemical cells (LECs) [31a]. PF com-
prising coplanar fluorene as repeating unit can be regarded
as that each adjacent pair of phenylene groups in the PPP
is flattened by methylene bridges [31b]. The 9-position
carbon atom of fluorene unit adopts a sp3 hybrid, where
various functional substituents can be introduced at this
position. Furthermore, the ease of functionalization of the
2,7-postions of fluorene allowed facile preparation of poly-
merizable monomers, which led to a large amount of PF
homo and copolymers to meet the requirements of organic
devices. During the past ten years, a tremendous amount
of fluorene-based conjugated polymers were published.
Hence only extremely important and highly representa-
tive examples will be presented here and other reported
fluorene-based polymers can be found in a recent review
[31a].
2.1.2.1.1. PFs as blue-light emitting polymers for PLEDs.
PFs are regarded as the most promising candidates for blue
PLEDs because of structural features that lead to facile func-
tionalization as discussed above, and promising properties,
such as excellent chemical stability, great thermal stability,
good film-forming property, and high fluorescence quan-
tum yield in solid state (˚PL = 0.55) [32]. However, PFs
with solubilizing alkyl substituents at the 9-position have
suffered from low EL efficiency, poor color stability, and
insensitive emission to human eyes. The three problems
will be separately discussed below, combined with their
suggested solutions to achieve better results.
(1) Reason of low EL efficiency and solutions
1837
Poly(9,9-dialkylfluorene), like poly(9,9-di-n-
octylfluorene) (12, PFO, Scheme 2.1.3), has a large
band gap with low HOMO and high LUMO energy
levels of −5.80 and −2.12 eV, respectively [33]. Partic-
ularly, a big difference between the HOMO level of PFO
and the work function of PEDOT modified ITO (−5.2 eV)
makes it difficult for hole injection from the anode.
On the other hand, PFO exhibits good hole transport
[34], but its electron affinity is very low, which results
in inefficient combination of charge carriers and
therefore low efficiency of exciton formation. The
unbalanced injection and transport of charge carriers
also can cause their combination in the region close
to electrodes, thereby leading to the quenching of the
excitons. Therefore, electron-rich and electron-poor
groups were introduced into PFs, in order to improve
the injection and transport of charge carriers, and thus
the EL efficiency.
Triphenylamine and its derivatives are typical
electron-rich compounds, which have been used to
enhance the hole injection and transport of PFs by
incorporating them either as side chains (13) [35], as
end-groups (14, 15) [36], or in the main chains (16, 17)
[37,38]. Among them, the triarylamine end-capped PFs
had a higher HOMO level of −5.48 eV and emitted in the
deep-blue region with brightnesses of up to 1600 cd/m2
and EL efficiencies higher than 1.1 cd/A at 8.5 V. The EL
efficiency increased by one order of magnitude com-
pared to the non-end-capped PDAF without disturbing
the electronic and chemical structure of the backbone.
In addition, carbazole is also used to improve the hole
injection and transport by being introduced into PFs
[39–41].
Although the problem of electron injection can be
overcome by using low work-function metals such as
calcium as cathodes, another layer of aluminum on top
of calcium must be used because of the reactivity of
such metals. Thereby, the electron-deficient units were
used to improve the electron accepting ability of PDAFs.
A PF polymer (18) containing electron-withdrawing
aryloxadiazole groups at the 9-position of fluorene
was developed, which had a LUMO level of −2.47 eV
and showed an EQE of 0.52% from an EL device, two
times higher than PDAF under same device processing
conditions [42]. Such electron-withdrawing units have
also been employed as comonomers inserted into the
main chains of PDAF (19) [43], as pendant groups of
PDAF (20) [44], and as end-capping groups (21) [45].
The other electron-deficient units introduced to PDAFs
for improving electron injection include cyano groups,
quinoxaline, thiazolothiazole, etc. [46–49].
Another approach was to develop a PF copolymer
bearing both electron-rich and electron-poor groups
such as copolymer 22. The HOMO and LUMO levels
of this polymer are −5.30 and −2.47 eV, respectively,
suggesting that the electron and hole injections were
simultaneously improved. The EL device with this poly-
mer as an active layer exhibited a much improved
EL efficiency (1.21%) compared to PFO 12 (0.2%)
[50].
(2) Reason of poor color stability and solutions
1838 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Fig. 1. Normalized fluorescence spectra of stepladder polyphenylenes 8, 9, 10, 11 and LPPP 3 in dilute toluene solution (10 ␮g/mL) at room temperature.
Ref. [30], Copyright 2007.
Reproduced from Wiley-VCH Verlag GmbH Co.
PDAFs suffer from the tendency to generate an unde-
sired long-wavelength emission band around 530 nm
during device operation, and upon heat treatment or pho-
toirradiation, which result in red-shifted emission spectra
and reduced device efficiency. It was initially believed to
arise from the formation of excimers [51–59]. However,
this point was argued [60] and subsequently a new point
of view was established, claiming that the long-wavelength
emission arose from fluorenone defects, probably formed
by oxidation of incomplete alkylated bridgeheads [61–63].
A possible mechanism for the formation of fluorenone
defects is provided in Fig. 2 according to the most accepted
approach [64–68].
To avoid these defects, careful purification of the
monomers and attempt to decrease polydispersity of poly-
mer were described [69,70]. Crosslinking PDAFs derivatives
containing functional end-groups was found to suppress
the long wavelength emission as well [71,72]. However, the
most widely used method to avoid the appearance of long
wavelength emission is to incorporate bulky groups such as
dendrimers, aryl substituents, and spiro-linked structures
into PFs to reduce defect formation or to suppress exciton
migration to defect sites.
Attachment of bulky dendrimers at bridgeheads has
been examined as a means to suppress interchain inter-
actions. The suppression of the long wavelength emission
could be achieved by attaching polyphenylene dendrimers
as 23 in Scheme 2.1.4. The emission from 23, however, is
still not completely stable over time, possibly because of
the susceptibility of the benzylic linkages to oxidation [73].
By directly attaching the dendrons to the bridgehead, poly-
mer 24 was developed, which was exceptionally thermally
stable and displayed stable blue EL [74]. Other dendrimers
such as Fréchet dendrons (25 and 26) and carbazole-based
dendrons (27) have also been introduced into PFs as side
chains [75–77]. Suppression of the long-wavelength emis-
sion could be observed for these polymers but was related
to the number of the dendrimer generation.
Stable blue emission is also observed from the poly-
mers (28–30, Scheme 2.1.5) with alkyl or alkoxyl phenyl
groups attached at the 9-position of fluorene [73,78,79].
Additionally, above-mentioned polymers 13, 18, and 22
(Scheme 2.1.3) containing triphenylamine and oxadiazole
substituents at bridgeheads could not only improve the
injection and transport, but also prevent ketone defects,
as in 28–30 through their aryl groups inhibiting the green
emission. Another effective approach to obtain stable PL
and EL emissions is the application of spiro-linked struc-
tures. An alternating copolymer 31 has been found to
give a more stable emission than a homopolymer 12, but
green emission was still observed upon heating in air at
150 ◦ C [80]. By contrast spirobifluorene homopolymers 32
and 33 produced a more stable blue light without green
emissions even with annealing at 200 ◦ C [81,82]. Other
spiro-linkages have also been introduced at the 9-position
of fluorene for stabilizing the emission. Polymers, both 34
and 35, displayed stable blue PL and EL upon annealing
[83,84].
It should be noted that both aryl-substituted and
dendronized PFs can stabilize the blue emission. Bulky den-
drimers in 24, on the other hand, can increase the lifetime
of triplet excited states, which may reduce the efficiency
of LEDs because of increasing singlet–triplet quenching
[85,86]. Thus the small-size aryl substituents are recom-
mended rather than bulky dendrimers for suppressing the
long wavelength emission.
Copolymerization with other emitting or bulky units
is another method used to obtain stable blue emission
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1839

Scheme 2.1.3. PFs with charge-carriers injection and transport units.

1840 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Fig. 2. Proposed mechanism for formation of fluorenone defects in PDAFs.

Scheme 2.1.4. PFs with bulky dendrimers on bridgehead carbon atom.

from PFs. A copolymer 36 (Scheme 2.1.6) containing 15% 3,6-carbazole (37) and more twisted units through seven-
anthracene has been reported to produce a stable blue membered ring formation with O or S bridging as in 38
emission, which remains stable even upon annealing up and 39, have also been made for suppression of long-
to 200 ◦ C for three days [87]. PF copolymers containing wavelength green emission bands [88,89]. Hyperbranched

Scheme 2.1.5. PFs with aryl and spiro-linked substituents on bridgehead carbon atom.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.6. PFs with bulky units in the main chain and as end groups.
comonomers with strong steric effects were copolymer-
ized with fluorene to produce network polymers such as
40 and 41, which have high fluorescence quantum yields
in both solution and solid-state, and display stable blue EL
[90,91]. In addition, attachment of bulky substituents at the
chain ends such as polyhedral siloxanes (42), has also been
found to significantly reduce the long wavelength emission
compared to PDAFs without end-capped groups [92].
(3) Reason of insensitive emission to human eyes and solu-
tions
A human eyes sensitivity curve is shown in Fig. 3,
defined by the Commission Internationate del’Eclairage
Fig. 3. Curve of human eyes sensitivity to light according to its color [95].
(For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
1841
(CIE), and describes the visual light characteristics of
human eyes. The human eye is most sensitive to a color
at around 555 nm, in the yellow-green region of the opti-
cal spectrum. The sensitivity decreases rapidly toward the
blue and red regions. In the blue region, the human eye is
most sensitive around 440–450 nm [93,94], while PFs typi-
cally emit at 420 nm. Thus for better eye catching visibility,
the emission color of PFs need a moderate shift to longer
wavelength. On the other hand, in order to ensure a high
color purity, the CIE coordinates should be in a pure blue
region as well, apart from the emission wavelength within
the appropriate range.
One solution is to prepare new conjugation extended
polyphenylenes with chemical structures intermediate
between those of PF and LPPP, for example ladderized
polytetraphenylene and polypentaphenylene (10 and 11,
Scheme 2.1.2), which will be discussed in Section 2.1.2.2.
Another solution is to tune the emission color of PFs to the
pure blue region by incorporating a lower energy unit com-
pared with PF, which traps the excitons and becomes the
emitter. This is a so-called “host–guest” or “host–dopant”
system, where PF serves as a host, but the low energy unit
as a guest or dopant (hereinafter referred to as dopant). In
fact, this strategy cannot only improve the color purity by
tuning the emission color of PFs, but also the EL efficiency
on account of the energy transfer from PF host to dopant
units. However, it is difficult to seek out a proper blue
dopant since it must possess a suitable band gap, ensuring
pure blue emission after incorporating into PFs, and good
spectroscopic overlap with the PF host.
A few fluorene-based copolymers with the CIE coor-
dinates in the pure blue region have been reported. A
PF copolymer (43, Scheme 2.1.7) that contains bis(2,2-
diphenylvinyl)fluorene attached orthogonally to the
9-positions of fluorene was reported to show a maximum
external quantum efficiency of 1.06% with color coordi-
nates of (0.15, 0.17) [96]. Its analog with triphenylamine
replacing 2,2-diphenyl (44) exhibited a high EL perfor-
mance with an LE of 2.87 cd/A and CIE coordinates of
(0.15, 0.18), but this was realized by blending 44 in a host
polymer and the maximum emission shifted to 461 nm
that was close to green-blue region [97]. Covalent
1842 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 2.1.7. PFs derivatives with highly efficient pure blue emission.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1843

attaching a fluorescent dye 4-dimethylamino-1,8-
naphthalimide (˚PL = 0.84) to the side chains of PF,
an efficient blue light-emitting polymer 45 was developed.
The single-layer device exhibited the maximum luminance
efficiency (LE) of 6.85 cd/A with the CIE coordinates of (0.15,
0.19) [98]. By incorporating 1 mol% 2-hexylbenzotriazole
(HBT) into the main chain of PFO (46) a fluorene-based
copolymer with the CIE coordinates of (0.15, 0.17), an
LE of 2.69 cd/A, and good EL spectroscopic stability was
developed [99]. Copolymer 47 consisting of alternating
dialkylfluorene and substituted meta-phenylene units
carrying hole (carbazole and triphenylamine) as well
as electron (oxadiazole) transporting units in the side
chain showed a maximum efficiency of 2.50 cd/A with CIE
coordinates of (0.16, 0.08) [100].
By incorporating 7,7,15,15-tetraoctyldinaphtho-s-
indacene (NSI) into the backbone of PFO (12), a series of
blue light-emitting copolymers (48) were developed. The
insertion of the NSI unit into the PFO backbone led to
an increase of local effective conjugation length, forming
low-energy fluorene–NSI–fluorene (FNF) segments which
served as exciton trapping sites. Energy transfer could
occur from the high-energy PFO segments to the low-
energy FNF segments, which caused these copolymers
to show red-shifted emissions compared with PFO, with
a high efficiency, good color stability, and high color
purity. The best device performance with a maximum
EL at 448 nm, an LE of 3.43 cd/A, a maximum brightness
of 6539 cd/m2 , and CIE coordinates of (0.15, 0.16) was
achieved [101].
2.1.2.1.2. PFs as host materials for RGB and white PLEDs.
PFs are excellent host materials owing to their high PL
efficiency, large band gap, and good charge carrier trans-
porting properties. They were widely used as a host to
realize highly efficient RGB and white PLEDs through either
physical blending or chemical doping. In this review, we
focus on the chemical variations, namely, the host/dopant
system in which, as previously mentioned, efficient and fast
Förster energy transfer from larger-band-gap PF segments
to a narrow-band-gap dopant may occur leading to highly
efficient emission solely or predominantly from the latter
[101,102]. Meanwhile, the trapping of excitons formed on
PF segments at low-energy sites resulted in an improved
color stability. Blue light-emitting polymers with PF as a
host have been discussed above, and thus green, red, and
white light-emitting polymers with PF as a host will be
further presented next. The EL performances of typical PF-
based polymers are listed in Table 1.
Copolymer 49 (Scheme 2.1.8) containing benzothiadi-
azole (BTZ) in the PF backbone is a representative green
light-emitting polymer. A device comprised of this poly-
mer has a low turn-on voltage of 2.25 V and exhibits a
peak efficiency of 10.5 cd/A at 6600 cd/m2 at 4.85 V with
very good stability [103]. By tuning the content of BTZ
unit in the PF backbone, an LE as high as 10.9 cd/A and
a maximum brightness of 22,800 cd/cm2 was obtained
[104]. Attaching a naphthalimide derivative as the pendant
of PF, polymer 50 was synthesized and a maximum LE
of 7.45 cd/A with CIE coordinates of (0.26, 0.58) were
observed based on a single-layer device [105]. Apart from
incorporating electron-withdrawing units into PFs for real-
ization of green emission, copolymerization with some
electron donor units such as thienothiophene (51) [106],
bisthiophene (52) [107], and perylene (53) [102] were

Table 1
EL performances of typical PF-based polymers (Vonset : onset voltage; Bmax : maximum brightness; LEmax : maximum luminous efficiency; PEmax : maximum
power efficiency; EQE: external quantum efficiency; CIE1931: CIE color coordinates created by the CIE in 1931).

Polymer Vonset (V) Bmax (cd/m2 ) LEmax (cd/A) PEmax (lm/W) EQE (%) CIE1931 (x, y) Ref.

Blue 13 ∼4.0 – 0.84 0.45 – 0.19, 0.18 [35]

14 3.5 1600 1.1 0.4 – 0.15, 0.08 [36]
18 5.3 2770 0.25 0.08 0.52 – [42]
22 4.4 4080 0.63 0.19 1.21 0.19, 0.14 [50]
24 6–7 380 – 0.06 – 0.19, 0.24 [74]
28 3.7 820 0.03 – – 0.14, 0.16 [78]
33 – – – – 0.017 0.16, 0.07 [81]
34 6.0 1600 0.19 0.06 0.20 0.17, 0.12 [83]
43 4.6 3137 1.42 – 1.06 0.15, 0.17 [96]
45 3.5 ∼9000 6.85 5.38 3.54 0.15, 0.19 [98]
48 3.3 6539 3.43 – 2.42 0.15, 0.16 [101]

Green 49 2.25 10,000 10.5 – – 0.40, 0.58 [103]

50 4.8 21,595 7.43 2.96 – 0.26, 0.58 [105]
53 12 – 0.9 – 0.6 0.36, 0.56 [102]

Red 55 10.6 ∼850 1.45 – 2.54 0.66, 0.34 [109]

56b – 2104 0.91 – 3.1% 0.64, 0.33 [111]
59 8 – 1.6 – 0.5 0.64, 0.34 [102]
60 4.9 4321 2.8 – 1.59 – [113]
61 ∼3.5 ∼10,000 8.3 7.5 – 0.63, 0.35 [116]

White 62a – 11,100 5.3 2.8 – 0.25, 0.35 [125]

63 3.5 18,480 12.8 8.5 5.4 0.31, 0.36 [129]
64 5.8 12,040 18.0 8.38 6.36 0.33, 0.35 [135]
66 4.0 12,710 7.3 4.17 – 0.31, 0.32 [136]
67 7.2 6994 6.2 – 3.84 0.35, 0.34 [140]
69 2.8 ∼1000 8.2 7.2 3.7 0.35, 0.38 [143]
71 3.1 6770 2.96 2.33 1.37 0.34, 0.35 [146]
1844 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.8. PF-based green light-emitting polymers.
proven to shift the emission of PFs to the green visible
region.
Red light-emitting polymers could be obtained by incor-
porating small-molecule red emitters into PFs. Polymer
54 (Scheme 2.1.9) is a typical red light-emitting material,
which exhibited an LE of 1.5 cd/A with CIE coordinates of
(0.67, 0.33) [103]. Attaching two alkyl chains at the thio-
phene units of 54 improved the fluorescence quantum yield
of polymer 55 in the solid state, but the EL efficiency and
CIE coordinates (1.45 cd/A and (0.66, 034), respectively)
were similar to those of the parent polymer [108,109].
Benzoselenadiazole (56a) and naphthoselenadiazole (56b)
have also been used as low-band-gap units to realize red
emissions, leading to a red-shift of 50 nm compared with
analogs containing benzothiadiazole [110–112]. For exam-
ple, polymer 56b emitted at 657 nm and the external
quantum efficiency based on a single-layer reached 3.1%
with CIE coordinates of (0.64, 033) [111]. Perylene dyes,
a class of typical red light-emitting chromophores, could
be attached to PF chains either as end-capping groups at
the chain termini (57), as pendant side groups (58), or as
comonomers in the main chain (59), to achieve red emis-
sions. The best EL efficiency from these polymers is up to
1.6 cd/A [102].
Another class of red light-emitting small molecules
introduced into PFs is iridium-based complexes with triplet
emissions. In such polymers, the singlet energy is trans-
ferred from the PF sections to the iridium complexes
where finally red phosphorescence is emitted. The first
reported red electrophosphorescent PF-based material was
polymer 60, from which an EL efficiency of 2.8 cd/A was
achieved [113]. Then many such materials were reported
and recently a maximum LE of 8.3 cd/A with CIE coordi-
nates of (0.63, 0.35) was realized based on a polymer 61
[114–116].
White EL from polymers can be realized using several
strategies such as the multilayer-device system [117–119],
the single-layer polymer-blend system [120–124], and a
single-polymer system [125]. However, the first two have
some disadvantages, for instance, the interfacial mixing
of different layers for the former and the intrinsic phase
separation for the latter, which limit their applications.
These problems are avoidable in a single-polymer sys-
tem. An important approach for designing a single-polymer
emitting white light is based on the color principles to
introduce two or three different emission components (for
instance blue and orange, or blue, green, and red) into a sin-
gle polymer which can produce balanced emissions from
every component by controlling partial energy transfer and
charge trapping. PF is usually used as a host polymer serv-
ing for a blue emission and one or two dopant units are
introduced as long-wavelength emission components.
The first single white polymer 62a (Scheme 2.1.10) was
reported in 2004, exhibiting an LE of 5.3 cd/A with CIE
coordinates of (0.25, 0.35) [125]. Although the color coor-
dinate was not quite close to a pure white-light point of
(0.33, 0.33), this propelled a number of studies on single-
component white light-emitting polymers. Successively,
many similar two-color white polymers such as 62b and 63
were reported with improved EL efficiency and more pure
color coordinates [126–131]. Other ways such as introduc-
ing iridium complexes as long-wavelength emission units
[132,133] and constructing polymers with star-like archi-
tectures [134,135] have also been used to design single
white polymers. In particular, a star-like single polymer 64
using orange emissive species as the central core and PFs as
the outer arms has been made and exhibited a high current
efficiency of 18.0 cd/A and a power efficiency of 8.38 lm/W
with CIE coordinates of (0.33, 0.35) [135].
The three-color white single polymers have been
prepared by realizing simultaneous singlet emissions
from blue, green, and red components (65, 66 and 67,
Scheme 2.1.11) [136–142] and mixing singlet and triplet
emissions in PF polymers (68 and 69) [143–145]. It was
found that the EL efficiency was higher when moving a
dopant unit from polymer backbone to side chains. For
example, polymer 66 with both green and red dopants at
side chains showed a higher current efficiency of 7.3 cd/A
compared to 1.6 cd/A for polymer 65 with green dopant at
side chains and red dopants in main chains [136].
All of the single white light-emitting polymers dis-
cussed above, regardless of consisting of two- or three-
color and singlet or mixed singlet and triplet emitters, were
achieved based on a mechanism of partial energy transfer
and charge trapping on dopant in the EL process. Another
strategy to realize white EL from a single polymer was pro-
posed based on a new mechanism of electron trapping on
the host rather than charge trapping on the dopant. Sev-
eral polymers (70, 71 and 72, Scheme 2.1.12) containing
phosphonate-functionalized PFs as the blue light-emitting
host have been designed according to such a mechanism.
The single polymers containing phosphonate groups show
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.9. PF-based red light-emitting polymers.
white EL with CIE coordinates (0.34, 0.35) at 8 V when the
dopant content is up to a centesimal level, which is two
orders of magnitude higher than for those without phos-
phonate groups. Moreover, the EL devices based on these
phosphonate-substituted polymers can be fabricated using
high-work-function and air-stable Al as cathode without
inserting an electron-injection layer [146].
2.1.2.1.3. PFs as donor materials for polymer solar cells.
PF-based polymers have also been widely applied in the
PSCs. However, the homopolyfluorenes are inappropriate
for the solar-electricity conversion owing to their weak
absorptions in the visible region of the solar spectrum.
By copolymerizing fluorene units with other aromatic
building blocks, in particular electron-deficient units, the
absorptions of the resulting polymers could be remark-
ably red shifted. The fluorene units in such copolymers
are responsible for improving the solubility via attaching
solubilizing groups at the 9-position and maintaining the
conjugation in the whole copolymer backbone. They are in
most cases used as donor materials blended with fullerene
derivatives such as PCBM to fabricate bulk-heterojunction
solar cells. The performances of such PF-based PSCs are
summarized in Table 2.
One of the most important fluorene-based polymers for
solar cells is an alternating copolymer 73a (Scheme 2.1.13),
1845
whose films showed obvious red-shift with the maxi-
mum absorption wavelength at approximately 545 nm
compared with PDAFs. This could be attributed to the
neighboring BTZ, thiophene, and fluorene moieties by low-
ering the band-gap and thereby largely improving the
light absorption in the visible range. The PSC with a con-
figuration of ITO/PEDOT:PSS/73a:PCBM/LiF/Al showed a
PCE of 2.2% [147]. Polymers 73a–d were synthesized by
introducing different alkyl chains to investigate the influ-
ence of substituents on the packing of the polymers and
the morphology of the active layer, which will lead to dif-
ferent photovoltaic performances [148]. Among them, the
polymer 73c with octyls exhibited the best PCE of 2.6%
[149,150].
Many additional PF copolymers such as 74–78 with
other acceptor units to replace BTZ in 73 have successively
been reported [151–161]. A typical alternative of BTZ is
thienopyrazine, which was incorporated into PF main
chains to prepare polymers 74a–c. Within this series of
polymers, the polymer 74b provided a best PCE of 2.2%
when blended with PCBM [157]. Other acceptor units
flanked with two thiophenes were introduced in the PF
backbone, including thiadiazoloquinoxaline (TQ) [154],
quinoxaline [155–157], pyrazino[2,3-g]quinoxaline [158],
diketopyrrolopyrrole (DPP) [159,160] and so forth. The
1846 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 2.1.10. PF-based two-color white light-emitting polymers.

corresponding copolymers 75–78 exhibited narrow band
gaps and broad absorption bands. Among them, polymer
76 yielded a PCE of 3.7% based on a blend device with PCBM
under standard AM 1.5 solar illumination [156]. Polymer
78 containing DPP as an acceptor showed a moderate PCE
lower than 1%, but DPP has emerged as a promising accep-
tor to synthesize D–A polymers for high-performance PSCs
and OFETs. This will be discussed in detail in Section 2.4.
Recently, polymers 79a and b were reported with a new
acceptor containing thienopyrazine moiety. A PCE of 1.4%
was achieved from 79b/PCBM-based solar cells [162].
In addition to using electron-withdrawing units several
other methods have also been attempted to decrease
the band gap and tune the absorption behavior of the
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1847

Scheme 2.1.11. PF-based three-color white light-emitting polymers.

Table 2
Typical PF- and PCz-based polymers for the PSCs (Jsc : short-circuit current density; Voc : open-circuit voltage; FF: fill factor; PCE: power conversion efficiency).

Polymer:acceptor (w:w) Jsc (mA/cm2 ) Voc (V) FF PCE (%) Ref.

73a:PCBM (1:4) 4.66 1.04 0.46 2.2 [147]

74b:PCBM (1:3) 8.88 0.59 0.42 2.2 [155]
75a:C70 derivative (1:4) 3.4 0.58 0.35 0.7 [154]
76:PCBM (1:3) ∼6 ∼1 0.63 3.7 [156]
77:PCBM (1:3) 6.5 0.81 0.44 2.3 [158]
78: PCBM (1:2) 2.0 0.78 0.50 0.78 [160]
79b:PCBM (1:4) 5.35 0.52 0.50 1.38 [162]
107:PDI (1:4) 0.26 0.71 0.37 0.63 [221]
108e: PCBM (1:4) 1.56 0.8 0.55 0.8 [223]
109c: PCBM (1:4) 6.92 0.89 0.63 3.6 [225]
109c: PCBM (1:2) 10.22 0.89 0.51 4.6 [226]
109c: PCBM (1:4) 10.6 0.88 0.66 6.1 [227]
109c: PCBM (1:4)Alcohol/water-soluble polymer as the cathode interlayer 12.7 0.9 0.59 6.8 [228]
109c: PCBM (1:4) MoO3 -Al composite film as the cathode buffer layer 10.88 0.88 0.71 6.8 [229]
110c:PCBM (1:1) 5.16 0.41 0.29 0.61 [230]
111b:PCBM (1:2) 5.35 0.76 0.56 2.3 [159]
1848 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 2.1.12. Single-component white light-emitting polymers based on a mechanism of electron trapping on the host.

fluorene-based polymers, such as incorporating silole
moieties (80) [163,164], selenium-containing heterocycles
[110], rigid ribbon-type building blocks (pentacene and
anthradithiophene) [165], and heavy metal platinum [166]
into the PF main chains. All of these polymers possess
narrower band gap and red shifted absorption compared
to PF homopolymers, but the PCE of solar cells were
generally lower than 3%. In view of the high performance
(PCE higher than 7%) of other polymers for example
benzodithophene-based D–A copolymers, the research on
fluorene-based polymers for PSC have shown a downward
trend in recent years.
2.1.2.1.4. PFs as semiconducting polymers for FETs. PFs
are typical hole transporting materials and their charge
mobilities are highly sensitive to phase morphology [61].
It has been demonstrated that relatively high hole mobil-
ity of up to 8.5 × 10−3 cm2 /V s can be achieved when PFO
(12) was oriented in the nematic phase [167]. Another PF
derivative 81 (Scheme 2.1.14) with alkylidene substitution
has increased conjugation lengths and better coplanarity
compared to PDAFs. This polymer gave a FET mobility of
2 × 10−3 cm2 /V s and on/off ratios of 104 –106 at its nematic
mesophase [168].
Besides the PF homopolymers, many PF copolymers
have been developed for application in polymer FETs.
Some of them have been discussed above as light-
emitting and photovoltaic materials. The classical green
copolymer derived from 9,9-dioctylfluorene and BTZ
(49, Scheme 2.1.8) has higher electron-transport abil-
ity than PFO, and exhibits ambipolar properties with
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1849

Scheme 2.1.13. Typical PF-based polymers as donor materials for solar cells.

an electron mobility of 10−3 cm2 /V s and a hole mobil-
ity of 2 × 10−3 cm2 /V s [169,170]. Polymers 73c and 75a
that were widely investigated as PSC materials have
also been reported as hole conductors with mobili-
ties of 1.1 × 10−3 cm2 /V s and 0.03 cm2 /V s, respectively
[171,172]. The above-mentioned polymers 79a and b
showed even higher hole mobilities of up to 0.2 cm2 /V s
in OFETs [162].
The most promising fluorene-based polymers for OFETs
are fluorene and bithiophene copolymers, such as 82a and
b [173]. Polymer 82a possesses excellent thermotropic liq-
uid crystallinity and a hole mobility of up to 0.01–0.02 with
alignment of polymer chains in the LC phase [173,174].
Inkjet printing of this polymer after annealing led to a
transistor with a charge mobility of 0.02 cm2 /V s with an
on/off ratio of 105 [175]. By contrast, polymer 82b pro-
vided a relatively lower hole mobility of 8.4 × 10−5 cm2 /V s,
probably owing to its unaligned polymer chains [176].
Replacing thiophene rings in 82a by selenophene moi-
eties, polymer 83 was prepared and presented better FETs
performance. Solution-processable polymer FETs based on
83 with a thermotropic liquid-crystalline phase exhib-
ited a hole mobility of 0.012 cm2 /V s and a low threshold
voltage of −4 V [177]. Another polymer 84 containing a
fused thieno[3,2-b]thiophene in the PF backbone yielded
better FET mobility of 1.1 × 10−3 cm2 /V s by comparison
with 82a (4.0 × 10−4 cm2 /V s) under the same processing
conditions. This improvement could be attributed to
its higher crystallinity and a more ordered morphology
[178].
1850 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.14. Representative fluorene-based polymers for OFETs.
2.1.2.1.5. Alcohol/water-soluble PFs. Alcohol/water-
soluble PFs have become an important class of conjugated
polymers for sensor applications partially due to their ease
of accessibility and relatively high fluorescence quantum
yield. These polymers typically have a conjugated PF
main chain providing good conductivity for charge trans-
port and polar pendant groups endowing the polymers
with good solubility in highly polar solvents such as
methanol, ethanol, and even water. More importantly,
these alcohol/water-soluble polymers can be deposited as
electron injection and transporting layers (EIL) on top or
below another active layer casted from unpolar solvents
(principle of orthogonal solvents) for fabricating fully
solution-processed devices such as LECs, PLEDs and solar
cells [31a]. In such devices fabricated using alcohol/water-
soluble polymers as an EIL, high-work-function metals
(such as Al, Ag, or Au) can be employed as the cathode
because of their good environmental stability and the sim-
plicity for device processing. Typical polar groups attached
to PF side chains include dimethylammonium and their
quaternary salts (85–88) [179–182], diethanolammonium
(89 and 90) [183–185], and phosphonate (91) [186].
Several representative examples of alcohol/water-soluble
PFs are shown in Scheme 2.1.15.
Ammonium-functionalized polyfluorene 85 and its qua-
ternary salt analog 86 as EIL materials for highly efficient
PLEDs were first reported in 2004 [180]. The unique elec-
tron injection property of these alcohol/water soluble
conjugated polymers was demonstrated, leading subse-
quently to rapid development of EIL materials. A cationic
water-soluble polyfluorene 87 containing ion-transporting
side groups and alkali or alkaline earth metal ions was
synthesized. For PLEDs with polymer 87 as EIL, a high
LE of up to 15.4 cd/A was found for green fluorescence
using Al cathodes. In particular, when the Ca containing
derivative of 87 was used, an extremely high external
quantum efficiency of 4.8% was obtained, approaching the
theoretical limit of about 5% [181]. Although these poly-
electrolytes as EIL can improve electron injection from
high-work-function metals, they sometimes encounter
problems with counter ions migration into the emissive
layer, thereby reducing the long-term stability of such
devices [187]. In addition, it has also been demonstrated
that the electron injection ability of these polyelectrolytes
is strongly influenced by the nature of their counter ions
(88) [188]. Therefore, neutral PF-based organic surfactants
were developed as EIL materials.
The neutral organic surfactants, diethanolammonium-
functionalized PFs 89 and 90, were synthesized and applied
as EIL materials to improve the device performance of
PLEDs [183,184]. Highly efficient phosphorescent PLEDs
using 89 as the EIL exhibited an LE as high as 43.0 cd/A for
green emission and 14.2 cd/A for blue emission with a sta-
ble Al cathode. These efficiencies were much higher than
those made from commonly used CsF/Al cathode [183]. For
Li2 CO3 -doped polymer 90 as the ETL, white light-emitting
PLEDs with a maximum LE of 36.1 cd/A and PE of 23.4 lm/W
were achieved [185].
Phosphonate-functionalized PFs (91) are another class
of important neutral polyelectrolytes. Not only they serve
as EIL materials [101,116], but also as EL polymers them-
selves as well as candidates for chemo sensor applications
[186,189,190]. As chemosensory materials, these polymers
are highly sensitive and selective for Fe3+ with an emis-
sion quenching up to 210-fold upon addition of Fe3+ .
The PLEDs constructed with 91 as emitting layer and Al
as cathode display a maximum LE of 4.0 cd/A, which is
attributed to the efficient electron injection from Al to
the active layer due to the phosphonate groups. Addi-
tionally, the above mentioned single-component white EL
polymers 70–72 (Scheme 2.1.12) based on a mechanism
of electron trapping on the host were realized with this
phosphonate-functionalized PF as the blue light-emitting
host material [146]. Similar water/alcohol soluble light-
emitting polymers with green, yellow, and red emissions
(92) have also been obtained by doping different nar-
row band gap units in the ammonium-functionalized PFs
main chains [191–193]. The alcohol/water-soluble PFs as
conjugated polyelectrolytes for other applications such as
electrochromic color-changing displays, photodetectors,
and chemical and biological sensors can be found in a rel-
evant review [194].
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.15. Examples of alcohol/water-soluble PFs.
2.1.2.2. Other carbon bridged stepladder polyphenylenes.
Besides PFs and PIFs, ladderized polytetra- and polypenta-
phenylenes (Scheme 2.1.16) are important carbon bridged
polyphenylenes. Their alkyl-substituted homopolymers
were initially developed based on the consideration of
bathochromically shifting the emission of PF to the pure
blue region because they possess chemical structures
intermediate between PF and LPPP. Successively, many
derivatives based on these ladderized multi-phenylene
monomers have also been prepared and thoroughly
investigated. In particular, copolymers derived from inde-
nofluorene (IF) attracted a lot of research interest.
The alkyl-substituted PIFs 93a and b (Scheme 2.1.16)
were reported for the first time in 2000 [93]. Their absorp-
tion and emission bands are slightly red-shifted compared
with those of PFs, with the PL emission maxima in solution
occurring at around 430 nm. The color stability of PIFs,
however, was similar to that of PFs, demonstrating that
93a and b were green emitters with solid-state lumi-
nescence (PL and EL) at around 560 nm, although 93b
was slightly more stable with blue emission to start but
rapidly undergoing a red shift [55]. This red-shift was
ascribed to aggregation, and the green emission located at
560 nm observed from 93a was attributed to more efficient
exciton migration to defect sites [195]. To circumvent the
green emission problem, several approaches have been
adopted. Stable blue EL has been obtained from a copoly-
mer with anthracene 94, presumably because of exciton
1851
confinement on the anthracenes [196]. The polymer 95
bearing diaryl side chains was also synthesized. The emis-
sion from 95 was blue in both solution and the thin film
without green emission being observed [197]. Another
polymer 96 containing spiro-linked substituents at both
carbon bridges also served for blue emission [198].
Apart from endeavoring to achieve stable blue emis-
sion from IF homopolymers, several IF-based copolymers
have also been made and studied for organic electron-
ics. Bisthiophene and terthiophene have been used for
copolymerization with IF to afford polymers 97a and b,
both of which exhibited green emissions peaked at 529 nm
for 97a and 554 nm for 97b. The FETs of the two poly-
mers showed mobilities of 1.5 × 10−5 cm2 /V s for 97a and
1.1 × 10−4 cm2 /V s for 97b, respectively. The higher value of
terthiophene-containing polymer was attributed to highly
regular dense packing resulting in well-defined fibrillar
morphology. By contrast, such dense ␲-stacked structures
were not observed for 97a [199,200].
The IF was used to replace the fluorene in some of the
above-mentioned fluorene-based low-band-gap copoly-
mers. For the polymers applied in the PSCs, the IF unit was
regarded as a donor component to deepen HOMO level
and thus achieve higher Voc , while for those used in the
PLEDs it was expected to function as a blue light-emitting
host to realize long-wavelength and white emissions. By
replacing fluorene in polymer 73c (Scheme 2.1.13) with
IF, polymers 98a was synthesized. The absorption band of
1852 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 2.1.16. Polyindenofluorenes, ladderizedpolytetraphenylenes, ladderizedpolypentaphenylenes and their derivatives.

this polymer became more intense and was red-shifted
relative to that of the fluorene-based analog. A Voc of 0.77 V,
a Jsc of 5.50 mA/cm2 and a PCE of 1.70% were obtained
from the 98a/PC71BM-based solar cells [201]. The FETs of
the polymers with hexyl and dodecyl at carbon bridges
exhibited hole mobilities of up to 0.011 cm2 /V s [202].
Further replacing BTZ in 98a with thienopyrazine, polymer
98b was synthesized demonstrating a band gap of 1.6 eV
that was lower than that of 98a (1.9 eV). However, a PSC of
this polymer as a donor and PC71BM as an acceptor yielded
a PCE of only 0.45% [201]. Polymer 98c was prepared as an
EL material with the blue-green emission and low turn-on
voltages [203]. White EL from an IF-based polymer 99
was realized, in which IF functioned as a host material
to replace fluorene in polymer 67 (Scheme 2.1.10). By
controlling the content of green and red dopants, a white
EL device was achieved with a maximum brightness of
4088 cd/m2 at 8 V and CIE coordinates of (0.34, 0.32) [204].
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.17. Structures of poly(3,6-carbazole)s and poly(2,7-carbazole)s.
Another important IF derivative is polymer 100, which
was developed as the first air-stable ambipolar polymer.
The FETs based on this polymer exhibited balanced electron
and hole mobilities of 2 × 10−4 cm2 /V s with on/off ratios of
∼104 under ambient conditions [205].
The emission from PIFs is still in the deep blue region
and therefore polytetraphenylene 101 was synthesized as
a pure blue light-emitting polymer. The maximum emis-
sion occurred at 442 nm in both solution and thin film
that was more close to human eye sensitivity than those
from PFs and PIFs. However, the EL spectrum exhibited an
extra band at 510 nm, which did not appear to be a result
of defects from oxidation, as heating 101 in air produced
a band at 575 nm, but was interpreted to arise from an
interaction between the polymer and the metal cathode
[206]. When copolymerizing with dithienobenzothiadi-
azole (DTBT), this copolymer 102 showed promising
performances in solar cells. A PCE of 3.67% with a Voc of
1.06 V was realized using a 102/PC61BM blend, while a
higher PCE of 4.5% was obtained when using PC71BM as
the acceptor [202].
Continuing to extend the size of the ladderized multi-
phenylene monomers with carbon bridges, ladderized
pentaphenylene and its corresponding polymer 103 were
designed and synthesized. The emission from this poly-
mer was pure blue with an emission maximum at 445 nm
and a very small Stokes shift. The EL device provided a
best LE of 0.5 cd/A with CIE coordinates of (0.17, 0.09).
An analysis of the sensitivity curve proved that polymer
103 had its maximum at a region where the human eye
is 3 times as sensitive as for PIFs and 6 times as sensi-
tive as for PFs, generating a sufficiently pure blue emission
spectrum optimized to the human eye. Although the blue
emission from 103 was much more stable than that from
alkyl-substituted LPPP, a long wavelength emission band
still appeared rapidly upon heating in air [94]. To replace
the alkyl chains at all bridgehead positions in 103 with
aryl substituents, polymer 104 was prepared, which gave
remarkably stable blue emission in PLEDs and was not
subject to oxidative degradation-induced defect formation
even after prolonged heating at 200 ◦ C in air [207].
2.1.2.3. Polycarbazoles (PCz) and other N-containing bridged
stepladder polyphenylenes. The incorporation of nitrogen
atoms instead of methylene bridges into a polypheny-
lene changes the chemical and electronic behavior of
the polymers [13]. This can be tracked back to vary-
ing reactivity of the positions around the benzene rings
and the increased HOMO energy levels resulting in
1853
electron-rich materials. The simplest nitrogen-bridged
polyphenylenes, namely polycarbazoles (PCz), are one
of the most widely studied organic semiconductors on
account of their photoconductive properties and ability to
form charge transfer complexes arising from the electron-
donating character of the carbazole moiety [31,208].
Other stepladder polyphenylenes containing nitrogen
bridges, for example poly(indolo[3,2-b]carbazole)s [209]
and poly(diindenocarbazole)s [206], have also been devel-
oped and studied as active materials in PLEDs and PSC.
Early studies on PCz were centered on non-conjugated
poly(N-vinylcarbazole) (PVK) that could be used as photo-
conductive polymers, and serve as host materials in PLEDs
because of their high energy singlet excited state with
absence of low energy triplet state. They also serve as
hole transporting material blended with TiO2 in DSSCs
[210]. Then conjugated PCz was synthesized and investi-
gated widely. PCz can be synthesized by two ways. The
first is to connect the carbazole units at the 3,6-positions
to form poly(3,6-carbazole)s (105, Scheme 2.1.17), and
the second is to link them via the inactive 2,7-positions
to yield poly(2,7-carbazole)s (106). While in carbazole
itself electrophilic substitution occurs at the 3,6-positions
rather than at the 2,7-positions as in fluorene. Poly(3,6-
carbazole)s and their derivatives can thus be easily
obtained using 3,6-disubstituted carbazole as monomers.
However, their applications in organic electronics are
limited owing to the difficulties of obtaining high molec-
ular weights and because of poor conjugation within the
kinked backbone. Despite this, 3,6-carbazole-based poly-
mers are still used as blue emitters themselves and as host
materials because of their large band gap and good hole
transporting ability [211–213]. An OFET based on n-butyl
substituted poly(3,6-carbazole) showed a hole mobility of
10−3 cm2 /V s [214]. On the other hand, poly(3,6-carbazole)
possesses a high triplet energy level, which renders them
interesting as hosts for blue or green phosphorescent emis-
sions with high EL efficiencies [215]: for example, green
electrophosphorescent polymers with poly(3,6-carbazole)
as host were recently designed and synthesized, showing
high efficiency of 33.9 cd/A [216].
Poly(2,7-carbazole)s cannot be prepared by routes
starting from carbazole owing to the weak reactivity of
2,7-positions as mentioned above. Following a route sug-
gested by Cadogan for the reduction of nitrobiphenyls in
order to synthesize 2,7-functionalized carbazole, poly(2,7-
carbazole)s and their derivatives were readily obtained
by various polycondensations and have attracted a lot of
research interests [217,218]. These polymers were initially
1854 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.18. Typical poly(2,7-carbazole)s-based polymers for solar cells.
applied in blue PLEDs. Poly(N-alkyl-2,7-carbazole)s 106
produced stable blue emission with maximum wave-
length at 437 nm in the solid state, without green emission
appearing after annealing or upon operating an LED
[218,219]. However, the EL efficiencies for devices using
these polymers were modest [220].
In recent years, poly(2,7-carbazole)s have been
regarded as a promising class of polymers for photovoltaic
applications thanks to good hole transporting properties,
great versatility to fine tune the bandgap, and low HOMO
energy levels that provide good air-stability and a high Voc
in BHJ solar cells [210]. The OPV data of these polymers are
presented in Table 2. The first solar cell using poly(n-alkyl-
2,7-carbazole) as active material was reported in 2006
[221]. Long and branched alkyl chains were introduced
(107, Scheme 2.1.18) to improve the solubility and pro-
cessability of the PCzs. In first attempts toward solar cells,
both perylenetetracarboxydiimide (PDI) and PCBM were
compared as acceptors. Thereby it was confirmed that
the 107/PDI (1:1) blend devices afforded a 3 times higher
PCE than those of 107/PCBM-based ones under the same
conditions. The device with 107/PDI (1:4) blend gave
an overall PCE of 0.63% [221]. Another small-molecule
acceptor based on 2-vinyl-4,5-dicyanoimidazole was also
applied to blend with 107 for BHJ solar cells, yielding a bit
higher PCE of 0.75% [222].
To improve the light-harvesting ability, oligothiophenes
were introduced into the poly(2,7-carbazole)s main chains
(108a–e). This method could tune the band gap of the poly-
mers depending on the addition of thiophene units. The
best device performance was achieved from 108e with a
PCE of 0.8% [223].
All the above-mentioned poly(2,7-carbazole)s-based
polymers exhibited modest efficiencies, typically lower
than 1%. The breakthrough in terms of PCE of poly(2,7-
carbazole)s was obtained by incorporating strong
acceptors into the polymer chains. Polymers 109a–f
with different acceptor units were therefore synthesized
and provided promising device results [224]. Polymer 109c
had a band gap of 1.88 eV, a HOMO level of −5.5 eV, and
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
exhibited a hole mobility of 1 × 10−3 cm2 /V s and a high
PCE of 3.6% [225]. Carefully optimizing the processing con-
dition of device fabrication allowed an improvement of the
PCE up to 4.6% [226]. The 109c-based device efficiency was
further improved to 6.1% when blending with PC71BM and
inserting a hole-blocking layer of TiOx under aluminum
cathode [227]. By inserting an alcohol/water-soluble PF-
based polyelectrolyte (85, Scheme 2.1.15) as an interlayer
between the active layer and Al cathode, the efficiency of
109c:PC71BM based devices was pushed further to 6.79%
[228]. Quite recently, a similar PCE of 6.77% with a FF of
70.7%, based on an inverted PSC with 109c:PC70 BM blend
as active layer, the MoO3 –Al composite film as the cathode
buffer layer, and the MoO3 /Al as the anode, was achieved
[229].
As alternatives to BTZ in 109c, as described for the
PF copolymers, TQ and DPP have also been introduced
into poly(2,7-carbazole) to develop polymers 110 and 111
[230–232]. TQ-based polymers usually showed low Voc
and thereby modest PCE. For example, the devices with
110c:PCBM (1:1) as the active layer exhibited a PCE of
0.61% with a low Voc of 0.41 V [230]. DPP-containing poly-
mer 111a delivered a PCE of 1.6% based on the 111a:PCBM
Scheme 2.1.19. Other stepladder polyphenylenes containing nitrogen bridges.
1855
BHJ solar cells, but the performance reached 2.3% by vary-
ing the alkyl side chains on both the carbazole and the
DPP units (111b) [159,232]. Another 2,7-linked carbazole-
based conjugated copolymer (112) containing ladderized
pentaphenylene with diketone bridge as an acceptor was
developed, showing potential for photovoltaic devices due
to the efficient energy and charge transfer between donor
and acceptor units in the solid state [233].
Apart from PCz, other nitrogen-containing bridged
stepladder polymers such as indolo[3,2-b]carbazole-based
polymers 113 and 114 with all-nitrogen bridges, and
polymers 115–117 with both carbon and nitrogen bridges
(Scheme 2.1.19) were developed for optoelectronic
applications [206,209,234]. Poly(diindenocarbazole)
115 displayed blue emission without an extra band at
510 nm in the EL spectrum compared with polymer 101
(Scheme 2.1.14) containing all carbon bridges. The EL
efficiency, however, from unoptimized devices was as low
as 0.1 cd/A [206]. Comparing 116 and 117, it was found that
the emission was red-shifted and the HOMO energy level
was higher for the latter because of the larger number of
electron-donating nitrogens. When applying them in solar
cells using blends of the polymers with a fullerene, polymer
1856 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.1.20. Heteroatom bridged stepladder polyphenylenes.
117 gave the best device result with a PCE of 0.74% [234].
Indolo[3,2-b]carbazole-containing homopolymers were
obtained by both meta- and para-linked ways and they
exhibited obvious differences in charge carriers transport
and conductivity [209,235]. Indolo[3,2-b]carbazole exhib-
ited stronger electron-donating ability and higher hole
mobility than carbazole [236] and thus were applied as a
donor unit for copolymerization with acceptors. Polymers
118a–e and their analogs with meta-coupled indolo[3,2-
b]carbazole in the main chains were thus developed for
PSC applications [237–239]. Within this series of polymers,
118c exhibited a best photovoltaic performance with a PCE
as high as 3.6%, a Voc of 0.69 V, JSC of 9.17 mA/cm2 and a FF of
0.57, applying a device structure of ITO/PEDOT:PSS/118c:
PCBM/LiF/Al [238].
2.1.2.4. Other heteroatom bridged stepladder
polyphenylenes. Besides nitrogen, other heteroatoms
including silicon, germanium, sulfur, and phosphorus have
been used to replace the methine bridges in stepladder
polyphenylenes. Dibenzosilole (or silafluorene) contain-
ing a silicon atom at the bridge position is an analog
of fluorene. Silicon has similar electronic properties to
carbon, but cannot undergo oxidation to form a ketone.
Therefore, it was anticipated that dibenzosilole-based
homopolymers would not display an additional green
emission band as observed from the PF homopolymer. To
verify this, poly(2,7-dibenzosilole) with alkyl side chains
(119, Scheme 2.1.20) has been reported to show similar
EL emission to PF with a maximum wavelength at 425 nm
but no degradation visible upon heating in air at 200 ◦ C
for 4 h, whereas its PF analog produced a strong green
emission under the same conditions [240]. Like carbazole,
dibenzosilole can also be polymerized at 3,6-postions to
form polymer 120, which has a large band gap of 4.0 eV,
and thus can serve as a potential host for long-wavelength
singlet and triplet emissions [241].
Dibenzosilole was incorporated into the PF backbone
to prepare blue light-emitting copolymers [240,242]. The
3,6-dibenzosilole introduced into the PFO main chains
(121) cannot only inhibit the additional emission bands
but also enhance the color purity and luminous efficiency
of the copolymers. The device with the configuration of
ITO/PEDOT:PSS/PVK/121/Ba/Al yielded an EQE of 3.34% and
an LE of 2.02 cd/A with the CIE coordinates of (0.16, 0.07)
[242]. The copolymer (122a) containing 3,6-dimethoxy-
2,7-dibenzosilole in the PFO main chains exhibited an
obvious steric hindrance effect which lowered the degree
of polymerization and in addition resulted in a blue-shift
of the PL [243]. To replace the silicon in polymer 122a
by a germanium atom, polymer 122b was designed and
synthesized. A single-layer EL device of 122b exhibited an
efficient blue-light emission with a maximum brightness
of 2630 cd/m2 at 7.8 V. This polymer was also employed as
a host material for phosphorescence with high brightness
and efficiency [244].
Similar to fluorene and carbazole, dibenzosilole has
also been copolymerized with electron-accepting DTBT to
produce polymer 123a for PSC. From a film of this poly-
mer two broad absorption peaks at 391–560 nm were
measured providing an optical band gap of 1.85 eV. A
123a:PCBM blend device displayed a PCE of 1.6% under
AM 1.5 (90 mW/cm2 ) illumination [245]. A higher PCE of
5.4% with a similar device structure was achieved for this
polymer with higher molecular weight [246]. A structurally
similar polymer 123b with germanium in place of silicon
was reported to display a PCE of 2.8% from a blend device
with PC71BM [247].
Another analog of fluorene is dibenzothiophene that
contains sulfur at the bridgehead. The sulfur atom can
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Fig. 4. Important examples of PAHs.
be easily oxidized to a sulfonyl group as an electron-
withdrawing building block. Both of them were used
to prepare sulfur bridged stepladder polymers upon
copolymerizing with fluorene (124 and 125) [248–250].
The introduction of sulfur-containing moieties into PFs
improves the color purity, lowers the LUMO energy, and
balances the charge injection and transport [248,249]. The
sulfone-based polymer 125b as the active layer enabled
fabrication of PLEDs emitting saturated blue light with
an LE of 3.1 cd/A and an EQE of 3.9% [250]. Reports
on phosphorus-bridged polyphenylene are relatively rare.
One example is polymer 126a containing a repeating unit
of dibenzophosphole that is a phosphorus-bridged ana-
log of fluorene, whose fluorescence turned green with a
maximum emission at 516 nm in the solid state, being
a candidate for PLEDs [251]. The introduction of this
phosphorus-bridged building block into PFO main chains
produced copolymer 126b, which displayed red-shifted
absorption and emission bands along with a reduced band
1857
gap because of the oxidation of the phosphorus center
[252].
2.2. Polycyclic aromatic hydrocarbons-based conjugated
polymers
Polycyclic aromatic hydrocarbons (PAHs) define a
unique class of compounds that consist of fused aromatic
rings that do not contain heteroatoms or carry substituents.
PAHs have attracted enormous research interest due to
their unique electronic and optoelectronic properties as
well as the potential applications in organic electronics
[253]. Some examples of PAHs are shown in Fig. 4. Among
them, several well-known PAHs with simple structures
such as phenanthrene, triphenylene, and pyrene have been
utilized to prepare conjugated polymers. Other unconven-
tional PAHs containing methylene bridges have also been
developed as building blocks to construct novel polymer
semiconductors. The optoelectronic properties of these
1858 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.2.1. Phenanthrene, triphenylene, and pyrene-based conjugated polymers.
PAHs-based conjugated polymers were carefully investi-
gated and some of them were also applied in PLEDs and
PSCs.
Phenanthrene is one of the simplest PAHs and can be
polymerized at different positions to form two kinds of
polymers, poly(2,7-phenanthrylene)s 127 and poly(3,6-
phenathrylene)s 128 (Scheme 2.2.1). The introduction of
alkyl or aryl substituents at the 9,10-positions of the
phenanthrene rendered these molecules soluble and pro-
cessable. In case of alkyl substitution, however, strong
aggregation was indicated by a large bathochromic shift
of the fluorescence of the film compared to their solu-
tion property. This aggregation could then be efficiently
suppressed by aryl substitution. The arylated polymers dis-
played deep blue EL and good color stability when tested
in PLEDs [254].
Triphenylene, a small discotic PAH, has also been used
as a repeating unit to synthesize homo-and co-polymers
(129 and 130) with a variety of surrounding alkyl and aryl
substituents for PLEDs [255,256]. Because of the twisted
phenyl rings around the triphenylene core, ␲–␲ stacking
in the polymers was prevented, resulting in almost iden-
tical PL spectra in both solutions and films. All polymers
exhibited narrow emission in the range of 430–450 nm,
where the human eyes are most sensitive for the blue range.
The best performance in terms of turn-on voltage (4.6 V)
and LE (0.73 cd/A) was obtained by blending with a hole-
transporting material.
Pyrene, a well-known PAH with unique properties,
has inspired researchers from many scientific areas, mak-
ing pyrene the chromophore of choice in fundamental
and applied photochemical studies [257]. For preparing
pyrene-based conjugated polymers, there are three ways
to link the pyrene into the polymer main chains, as shown
in Fig. 5. The 1-, 3-, 6-, and 8-positions of pyrene are
reactive for the electrophilic substitution, while the 2-
and 7-substituted pyrenes are not directly accessible from
pyrene itself. Taking this into account, 2,7-linked conju-
gated polypyrenylene 131 bearing four aryl groups was
synthesized by introducing substituents prior to the annu-
lation of pyrene. This polymer exhibits an intriguing blue
fluorescence and a remarkable long-wavelength tail [258].
For another 2,7-linked poly(tetraalkoxypyrenylene) 132, it
was very important to verify that the fluorescence maxima
in solution and in the film were almost identical, such that
the alkoxy groups seem to hinder aggregation induced red
shifting of the fluorescence. In the LED devices, however, a
strong red shift appeared [259].
Pyrene was introduced via 1,6-linkages into the
backbones of PPV and polyfluorenevinylene to produce
copolymers 133a and b [260,261]. For both polymers red-
shifted emissions in thin films and significant decrease
of PL efficiencies were found, while blue-green fluores-
cence were observed in solution, indicating the formation
of excimers/aggregates in the solid state. This result
suggested that the introduction of double bond at the 1,6-
positions of pyrene into the polymer main chains is not
effective on avoiding aggregation.
A novel 1,3-linked polypyrenylene 134 was reported
with stable blue emission. No aggregation was observed
in thin films due to the large dihedral angle of ca. 70◦
between the neighboring pyrene units providing a highly
twisted structure of the polymer backbone. OLED devices
with the setup ITO/PEDOT:PSS/134/CsF/Al exhibited bright
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1859

Fig. 5. The numbered positions of pyrene and different options to extend pyrene into polymers.

Scheme 2.2.2. PAH-based conjugated polymers containing methylene bridges.

blue turquoise EL with a maximum at 465 nm and a profile
similar to the solid state PL [257,262]. Modest LE of 0.3 cd/A
and luminance of 300 cd/m2 were obtained [262].
Some PAHs have been fused by five- or six-membered
rings to form new aromatic units carrying solubil-
izing alkyl chains for preparing soluble conjugated
polymers. For example, a new fused building block,
cyclopenta[def]phenanthrene, can be considered either
as a phenanthrene fused with a five-membered ring at
the bay position or as a fluorene bridged by a double
bond. Homopolymer 135a (Scheme 2.2.2) exhibited stable
and efficient blue electroluminescence without additional
emission bands relative to PDAFs. Its monolayer PLEDs gave
a maximum LE of 0.70 cd/A at 180 mA/cm2 with CIE coor-
dinates of (0.17, 0.12) [263,264]. To incorporate BT and
DTBT into the backbone of 135a, copolymers 135b and
135c were synthesized [265,266]. The introduction of BT
units induced a red shift of the emission to the green region
with maximum peaks between 510 and 535 nm owing to
an energy transfer process and an increased electron affin-
ity of polymer 135b. EL devices based on a copolymer with
a BT content of 30% yielded the highest LE of 1.25 cd/A
[265]. Copolymer 135c has a low band gap of 2.0 eV and
emits red light in diluted solution, with an emission maxi-
mum at 621 nm. A PSC fabricated from 135c/PC71BM blend
afforded a PCE of 1.0% [266].
Another novel building block, dinaphtho-s-indacene,
a fused naphthalene–phenylene–naphthalene with two
methylene bridges, and its conjugated polymers (136 and
137) have been developed as EL materials [267]. These
two polymers were designed by replacing two benzene
units in indenofluorene with naphthalenes, which caused
an extension of conjugation perpendicular to rather than
along the polymer backbone. This provided slightly red-
shifted emission making the polymer more sensitive to
the human eye, while the steric hindrance between the
1860 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
adjacent repeating units favors the amorphous charac-
ter, and thereby enhances their spectral stabilities in the
solid state. Both polymers exhibited more stable PL spec-
tra than that of PFO while annealing upon 200 ◦ C in an
inert atmosphere. The EL devices with the configuration of
ITO/PEDOT:PSS/136/Ca/Al turned on at 3.7 V, and emitted
at a maximum of 461 nm with a maximum LE of 1.40 cd/A,
a maximum brightness of 2036 cd/m2 , and CIE coordinates
of (0.19, 0.26). Meanwhile, the emission color of the devices
was independent on the driving voltage and remained
unchanged during continuous operation [267]. By incorpo-
rating alkylated dinaphtho-s-indacene into the backbone of
PFO (48, Scheme 2.1.7), higher LE (3.43 cd/A) and bright-
ness (6539 cd/m2 ) as well as purer blue emissions were
achieved, as discussed above [101].
Stepladder and ladder polymers 138 and 139 were
prepared containing planarized 9,10-diphenylanthracene
within the main chain. The idea underlying the design
of these two polymers was to planarize 9,10-anthrylene
and phenylene units, whose alternating connection oth-
erwise induces a strong twist around the aryl-aryl bond
limiting conjugation. Upon bridging the aryl units with
methylene carbons and attaching solubilizing substitutents
paved the way to these new polymers. This planariza-
tion led to a strong bathochromically shifted fluorescence
with yellow emission for the stepladder polymer 138
(max em = 584 nm) and even red emission for the ladder-
ized polymer 139 (max em = 693 nm). Upon irradiation with
visible light in air, however, both polymers underwent
photo-oxygenation with colorless endoperoxides being
formed. The peroxide formation proved to be reversibly,
since the oxygen could be removed upon thermal treat-
ment [268].
A new fused unit, 5,10-dihydroindeno[2,1-a]indene, has
also been reported and the corresponding homopolymer
and D–A copolymers were synthesized for PLED and PSC
applications. Polymer 140a can be seen as an analog of PPV,
in which the vinylene group in the main chain was cyclized
using two five-membered rings, therefore reducing the oxi-
dation ability of the vinylene groups. As a result, polymer
140a exhibited higher stability than PPV as demonstrated
by their UV–vis, and PL, and EL spectra under the same
conditions. The copolymers made from this new build-
ing block and BTZ as well as DTBT (140b and 140c) were
introduced as the active layer in a PSC. The best perfor-
mance was observed by blending DTBT-based polymer
140c with PCBM where a PCE of 1.88% was achieved [269].
2.3. Thiophene-containing conjugated polymers
The thiophene ring has become one of the most widely
used building blocks for construction of conjugated poly-
mers. These thiophene-containing polymers have attracted
comprehensive research interest as active components in
organic electronic devices. Thiophene chemistry has been
well established and developed for a long time, allowing
tuning of the electronic properties in a wide range via
enormous and attractive variations in structure. In partic-
ular, the polymers containing thiophene moieties present
intriguing electronic, optical, and redox properties as well
as unique self-assembling abilities on solid surfaces or in
the bulk. Moreover, the high polarizability of sulfur atoms
in thiophenes leads to a stabilization of the conjugated
chains and to excellent charge carrier transport, which are
crucial assets for optoelectronic applications [270].
Because of the strong electron-donating nature, thio-
phene and its benzo- and thieno-fused derivatives have
been widely utilized as donor units to construct D–A
polymers for applications in organic electronics. Through
homopolymerization or copolymerization with other
electron-rich units, the resulting conjugated polymers
possess tunable optical and electronic properties owing to
the enlargement of the ␲-conjugation systems. In major-
ity, these thiophene containing polymers exhibit hole
transport characteristics, and have been applied as p-type
semiconductors for OFETs and OPV. In this section, the
focus will be on the one-dimensional thiophene and fused
thiophene-based conjugated polymers without additional
electron-deficient units, while such D–A polymers contain-
ing thiophene moieties will be separately discussed in the
next section.
First, we briefly summarize several representative poly-
thiophene derivatives (Scheme 2.3.1) taking their impor-
tance into account, although they have been mentioned
in many reviews. Then we will discuss thiophene-based
polymers containing various fused-thiophene building
blocks including multi-thienothiophene (Scheme 2.3.2),
bridged dithiophene (Scheme 2.3.3), benzodithiophene
(Scheme 2.3.4), naphthodithiophene (Scheme 2.3.5), and
other complex fused thiophene (Scheme 2.3.6).
2.3.1. Polythiophenes and their derivatives
The early research on polythiophenes without sub-
stituents in the 1980s was carried out for FETs applications,
showing mobilities of only 10−5 cm2 /V s [271]. In order to
improve the solubility and film-forming property, a variety
of side chains were introduced into polythiophene back-
bones, leading to the emergence of a large number of
polythiophene derivatives and related studies. One of them
is poly(3-hexylthiophene) (P3HT, 141, Scheme 2.3.1), a key
polymer material applied in OFETs and OPV. The regioreg-
ularity of P3HT plays an important role in the molecular
arrangement and subsequent device performances [272].
Regioregular P3HT (head-to-tail coupling) exhibits mobi-
lities from 0.05 to 0.2 cm2 /V s by adopting an edge-on
orientation [272,273]. The performance of P3HT in OPV is
also constantly enhanced by various optimization strate-
gies, and a record PCEs of 6.5% has been achieved when
using proper acceptors [274].
To improve the stability of polythiophene-based FETs,
new polymers containing longer but reduced number of
chains were synthesized. Solution-processable regioregu-
lar polythiophene 142a with half of the thiophene rings
substituted by alkyl chains afforded excellent hole mobil-
ity of 0.14 cm2 /V s with on/off ratio higher than 107 under
ambient conditions [275]. A selenophene-containing ana-
log 142b exhibited a lower mobility of 0.02 cm2 /V s [276].
In fact, the selenophene-based polymers were initially
developed as alternatives to polythiophenes for OPV appli-
cations, however studies found that this kind of polymers
showed generally ambipolar charge transport [277]. For
examples, polymers 143 and 144 provided electron and
X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1861

Scheme 2.3.1. Polythiophenes and their derivatives.

Scheme 2.3.2. Multi-thienoacene-based polymers.

1862 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.3.3. C, N, and Si-bridged bithiophene-based polymers.
hole mobilities at the level of 10−2 cm2 /V s [277,278].
Introducing big aromatic units such as naphthalene (145)
can increase the torsion of the polythiophene backbones,
resulting in lower HOMO levels and thus better stabil-
ity, but this approach usually sacrifices the charge carrier
mobility [279].
Recent developments in polythiophenes concentrated
on 3,4-disubstituted polyalkylthiophenes. Polymer 146a–c
had comparable transistor mobilities of 0.17 cm2 /V s and
greater environmental stability than regioregular mono-
substituted poly(3-alkylthiophenes), although they did not
undergo more distinct ␲–␲ stacking as evidenced from
X-ray diffraction studies. The PCEs of these polymers in
polymer:fullerene BHJ solar cells reached 4.2% [280]. Fur-
ther studies on these polymers in comparison with P3HT
demonstrated that the degree of polymer backbone twist-
ing induced by 3,4-disubstituents increased the ionization
potential and enhanced the Voc while retaining the Isc . This
molecular design provides a simple method to tune the
degree of backbone twisting in polymer backbones for the
optimization of organic electronic devices [281].
2.3.2. Thienoacene-containing conjugated polymers
Fused aromatic units like thieno[3,2-b]thiophene or
even larger oligothienoacenes introduced into the poly-
thiophene backbones can lower the HOMO level and
increase the stability of the polymers. This is due to the
larger resonance stabilization energy of the extened conju-
gated units compared to the single thiophene ring improv-
ing the delocalization of electrons [282]. Thieno[3,2-
b]thiophene-based polythiophenes 147a–e (Scheme 2.3.2)
were thus synthesized and show HOMO levels of 0.3 eV
lower than that for P3HT. Transistors based on these poly-
mers exhibited mobilities of 0.2–0.7 cm2 /V s, whereas 147c
can provide a value higher than 1.0 cm2 /V even using high
work function metals such as Pt as the source and drain
electrodes [282–284]. By tuning the dip-coating speed, a
monolayer and subsequent microstructure of 147c on the
surface can be precisely controlled. At a low dip-coating
speed, the polymer chains are uniaxially oriented, yielding
pronounced structural anisotropy and high charge carrier
mobilities of 1.3 cm2 /V s in the alignment direction [285].
Other thienoacenes (148–150, Scheme 2.3.2) with fur-
ther extended conjugation have also been incorporated
into polythiophene backbones to develop p-type semi-
conductors. For the trithienoacene polymers, 148c with
alkyl chains only at thiophene rings exhibited an excellent
hole mobility of 0.3 cm2 /V s with a very high current on/off
ratio of over 107 [286], remarkably higher than those of
the other two polymers (1.7 × 10−3 cm2 /V s for 148a [287]
and 0.05–0.06 cm2 /V s for 148b [288]). Polymer 148b has
also been investigated in a PSC device by blending with
PC71BM, affording a best PCE of 3.2% [288]. Comparison
of tetrathienoacene polymers 149a–c indicates that 149b
with bithiophene as a comonomer affords higher mobil-
ity of 0.33 cm2 /V s [289] than 149a and 149c (10−2 cm2 /V s
for both) [290], whereas for pentathienoacene polymer
150 a lower mobility of only 2.3 × 10−3 cm2 /V s was found
[287]. The difference in the field-effect behavior of these
thienoacene-based polymers could be attributed to the
influence of C2 symmetry of different thienoacenes on the
lamellar spacing [290].
2.3.3. Bridged bithiophene-containing polymers
Bridged bithiophenes are a class of very promising fused
aromatic building blocks with structural similarity to the
aforementioned bridged biphenyl (fluorene, carbazole, and
dibenzosilole). They exhibit a completely planar struc-
ture, indicating good ␲-conjugation across the fused
rings. Typical bridged bithiophenes include dithieno[3,2-
b:2 ,3 -d]pyrrole (DTP), dithieno[3,2-b:2 ,3 -d]silole (DTS),
and cyclopenta[2,1-b:3,4-b ]dithiophene (CPDT). Unlike
sulfur-bridged bithiophene (trithienoacene, corresponding
polymers 148 in Scheme 2.3.2), the nitrogen-, silicon-, and
carbon-bridged bithiophene can be introduced with var-
ious solubilizing groups at the bridge atoms and they do
not interfere with the conjugation of the backbone. Many
p-type polymer semiconductors derived from these build-
ing blocks have been developed in recent years and several
examples are presented in Scheme 2.3.3.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1863

Scheme 2.3.4. Benzodithiophene-containing polymers.

DTP was copolymerized with several alkyl substituted
thiophene and bithiophene comonomers to yield polymers
151a–f [291]. The incorporation of soluble substituted thio-
phenes and planar DTP units resulted in low band gap
polymers with high conductivity. Optical characterization
revealed that the band gaps of 151a–f were between 1.74
and 2.00 eV, lower than for regioregular P3HT. Their HOMO
energy levels were estimated from CV characterization
between −4.68 and −4.96 eV. Among these polymers, thin
films of 151c and 151d just drop-casted exhibited poorly
defined, randomly ordered lamellar structures, which
improved significantly after thermal annealing. Interest-
ingly, the mobilities of the less ordered samples were much
higher than those observed after annealing. The highest
performance was obtained from 151d with a maximum
mobility of up to 0.21 cm2 /V s. These results suggest that
the presence of highly ordered microcrystalline structures
in thin films of organic semiconductors is not always nec-
essary for decent performance of organic transistors [280],
but this finding rather seems like an exception and cannot
be generalized.
DTS has been used as a repeating unit to prepare
homopolymer and mono- and bithiophene-containing
copolymers (152a–c) with good hole mobility, solution
processibility, and air stability [292]. FETs fabricated on
HMDS-passivated SiO2/Si substrates under ambient con-
ditions gave hole mobilities of 0.08 cm2 /V s, low turn-on
voltages, and current on/off ratios 106 . CPDT and fluo-
rene alternating copolymers 153a and 153b have also
been investigated as semiconductor layers in polymer
FETs. However, they only exhibited hole mobilities at a
level of 10−6 –10−7 cm2 /V s because of being amorphous
in the solid state [293], while pentacene-containing poly-
mer 153c gave mobility between 10−3 and 10−4 cm2 /V s.
1864 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 2.3.5. Naphthodithiophene-containig polymers.

Scheme 2.3.6. Other fused thiophene-based polymers.

 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
The impact of regioregularity and direction of conjuga-
tion extension on thin-film order and device performance
has also been demonstrated for 153c [294]. In fact, CPDT
is a very promising electron donor when combining with
acceptors in a D–A polymer system, which will be discussed
in the next section.
2.3.4. Benzodithiophene-containing conjugated polymers
Benzodithiophenes (BDT) are another class of important
building blocks containing fused-ring thiophenes. There
are several structural isomers which possess different link-
ages and thereby varying geometries (Scheme 2.3.4). The
influence of the degree of curvature along BDT-based poly-
mer backbones on the solubility, the electronic levels, the
film morphology, and the charge carrier mobility in OFETs
has been investigated in depth, e.g. by comparing the five
copolymers (154a–e) containing different BDT isomers and
alkyl substituted bithiophene as comonomers [295]. It has
been shown that the optical gap increased with increasing
curvature of the polymers, probably because of a reduced
effective conjugation length. The order in bulk is reduced
by increasing the curvature, but the ␲-stacking distance
remains unaffected. The more highly curved polymers
possess reduced order in the film, whereas the less curved
ones have too low solubility for processing. As a result,
FETs measurements revealed that polymer 154c with an
intermediate degree of curvature possessed good solubil-
ity combined with high order and thus highest mobility
of 0.13 cm2 /V s in this series of polymers. These findings
may serve as a guideline for the rational design of other
semiconducting polymers.
Further studies focused on the benzo[2,1-b;3,4-
b ]dithiophene-containing homo- and copolymers 155
and 156a–c. After rationally optimizing the molecular
structure by regulating the positions at which alkyl chains
were attached, the best polymer 156c (same as 154c) was
sought out displaying an easy way of solution processing,
low hysteresis behavior, and high charge-carrier mobil-
ity without any long-term annealing. The curvature of
the monomer unit guarantees an optimum compromise
between solubility and aggregation tendency toward for-
mation of highly ordered films. Top-gate devices based on
156c on a polyethylene terephthalate (PET) film exhibited
a mobility as high as 0.5 cm2 /V s [296].
Benzo[1,2-b:4,5-b ]dithiophene carrying solubilizing
alkyl chains at the central benzene ring is the most widely
used BDT isomer for the synthesis of conjugated poly-
mers [297]. A homopolymer 157 with dodecyl-substituted
benzo[1,2-b:4,5-b ]dithiophene as a repeating unit exhib-
ited a modest mobility of 0.012 cm2 /V s [298], while a
hexyl-substituted bithiophene-containing copolymer 158
afforded higher mobilities of 0.15–0.25 cm2 /V s with cur-
rent on/off ratios of 105 –106 in the top-gate OFETs, which
was achieved without thermal post-treatment. Investiga-
tions of the durability carried out over 30 days proved no
significant changes in the transistor characteristics of 158
[299].
Recently, alkyl chains at the central benzene ring of
benzo[1,2-b:4,5-b ]dithiophene were replaced by alkoxy,
thioalkoxy, and phenylethynyl side chains to synthe-
size BDT-based polymers (159a–c and 160a–c) for PSC
1865
applications [300,301]. The change from alkoxy groups to
thioalkoxy groups lowered the HOMO energy level of the
conjugated polymers from −5.31 to −5.41 eV, and conse-
quently enhanced the Voc . As a result, polymers 159a–c dis-
played Voc of 0.99, 0.91, and 0.83 V, respectively. The poly-
mer 159b-based PSC presented a PCE of 4.0%, which is one
of the highest efficiencies reported from a homopolymer-
based PSC without thermal/solvent annealing or incorpo-
rated additives. However, the hole mobilities of these poly-
mers were low with values of 1.3 × 10−5 cm2 /V s for 159b
and 1.1 × 10−6 cm2 /V s for 159a [300]. For phenylethynyl-
substituted polymers 160a–c, the spacing between alkyl
substituents increased by introduction of thiophene and
bithiophene units in the backbone of the polymer was sys-
tematically studied. As the spacing between the side chains
increased, an increase of the weight ratio of polymer to
fullerene acceptor was required for achieving the highest
PCE of BHJ solar cells. However, these polymers exhibited
moderate PCEs lower than 2% [301].
2.3.5. Naphthodithiophene-containing conjugated
polymers
Naphthodithiophene (NDT), a very recently developed
building block, is expected to provide a highly rigid pla-
nar backbone when introduced into the polythiophene
system. An advantage of the structure of NDT over benzoth-
ienobenzothiophene (BTBT, 161, Scheme 2.3.5) with two
benzene rings fused at the end of thieno[3,2-b]thiophene
is to avoid twisting between the adjacent thiophene rings,
which would destroy the ␲-stacking and thereby reduce
the charge carrier mobility. The BTBT copolymer 161 gave
a highly twisted backbone (max < 400 nm) and no OFET
response, despite the fact that BTBT has been success-
fully applied as a small-molecule semiconductor in OFETs.
In sharp contrast, the naphtho[1,2-b:5,6-b ]dithiophene
cpolymers 162a–e exhibited high field-effect mobilities
(i.e. >0.5 cm2 /V s) as a result of the strong ␲-stacking [302].
Similar to BDT, NDT also occurs in several isomers
(163 and 164) with different structural motifs extend-
ing linearly, in bent fashion, or appearing disk shaped.
The symmetry of the different isomers and the related
curvature of the polymer chains have impact on their
HOMO levels and charge carrier mobility. NDTs with lin-
ear and angular shapes (163a–d) have comprehensively
been studied [303]. The angular-NDT-based polymers 163a
and b displayed lower HOMO levels and larger band gaps
than their linear counterparts (163c and d). The polymers
with angular NDTs, on the other hand, gave the highly
ordered structures with a very close ␲-stacking distance
of 3.6 Å, whereas those with linear NDTs had a very weak
or no ␲-stacking order, which resulted in higher mobili-
ties observed from the corresponding polymers 163a and
b than 163c and d. As a result, the polymer 163a bear-
ing naphtho[1,2-b:5,6-b ]dithiophene, an angular-shaped
NDT, exhibited the highest mobility of ∼0.8 cm2 /V s among
the four polymers with isomeric NDTs.
Recently a disk shaped NDT isomer, naphtho[2,1-
b:3,4-b ]dithiophene, has also been copolymerized with
thiophene and bithiophene to produce p-type polymers
164a and b recently [304]. Relatively, more highly ordered
intermolecular structures were found for 164b than for
1866 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
164a because the bithiophene unit in the former poly-
mer provided crystallinity with increasing planarity and
enough space for interdigitation of the long alkyl side
chains for high order. FETs measurements exhibited charge
carrier mobilities of 0.01 and 0.076 cm2 /V s with current
on/off ratios of 105 and 106 for 164a and 164b, respectively,
which was in agreement with observation of the structural
ordering.
2.3.6. Other fused thiophene-containing conjugated
polymers
Apart from those alluded to the previous discussion,
some more complex fused-thiophene building blocks have
also been reported to serve as repeating units for synthesis
of linear polythiophenes. Herein, we will introduce several
recent examples, as depicted in Scheme 2.3.6.
Indacenodithiophene (IDT) has further extended con-
jugation compared to NDT, consisting of five fused rings
along the backbone. It has been reported to homo- and co-
polymerize with several thiophene-based comonomers to
produce polymers 165a–e [305,306]. Among them, poly-
mer 165a exhibited amorphous thin-film microstructure,
as revealed by X-ray diffraction. FETs gave a mobility of
0.2 cm2 /V s with the current on/off ratio of 106 and excel-
lent ambient stability [305]. Polymers 165b–e were applied
in PSC devices. The maximum PCE based on 165c/PC71BM
system reached 3.3% [306].
Polymer 166 contains a larger fused ␲-system, tetrathi-
ahexacene as a repeating unit. The strong interchain
aggregation led to a highly ordered bulk material with short
␲–␲ distance, demonstrating the efficiency of introducing
larger sized monomers. In an FET, low contact resistance
and low hysteresis were measured but a mobility of only
10−3 cm2 /V s was obtained [307]. Another new heterohep-
tacene with the inclusion of carbazole and thiophene units
was synthesized and introduced into the polythiophene
backbone (167). The incorporation of heteroatoms in the
fused-ring system lead to small optical band gaps of these
polymers. Similar to 166, this polymer exhibited a low
mobility of 10−4 cm2 /V s in an FET [308]. A homopolymer
derived from this heteroheptacene bearing aryl side chains
displayed a lower FET performance [309]. Although both
examples did not show exciting charge carrier mobilities,
the results supported the potential of conjugated polymers
containing large fused building blocks.
Two isomers of S- and N-containing heteroacenes,
namely, dithienocarbazoles (DTC) were recently developed
and copolymerized with alkyl substituted bithiophene to
produce 168a–c and 169a and b [310,311]. These polymers
were quite soluble owing to the introduction of additional
alkyl substituents at the nitrogen atom. For polymers
168a–c, spun-casted films were characterized by a lamellar
layered structure oriented normal to the substrate. Bottom-
gate, top-contact OTFT devices based on these polymers
demonstrated that the mobility increased with an increase
of the alkyl chain length in bithiophene units, with values of
0.0064, 0.022, and 0.035 cm2 /V s for each polymer, respec-
tively [310]. The isomeric polymers 169a and b formed
ordered thin films in which the polymer backbones dom-
inantly adopted an edge-on orientation to the substrate
with a lamellar spacing of ∼24 Å and a ␲-stacking distance
of ∼3.7 Å upon thermal annealing. The OTFT devices with
mobilities of up to 0.39 cm2 /V s have been demonstrated
with 169b. This value is the highest among the conjugated
polymers containing heteroacenes larger than four fused
rings [311]. Especially the different directions of the
solubilizing side chains in 168 (all to one side) and 169
(alternating up and down of the plane of the backbone)
seem to control the face-on vs. edge-on alignment in 168
and 169, respectively. Thus a further investigation on the
impact of the molecular shape but also the backbone curva-
ture of the DTC-based polymers on the structural property
and charge carrier mobility should be quite worthwhile, as
described above for BDT- and NDT-containing polymers.
For instance a further improvement of the promising OFET
characteristics of 169b, can be anticipated if the ␲-stacking
distance could be further reduced, by slight changes of the
R groups or the annealing conditions.
New thiophene-based building blocks have also been
designed by fusing thiophene rings to form disk-shaped
molecules. Benzo[2,1-b:-3,4-b :5,6-b ]-trithiophene is one
of several benzotrithiophene (BTT, read more about BTT
in next section) isomers and has been used as a repeating
unit for copolymerization with thiophene and thieno[3,2-
b]thiophene (170a and b) [312]. The planar BTT core
induced strong aggregation effects in alternating copoly-
mers. The choice of the comonomer was found to play a
crucial role in determining the backbone conformation, the
interchain interactions, and the polymer solubility. A best
hole mobility of 0.24 cm2 /V s was achieved from 170a. The
asymmetry of this BTT isomer, however, leads to a regio-
random polymerization as described, making this issue of
gaining access to regioregular copolymers worth exploring.
All the above-discussed thiophene and fused thiophene
polymers without electron-withdrawing units have up to
date mainly been applied as p-type semiconductors in
OFETs. In principle, it is impossible for these polymers to
afford n-type transport owing to their exclusive electron-
donating nature. On the other hand, although some of
such polymers were also used as active components in
BHJ solar cells, the obtained PCEs were usually not high in
comparison with D–A polymers. Actually, the D–A poly-
mer approach provides a very broad potential for the
thiophene-containing moieties as donor units, which will
consequently be outlined in the following section.
2.4. Donor–acceptor polymers
Integration of electron donors and electron acceptors
in one polymer system (D–A polymers) has proved to be
an efficient strategy enabling us to tailor the properties of
conjugated polymers for the desired applications in OFETs
and PSCs. Concerning OFETs, the intra- and intermolecular
interactions between donor and acceptor units within
a D–A polymer can lead to self-assembly into ordered
structures and strong ␲-stacking of polymer chains, both
of which favor charge carrier transport [4]. The HOMO and
LUMO energy levels and hence band gaps can be well tuned
in a D–A polymer system via selection of different donor
and acceptor units because the HOMO is mainly located
at the donor unit but the LUMO mainly at the acceptor
unit [313]. This knowledge can be utilized to control
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
the Voc and Jsc so as to obtain high PCEs in PSC devices.
Such strategy offers a great opportunity for all afore-
mentioned electron-rich building blocks to act as donor
units in combination with appropriate acceptors yielding
well-designed D–A polymers. Some of the donors applied
like fluorene, indenofluorene, carbazole, indolocarbazole
have been discussed before and exhibited promising
performances in PSCs. Here many more high-performance
D–A polymers composed of novel donating and accepting
building blocks with cutting edge high-performance
will be comprehensively reviewed. Those D–A polymers
with further extended 2D structures will be discussed
separately in Section 3.3.
Many review articles have been published recently
that cover developments in the PSC [1,313–316] or OFET
[2,317,318] fields, or describe one or several classes of D–A
polymers [319–322]. This section focuses on the donor and
acceptor building blocks which are the most often applied
constructing units for D–A polymers. Many new donor
or acceptor units and corresponding polymers have been
reported in the last two years, which will be covered here
to present the latest developments in this exciting research
area.
Fig. 6. Donor Box A: Heteroacene donors containing bridging atoms.
1867
2.4.1. Donors and acceptors
As the name suggests, D–A polymers are made up of
electron donors and electron acceptors. The electron push-
ing/pulling ability (or strength) and molecular geometry
of the donor and acceptor as well as their interactions
determine the basic optical behavior and electronic prop-
erties of a D–A polymer. It is thus appropriate to rationally
design electron donor and acceptor units before combining
them to develop high-performance D–A polymers. In this
part we attempt to collect and classify the reported donor
and acceptor building blocks and then describe their cor-
responding D–A polymers according to our classification
given in the next section.
2.4.1.1. Donors. Donor, herein, refers to an electron-rich
unit which determines the HOMO energy of the D–A poly-
mer system. A large number of donor units, which are
derived from benzene and thiophene have been reported in
the past decade. Here these donors are classified into two
types according to the presence or absence of the bridging
atoms, and listed in two Donor Boxes A and B, as respec-
tively depicted in Figs. 6 and 7.
1868 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Fig. 7. Donor Box B: Heteroacene donors without bridging atoms.
The electron-donating ability is determined by the
HOMO level, however, because of the different standards
and methods as well as the systematic errors, the val-
ues from different publications are often not comparable.
Basically, there are several empirical principles to judge
the strength of donors. First, since the electron-donating
ability of thiophene is stronger than that of benzene, the
donors consisting only of thiophene moieties are stronger
than those built up only of benzene moieties. Thus, bridged
bithiophenes D11–D15 are usually regarded as strong
donors, whereas bridged biphenyls and terphenyls D1–D10
are weak donors. Those examples containing both ben-
zene and thiophene can be considered as medium donors.
Secondly, nitrogen bridging enhances the donor strength
compared to other bridging atoms thanks to the lone pair
of electrons of the nitrogen atom. In addition, the symme-
try of donor units affects the electron-donating ability, for
example, the C2 symmetrical D38 possesses higher HOMO
level than the other benzotrithiophene isomers accord-
ing to DFT calculations and CV experiments (see details
below).
Most of the donors used for construction of D–A poly-
mers are planar and possess symmetric geometries, which
is particularly beneficial for intra- and intermolecular
ordering of the polymer chains in the solid state. All
the donors listed here and their D–A polymers will be
mentioned in the following chapter. Emphasis, how-
ever, will be put to those examples with high device
performance.
2.4.1.2. Acceptors. Acceptor, herein, refers to an electron-
poor unit determining the LUMO level of an alternating
D–A copolymer. Most acceptor units possess at least one
or more strong electron-withdrawing groups, like an imine
nitrogen ( C N) or a carboxyl unit ( C O). Herin, we sort
them into five types according to their chemical structure,
namely, thiazole-, thiadiazole-, pyrazine-, annulated amide
or imide-, and carboxyl-containing donors, as illustrated in
Fig. 8. Some examples with other electron-poor groups are
listed as well.
The electron-accepting abilities of these acceptors are
described by their LUMO level which is experimentally
accessible through CV characterizations or photo electron
spectroscopy (PES), theoretically through DFT or ab initio
calculations. One can also visually estimate the acceptor
strength according to the absorption edges of D–A poly-
mers when copolymerizing different acceptors with the
same donor. Empirically, strong acceptors contain thia-
diazole or two thiadiazole rings such as in A6 and its
derivatives A20, A21, and A22, and further annulated rings
such as in A40, A42, and A45. Many D–A polymers with
excellent OPV and OFET performances are derived from
X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1869

Fig. 8. Acceptors classified by the chemical structure.

1870 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
these acceptors. Those containing thiazole or only one
amide or imide ring such as A1, A3, and A34 are usually
considered as relatively weak acceptors.
It should be mentioned here that acceptors A28 [323]
and A58 [324] were reported as donor units, however, in
view of the existence of imine nitrogens containing a free
electron pair (pyrazine ring in A28 and pyridine ring in A58)
they can also be considered as weak acceptors. Actually, the
definition of donors and acceptors in copolymers depends
on their combinations and individual HOMO and LUMO lev-
els, and is thus relative, e.g. a strong acceptor combined
with a weak acceptor let the latter become the electron-
donating moiety, for donors vice versa. Furthermore it is
clear that some acceptors mentioned in Fig. 8 also con-
tain mixtures of two accepting components themselves,
exhibiting some interesting properties, which will be sep-
arately discussed in Section 2.4.2.3. As for the extended
donor moieties mentioned, most of the acceptors are copla-
nar and even symmetric, which is critically important for
the properties of the copolymers. All the acceptors listed
here and their D–A polymers will be mentioned in the
following section, however, emphasis is focused on rep-
resentatives examples with high performances.
2.4.2. One-dimensional D–A polymers
Based on the donors and acceptors listed above, a large
library of D–A polymers has been developed for success-
ful applications in organic electronics. In this section, we
review typical examples of D–A polymers and their per-
formances in OPV and OFET devices, which are summarized
in Table 4. Every donor and acceptor will be referred by an
alias as assigned in Figs. 6–8 in the following discussions.
It must be noted in advance that benzothiadiazole (BT,
A6) and diketopyrrolopyrrole (DPP, A42) are the two most
common acceptors and both of them are often combined
with other donors by surrounding two thiophenes, namely,
4,7-dithienobenzothiadiazole (DTBT) and dithienyl-DPP.
For ease of discussion, they will be addressed by the two
acronyms “A6TT” and “A42TT”.
2.4.2.1. D–A polymers based on donors D1–D45. D–A poly-
mers based on the donors derived from bridged biphenyl
and terphenyl usually have low HOMO levels thanks to
the electron-deficient nature and aromaticity, which gen-
erally leads to high Voc in their OPV devices. Detailed
discussions regarding D1–D7-based D–A polymers can be
found in Section 2.1. Donor D8 was prepared by different
routes [325–327] and a polymer with D8 as a repeating
unit was also synthesized using hydrosilylation reactions
[328], but D–A polymers based on this donor remain elu-
sive. Monomer D9 has also been reported [329], however,
to the best of our knowledge polymers using this unit have
not yet appeared in the literature. Molecule D10, actually,
is not known so far but could be a target in the near future.
Donors D11–D15 based on bridged bithiophene have
emerged as a class of important building block for con-
structing D–A polymers, since they are highly planar
and the five membered thiophene rings cause less steric
hindrance with their neighboring acceptor units. Among
these five donors, cyclopenta[2,1-b:3,4-b ]dithiophene
(CPDT, D11), dithieno[3,2-b:2 ,3 -d]pyrrole (DTP, D12), and
dithieno[3,2-b:2 ,3 -d]silole (DTS, D13) have become most
popular and have been copolymerized with many accep-
tors such as A6, A6TT, A36, and A42TT. Scheme 2.4.1
presents several representative D–A polymers based on
D11–D13 copolymerized with the same acceptor A6.
CPDT-BT D–A polymer (171) has become one of the most
successful examples achieving excellent performances in
both OFET and OPV applications. Polymer 171a initially
exhibited a hole mobility of 0.17 cm2 /V s in FET devices
[330], but the optimization of the molecular weight of poly-
mer and the processing conditions of devices improved
continuously the hole mobilities to 1.4 and 3.3 cm2 /V s
[331,332]. Recently, an ultrahigh mobility of 5.5 cm2 /V s
based on 171a has been realized by reaching high molecu-
lar order and pronounced alignment in single fibers (Fig. 9)
within a short OFET channel via solvent vapor enhanced
drop casting [333]. With respect to OPV applications, poly-
mer 171b with different side chains from 171a displayed
a broad absorption spectrum with a band gap of 1.46 eV
and exhibited a preliminary PCE of 3.2% when blend-
ing with PC71BM [334,335]. By adjusting the thin-film
nanosphase segregation in blends 171b:PC71BM blends
using processing additives such as alkanedithiols and 1,8-
dihalo-octanes, PCEs were significantly enhanced up to
5.5% [336,337]. Donor D11 was also copolymerized with
various acceptors such as A6TT and A1 [338], A2 [339],
A24 [340], A36 [341], A56 [342,343], and A42TT [344], but
the PCEs from these polymers were not higher than that of
171b.
DTP (D12) contains an electron-rich nitrogen atom at
the bridging position, increasing the electron-donating
ability compared to D11 so that the D–A polymers using
D12 as a donor (172a–c) displayed a broader absorp-
tion range, narrower band gap (1.41–1.43 eV), and higher
HOMO energy levels (between −4.81 and −4.89 eV) com-
pared to 171. The narrow band gap is beneficial for
producing high Isc (12.3 mA/cm2 for 172c) in OPV devices
but high HOMO levels led to low Voc (0.55 V for 172c). The
PCEs based on these polymers (1.1–2.8%) were thus not
higher than those of 171b containing D11. It was demon-
strated that the PCEs of these polymers were also strongly
dependant on the length of alkyl chains [345]. D–A poly-
mers based on D12 containing other acceptors such as
A6TT [346], A42TT [347], and A36 [348,349] exhibited sim-
ilar properties as 172, namely, narrow band gaps (high Isc )
and high HOMO levels (low Voc ), and subsequently mod-
erate PCEs (lower than 3%.) It can thereby be concluded
that strong donors are unfavorable for the construction of
D–A polymers with high performances in OPV applications
but they are useful for preparing D–A polymers with high
charge carrier mobility [347] and with narrow band gap
absorbing light in the NIR optical range [350].
DTS (D13) is another appealing donor based on bridged
bithiophene. The longer C Si bond than C C bond in
D11 was expected to release some strain from the pla-
nar heterocycle and thereby to allow stronger ␲-stacking
interactions to occur. Polymer 173 is the first polymer
which showed similar absorption behavior and band gap
to 171 but higher hole mobility and an excellent PCE
of 5.1% (173:PC71BM = 1:1) without further optimization
[351]. Many D13-containing D–A polymers have appeared
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1871

Table 3
The acceptors that are not discussed in the main text and the corresponding references.

Acceptor A1–A5 A7 A8 A9&A10 A11&A13 A12

Ref. [320] [387] [224,413] [414] [415] [416]
Acceptor A14 A15 A16 A17 A18 A19
Ref. [387,416] [224,404,417,418] [419,420] [421] [422] [423]
Acceptor A20 A21 A22 A23 A24 A25
Ref. [350,424,425] [426,427] [172,330,428,429] [430] [155,224,357,431,432] [433,434]
Acceptor A26 A27 A28 A29 A30 A31
Ref. [153,154,161,201,237] [224] [323,404] [162,435] [435] [367]
Acceptor A32&A33 A34 A35 A37 A38 A39
Ref. [368] [436] [437,438] [439] [382] [440–442]
Acceptor A43 A44 A48–A50 A51 A52 A53
Ref. [443] [444] [316] [445] [281] [446]
Acceptor A54 A55 A56 A57 A58 A59&A60
Ref. [447] [448] [343,366] [205] [203,324] [449]

Scheme 2.4.1. Examples of D11–D13-based D–A polymers with A6 as an acceptor.

Fig. 9. Analysis of single 171a fiber on HMDS: (a) SEM and (b) SAED (arrow indicates the fiber axis), (c) schematic illustration of the polymer organization
in the fiber fabricated via a method of solvent vapor enhanced drop casting. Ref. [333], Copyright 2012.
Adapted from with permission from Wiley-VCH Verlag GmbH Co.
1872 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

to be effective in improving charge mobility and increasing
the Voc in OPV devices and therefore exhibiting outstand-
ing performances compared to D11- and D12-containing
polymers in PSC applications [351–354]. For example,
D13 combined with A36 as an acceptor had better hole
transporting ability and lower HOMO lever (−5.57 eV) in
comparison with the analogs containing D11 as a donor,
and afforded a PCE of 6.2% with simultaneously high Isc
(10.95 mA/cm2 ), Voc (0.9 V), and FF (63%) from a blend
device with PC71BM. By changing the processing solvent
and adding 3% DIO as an additive, a PCE as high as 7.3% was
achieved [352].
It should be pointed out that because of the popularity
of D11–D13 several polymers with the same or very similar
structures were separately reported by different research
groups. The published device properties (mobilities in FETs
and PCEs in PSCs), however, varied to quite an extent. These
differences could be attributed to the synthetic methods,
varying molecular weights and polydispersities of the poly-
mers, and the device processing conditions. Therefore, the
direct comparison of these donors with the same acceptor
in copolymers carried out under the same conditions for
synthesis and device fabrication was particularly impor-
tant and should be encouraged to be done also for other
polymers of high interest [355,356].
D14 has a sulfur atom at the bridging position, not
providing access to attach solubilizing groups at this posi-
tion. Alternatively, the alkyl chains can be placed at the
␤-positions of two outer thiophene rings. As discussed in
Section 2.3 it has been found that copolymers of the alkyl
substituted D14 with a non-alkylated bithiophene have
lower hole mobilities than those of unsubstituted D14 and
dialkylated bithiophene. In this regard, D–A polymers using
alkylated D14 as a donor and alkoxylphenyl-substituted
A24 [357], alkoxyl-substituted BT derivative A13 [358],
and A42TT [358,359] as acceptors, respectively, provided
relative modest mobilities (10−6 –10−2 cm2 /V s) and PCEs
(0.3–3%) in PSC devices. An unsubstituted D14 combined
with the alkyl substituted A42TT in a copolymer was
reported to exhibit more promising ambipolar FET per-
formance with hole mobilities up to 0.23 cm2 /Vs and
electron mobilities of 0.015 cm2 /Vs, as well as a high PCE
of 5.1% upon blending with PC71BM in a PSC device [360].
An analog with selenophenes replacing two surrounding

Table 4
OFET and PSC performances of selected D–A polymers.

Polymer PSCs OFETs Ref.

Jsc (mA/cm2 ) Voc (V) FF PCE (%) h,max (cm2 /V s) Ion /Ioff e,max (cm2 /V s) Ion /Ioff

171a – – – – 5.5 106 – – [333]

171b 16.2 0.62 0.55 5.5 – – – – [336]
172c 11.9 0.54 0.44 2.8 – – – – [345]
173 12.7 0.68 0.55 5.1 – – – – [351]
175 – – – – 0.04 ∼104 – – [4]
176 – – – – – – 0.45–0.85 106 [452]
177 Replacement of PCBM – – 0.07 105 [453]
3.79 0.53 0.44 0.88
178 Replacement of PCBM – – – – [454]
4.57 0.56 0.50 1.28
179 Replacement of PCBM – – – – [455]
3.63 0.68 0.66 1.63
180 – – – – – – 0.002 – [456]
181 Replacement of PCBM – – 0.013 104 [457]
4.2 0.63 0.39 1
182f Replacement of PCBM – – 10−4 –10−3 – [458]
3.31 0.74 0.47 1.15
Solvent optimization results in a PCE of 2.23%
183b – – – – 4.0–8.2 105 –107 – – [5]
184 – – – – 4.97 1.6 × 107 – – [459]
185 – – – – 0.01 – 3 104 [6]
186 – – – – 0.0043 2.6 × 104 0.046 6.0 × 105 [460]
187 – – – – 3.97 104 2.20 10 [462]
189 15.0 0.58 0.61 5.4 1.42 105 0.063 103 –104 [463]
191 – – – – 0.79 107 – – [469]
192 13.7 0.70 0.69 6.3 – – – – [470]
195a 7.87 0.79 0.68 4.22 – – – – [472]
197 – – – – 3.62 106 – – [473]
199 – – – – 2.48 106 – – [461]
200 – – – – 1.85 106 –107 0.43 105 –106 [474]
202a – – – – 0.35 – 0.40 – [477]
202b – – – – 0.1 – 0.09 – [478]
204 – – – – 0.46 ∼104 0.84 ∼104 [466]
206b – – – – 1.17 – 1.32 – [480]
207 Replacement of PCBM – – 0.02 – [481]
0.95 1.1 – 0.31 [482]
209 – – – – 0.16 – 0.14 – [483]
210 5.6 0.79 0.56 2.5 – – – – [484]
211 17.2 0.68 0.67 7.9 – – – – [485]
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
thiophenes at both sides of DPP also yielded decent perfor-
mance in OFETs (0.13 cm2 /V s for holes and 0.01 cm2 /V s for
electrons) and OPVs (PCE of 4.05%) [360].
D15 with a germanium bridge was recently developed.
Compared with D13, the longer C Ge bond in D15 can
further lower the steric hindrance between neighboring
polymer chains and thus improve the intermolecular ␲–␲
stacking. D15 with 2-ethylhexyl chains attached at the ger-
manium atom was copolymerized with n-octyl substituted
A36, delivering a best PCE of 7.3% as blending with PC71BM
and using 5% DIO as processing additive, higher than that
of the D13 corresponding copolymer analog (6.6%) under
identical device processing conditions [361]. This promis-
ing polymer was also applied in an inverted PSC, displaying
a best PCE of 8.5% and a certified PCE of 7.4%, which
allows for the realization of a high-efficiency PSC with
large-scale roll-to-roll processing [362]. Recently, D15 was
also copolymerized with fluorinated A6TT (F at thiophenes
rather than at BT) producing a polymer with a significant
enhancement in OPV performance in comparison with an
analog without fluorine substituents [363].
Donors D16–D20 can be prepared by bridging
thiophene–phenylene–thiophene (Th–Ph–Th) with C
and other heteroatoms. The combination of benzene and
thiophene in these donors makes their electron-donating
abilities be medium as compared to the aforementioned
oligophenyl- and bithiophene-based donors. The rigid-
ity and coplanarity of these ladder-type molecules can
lead to strong ␲–␲ interactions of the final polymers
which improve the charge carrier mobility even upon
combination with acceptors.
The C-bridged donor D16, namely, indacenodithio-
phene (IDT), with n-hexylphenyls groups attached at the
bridge positions was initially copolymerized with A6 con-
taining additional thiophene or bithiophene moieties in the
main chains, demonstrating a PCE of 4.4% [364]. A copoly-
mer of n-hexadecyl substituted D16 and A6 was applied
in OFETs, exhibiting a hole mobility of up to 1 cm2 /V s
with good ambient stability [305]. Subsequent studies
demonstrated that the substituents at the bridging cen-
ters strongly affected the OFET and OPV performances of
these IDT-BT copolymers. A very long linear chain is most
beneficial for OFETs, whereas 2-ethylhexyl side chains can
lead to very desirable phase separation in the polymer and
extremely good OPV performance with a best PCE of 5.5%
[365]. The donor D16 with n-hexylphenyl side chains has
also been combined with many acceptors such as dithienyl
A1, A2, A6, and A56 [366], A24 bearing phenyl groups [367],
A31 [367], A32 [368], and A33 [368], and most of them
exhibited excellent PCEs of around 6%. Particularly, a D16-
based D–A polymer with octoxylphenyl substituted A24 as
an acceptor and two additional thiophenes in the backbone
was recently reported to give a PCE as high as 7.51% upon
carefully optimizing the polymer/PC71BM ratios [369].
Other heteroatom bridged (thienyl-phenylenyl-
thienyl)s D17–D20 and their D–A polymers with various
acceptors were successively reported in last two years
[370–375]. All of them are promising as polymer semi-
conductors applied in OFETs and OPV but the performances
are not better than those containing D16. This result is
similar to the aforementioned bridged bithiophene donors,
1873
in which C-bridged D11 polymers revealed again the best
performance.
More coplanar ␲-conjugated bridged heteroacenes
including D21–D29 were synthesized and applied to design
D–A polymers [308,309,376–385]. The heteropentacenes
D21 and D22 represent two dithienocarbazole isomers,
which led to distinct backbone curvature of the resulting
D–A polymers. As a result, copolymers of D21 combined
with A36, A42TT, and A45 as acceptors demonstrated
low OFET mobilities in the level of 10−3 cm2 /V s, whereas
the corresponding D22 containing copolymers had bet-
ter performances, particularly, a hole mobility as high as
1.36 cm2 /V s was achieved from the D22–A42TT polymer
[377]. Hexacyclic donors D23 and D24 with the above
acceptors were also synthesized and applied in OFETs and
OPV [378,379]. By carefully choosing the acceptor, a PCE
of 5.52% was reached for the D24–A12 polymer [379].
A heteroheptacene D25 with the inclusion of carbazole
and thiophene units, and its D–A polymers were reported
separately by several research groups, but their perform-
ances in OFETs and OPV were moderate [308,309,380]. A
structurally similar analog D26 with a silicon instead of
a nitrogen bridge exhibited a slightly better PCE of 4.2%
when copolymerized with A6 [381]. A best performance
of this kind of heptacyclcic donors in OPV devices was
achieved from a carbon-bridged D27 polymer with A6 as
an acceptor as well, providing a PCE of as high as 7.0% [382].
Two more heptacyclic donors D28 and D29 were reported
quite recently [383–385]. The corresponding D–A polymers
exhibited modest field-effect mobilities between 10−4 and
10−2 cm2 /V s, but good performance in OPV devices. A PCE
of 6.6% was obtained for the D28–A36 polymer by opti-
mizing the device processing conditions [383]. A polymer
derived from D29 and A12 exhibited a PCE of 7.0% with a
large Voc of 0.95 V without any additives or thermal anneal-
ing processes. The higher PCE compared with the D16–A12
copolymer was attributed to the improved charge carrier
mobility and higher absorption coefficient [385].
By fusing benzene and thiophene to design donor
units, one can obtain several isomers of a class of
molecules with same numbers of benzene and thiophene.
This characteristic was typically reflected by compar-
ing the isomers of benzodithiophenes (BDT, D33–D35),
benzotrithiophenes (BTT, D36–D38), and naphthodithio-
phenes (NDT, D39–D41). As for thienothiophenes, there
exists also three isomers (D30–D32) but they are employed
as donors in only a few cases. Particularly D31 derivatives
containing electron-withdrawing substituents (A48–A50
and A55) are a class of important acceptors for synthesizing
high-performance OPV polymers, which are summarized
in a recent review [316].
Among all BDT isomers, benzo[1,2-b:4,5-b ]dithiophene
(D33) has attracted the widest interest for synthesizing
D–A polymers with excellent PCEs even exceeding 6.5%
[12,386–389]. Further details of these polymers and their
applications in OPV devices can be found in related reviews
[390,391]. For D33, on the other hand, two additional
aromatic substituents can be introduced at the central ben-
zene, leaving the planarity of the whole unit intact. This has
been utilized to construct D–A polymers with 2D architec-
tures and recently a PCE as high as 8.8% has been achieved
1874 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Fig. 10. Molecular structures of seven benzotrithiophene isomers and their calculated frontier orbitals (DFT-B3LYP 6-31G*). The HOMO (lower) and LUMO
(upper) orbital energies are given in eV.
based on such a 2D D–A polymer [8] (see also Section
3.3). Two other BDT isomers D34 and D35 possess a sim-
ilar coplanarity and electron-donating ability as D33 but
different topology such that their polymers demonstrated
deeper HOMO energy levels and higher Voc [160,392,393].
Higher PCEs, however, were not achieved.
BTTs have emerged as a class of attractive donor units
for the design of D–A polymers in recent years. The copla-
narity and extended ␲-conjugation of the BTT skeleton
should promote intermolecular ␲-stacking, which would
induce strong aggregation and enhanced packing in the
solid state of the BTT-containing polymers. As outlined
above these features are particularly desirable for improv-
ing charge carrier transport in OFET devices [4]. There
are seven BTT isomers as presented in Fig. 10. Among
them, BTT1 [394,395], BTT2 (D36) [396,397], and BTT3
(D37) [398–401] have been synthesized and widely stud-
ied, particularly, D37-containing D–A polymers thereby
demonstrated promising potential for PSCs. Another iso-
mer BTT7 (D38) has also been synthesized recently with
higher HOMO level than for the other isomers as estimated
by DFT calculations [402]. Its copolymers with A6 and
A6TT as acceptors (174 and 175, Scheme 2.4.2) exhibited
a pronounced difference in their supramolecular orga-
nization and only 175 promising OFET performance. No
charge carrier transport was found for 174 even though
a good ␲-stacking distance of only 0.35 nm in the bulk
was evidenced. In stark contrast, polymer 175 exhib-
ited a hole mobility of 0.04 cm2 /V s, in agreement with
the well-ordered film and the organization into lamellar
structures with a ␲-stacking distance of 0.37 nm. This vari-
ation in device behavior was attributed to the evidently
different degree of curvature in the polymer backbone
Scheme 2.4.2. D38 containing D–A polymers.
induced by the additional two thiophene units in 175
[4].
Three NDI isomers have been applied to synthesize D–A
polymers which also exhibited promising PSC perform-
ances. D39 with different side chains was copolymerized
with alkyl substituted A6TT to investigate the influence of
the size of the side chains on the photovoltaic properties.
The overall efficiency of these OPV devices varied signifi-
cantly from 1.20% to 3.36%, depending on the different side
chains [347]. When replacing A6 with A12, the PCE was
improved up to 5.6% [403]. This donor was also combined
with dialkylthienyl A15 thereby exhibiting a PCE of 6.2%
with a high Jsc of 14.16 mA/cm2 [404]. Two other isomers
of NDT, D40 and D41, possess linear extension leading to
small ␲–␲ stacking distance. Polymers combining D40 and
dialkylthienyl carrying acceptors A6 and A21 presented
a very close ␲–␲ stacking of 3.5 Å. Particularly, the lat-
ter exhibited a hole mobility of 0.54 cm2 /V s and a PCE of
4.9% [405]. D41 has been combined with A36 and A42TT in
corresponding copolymers yielding PCEs of 4.0% and 5.4%,
respectively [406,407]. For copolymer D41–A42TT in an
inverted PSC the PCE reached up to 6.9% [407].
Additionally, larger fused donating units with extended
␲-conjugation have emerged in developing narrow
band gap polymers for the PSCs. A polymer containing
tetrathienoanthracene D42 with A50 as an acceptor was
reported to result in a high PCE of up to 5.6% by using 2%
DIO as an additive during device fabrication [408]. Two
anthradithiophene isomers D43 and D44 having different
linear and angular shapes were both copolymerized with
A42TT. The polymer based on D43 with additional ethiny-
lene units in the backbone exhibited hole mobilities on
the order of 0.1 cm2 /V s, while the bent isomer containing
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.4.3. D–A polymers with A40 and A41.
polymer (D44) gave a lower FET mobility but a promising
PCE of 4.24% in an OPV device when using a processing
additive [409,410]. Phenothiazine D45, that is a tricyclic
nitrogen–sulfur heterocycle, can also serve as a donor
unit. When copolymerized with NDI (A40) and PDI (A41),
the polymers exhibited n-channel field-effect behavior
with electron mobilities of 0.05 cm2 /V s [411]. D45 and
its derivative with an oxidized sulfur group (S,S-dioxides)
were also combined with A6TT and the resulting polymers
were investigated in OFET and OPV devices, but the
performances in both cases were only moderate [412].
2.4.2.2. D–A polymers with acceptors A1–A60. As depicted
in Fig. 8, we classify the reported acceptors units into
six types. Among these acceptors, A6, A36, and A42 have
received the greatest attention. Almost all donors have
been subjected to copolymerization with these acceptors
and most of the resulting polymers have already been dis-
cussed above. Especially, polymers containing A42 have
reached record values for both p- and n-type mobili-
ties, as well as very high PCEs in PSCs. Therefore, we
shall now concentrate on the latest developments of A42-
based polymers and another two more classes of polymers
based on tetracarboxydiimides (A40 and A41) and isoindi-
gos (A45–A47). The other acceptors are listed in Table 3
together with corresponding publications, in which the
preparation and performance in electronic devices of the
corresponding D–A polymers can be found in detail.
The tetracarboxydiimides (A40 and A41) have strong
electron-withdrawing ability, which can be employed to
impart n-type characteristics to organic/polymer semi-
conductors [452]. Most of these polymers exhibited
dominant electron transporting property and were tested
as alternatives to fullerene for fabricating all-polymer solar
cells (all-PSCs).
Many D–A polymers with A40 as an acceptor and
oligothiophenes as donors have been reported [450,451].
1875
Among them, polymer 176 (Scheme 2.4.3) provided excel-
lent OFET performance with an electron mobility as high
as 0.45–0.85 cm2 /V s under ambient conditions [452]. A
new polymer 177 with biselenophene replacing bithio-
phene in 176 was reported to give an electron mobility
of 0.07 cm2 /V s. It was also applied as the acceptor com-
ponent blended with P3HT in an all-PSC, yielding a PCE
of 0.9% [453]. A D–A block copolymer 178 composed of
P3HT and poly(A40) segments was recently synthesized
and blended with P3HT to make the all-PSCs with a PCE
of 1.28% [454]. A slightly higher PCE of 1.63% for an all-PSC
was obtained from 179 after optimizing the morphology
with 1,8-diiodooctane as a solvent additive also providing
a decent FF of 0.66 [455].
Polymer 180 containing A41 exhibited a lower electron
mobility of 2 × 10−3 cm2 /V s and worse stability compared
to the analog polymer 176 with A40 as the acceptor [456].
Another polymer 181 with D14 as the donor resulted
in a relatively high electron mobility of 0.013 cm2 /V s.
This polymer was also tested as an acceptor material to
fabricate all-PSCs, giving an average PCE over 1% [457].
More donor units have been combined with A41 to make
polymers 182a–f applied in all-PSCs. By optimizing the
solvent mixtures and controlling the phase separation,
a high PCE of 2.23% from the all-PSCs with 182f as the
acceptor material was achieved [458]. Up to now, the
reported PCEs from the all-PSCs are still not comparable to
those of polymer/fullerene PSCs. More investigations are
needed to precisely control the energy levels of the donor
and acceptor components as well as carefully optimize
their mixing conditions and the morphology.
Diketopyrrolopyrrole (DPP, A42) has emerged as
extremely attractive acceptor to construct D–A polymers
for both OFETs and PSCs in recent years. The coplanarity
of the DPP unit as well as its ability to readily form
hydrogen bonds with neighboring units in the polymer
backbone, result in strong intermolecular ␲–␲ stacking.
1876 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.4.4. Recent examples of DPP polymers.
Moreover, solubilizing and functional substituents can be
easily attached to the nitrogen atoms of the DPP unit for
improving the solubility and tuning the microstructure of
the polymer [5].
Numerous DPP-based D–A polymers have been
reported as active materials in OFETs and PSCs. Many
DPP-containing polymers are listed in related reviews
[321,322] but record p- and n-type mobilities and very
high PCEs were reached only in 2012 (Scheme 2.4.4).
An important breakthrough with a record hole mobil-
ity was recently achieved for polymers 183a and 183b.
In the two polymers, the highly ␲-extended (E)-2-(2-
(thiophen-2-yl)vinyl)thiophene was used as a donor unit,
which improves coplanarity and promotes intermolecular
␲–␲ stacking. The studies demonstrated that the lengths
of the branched alkyl chains significantly influence the
film-forming ability, intermolecular interaction forces, and
charge-carrier transport characteristics. The polymer 183b
with longer side chains exhibited more uniform thin films
and closer ␲–␲ stacking distances compared to those of
183a. Therefore, the polymer 183b exhibited an unprece-
dented high mobility of up to 8.2 cm2 /V s with a current
on/off ratio of 105 –107 , and a good environmental stabil-
ity. For 183a still a high mobility of 2.0–4.5 cm2 /V s was
measured with a current on/off ratio of 105 –107 . FETs fab-
ricated from these polymers can well compete with those
of organic small-molecule semiconductors and amorphous
silicon semiconductors [5]. An analog of 183b, polymer
184 with selenophene replacing thiophene at both sides
of the vinylene unit, was reported soon after. Similar
to the thiophene–vinylene–thiophene unit in 183b, the
selenophene–vinylene–selenophene group in 184 can also
serve to extend the conjugation length, leading to enhanced
intermolecular interactions. Furthermore, the lone pair of
selenophene atoms is more mobile than that of thiophene,
because it participates less in aromaticity, which leads to
enhancement of the chain interaction between neighbor-
ing chains and to the carrier transport phenomena. As a
result, a highly ordered structure and a remarkably high
carrier mobility of 4.97 cm2 /V s with a current on/off ratio
of 1.6 × 107 was found for polymer 184 [459].
There are some interesting reports on the modifi-
cation of side chains attached to the nitrogen centers
of the DPP unit. Polymer 185 has an alternating con-
jugated backbone between DPP and bithiophene but
one of the DPP comonomers is functionalized with tri-
ethylene glycol (TEG) side chains. This was found to
induce spontaneous chain crystallization while provid-
ing maximum solubility and allowing the synthesis of
high-molecular-weight polymers. Carefully engineered
top-gate OFETs based on the polymer 185 exhibited a
maximum electron mobility of 3 cm2 /V s [6]. In another
case 186, one of the DPP comonomers was protected
by thermally labile tert-butoxycarbonyl (t-BOC) groups
which can be thermally cleaved leading to the formation
of a hydrogen-bonded network within the DPP-based
polymers to enhance intermolecular charge-carrier hop-
ping. Upon a solution-shearing process, the polymer 186
presented p-channel dominant characteristics, with hole
and electron mobilities of 0.0132 and 0.0026 cm2 /V s,
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
respectively. After the thermal cleavage of t-BOC groups at
200 ◦ C, the dominant polarity of charge carriers changed
from positive to negative, resulting in superior elec-
tron mobility of 0.0460 cm2 /V s compared with the hole
mobility of 0.0043 cm2 /V s [460]. Inspiration was also
taken from the initial discovery which demonstrated that
siloxane-terminated solubilizing groups as side chains in
an isoindigo-containing polymer could enhance charge
transport by inducing a denser ␲–␲ spacing and a larger
crystalline coherence length [461]. Thus a DPP-based poly-
mer 187 bearing siloxane-terminated solubilizing groups
was also reported quite recently [462]. By optimizing the
solution-processing techniques, high hole and electron
mobilities of up to 3.97 and 2.20 cm2 /V s with relatively
well-balanced polarities were achieved.
In addition to the numerous variations of the
comonomer unit, the thienyl units introduced at both
sides of the DPP unit were also replaced with other
aromatic groups to further optimize the electrical proper-
ties of DPP-containing copolymers. A typical substitute is
thieno[3,2-b]thiophene that was directly linked with DPP
units to design polymers 188 and 189 reaching a maxi-
mum hole mobility of 1.95 cm2 /V s. PSCs comprising the
polymer 189 and PC71BM gave a PCE of 5.4% [463]. Other
electronic moieties such as furan and selenophene were
applied to replace thiophene in DPP copolymers [464–466].
More examples can be found in the recent review on DPP
containing polymers [322].
Isoindigo (A45) is a structural isomer of the famous
pigment indigo and has been developed as an electron
acceptor for designing D–A polymers recently [467]. Its
homopolymer presented an n-type character, capable of
serving as an acceptor material to fabricate all-PSCs. When
blended with P3HT it yielded a PCE of 0.5% [468]. After
copolymerization with donor units, many A45 containing
D–A polymers were synthesized for OFET and PSC devices.
Polymers 190 and 191 displayed similar photophysical and
electrochemical properties but completely different OFET
performance. The latter exhibited an air-stable hole mobil-
ity as high as 0.79 cm2 /V s with a current on/off ratio of
107 [469]. For the application in solar cells, polymer 192
afforded a PCE of 6.3% when blended with PC71BM, which is
a record reported for isoindigo polymers [470]. Other donor
units such as DTS (D13) [471] and BDT (D33) [472] were
also combined with A45, producing polymers 193–195,
which exhibited acceptable PCEs higher than 4%.
A promising approach was the investigation of the influ-
ence of the branching position of the alkyl side chains on the
FET performance by comparing isoindigo-based polymers
191, 196–198 [473]. The highest mobility was achieved
from 197 with an impressive value of 3.62 cm2 /V s. As
described for the DPP-based polymers, the introduction of
siloxane-terminated side chains can remarkably improve
the charge transport. This strategy was employed for
the isoindigo-based polymer 199 [461]. The solution-
processed FETs based on this polymer gave a maximum
hole mobility of 2.48 cm2 /V s, which was much higher than
that (0.57 cm2 /V s) obtained from a reference polymer with
branched alkyl chains. The result was supported by the
polymer packing where 199 exhibited a closer ␲–␲ stack-
ing distance of 3.58 Å, compared to the analog (3.76 Å).
1877
Isoindigo was structurally modified to design new
acceptors. Fluorination of the isoindigo unit gave a new
acceptor A46 which was expected to lower the LUMO
level of the corresponding polymer and increase the elec-
tron mobility. As a result, the LUMO level of polymer 200
was reported at −3.88 eV which was 0.18 eV lower than
that of the polymer without fluorine. FET devices apply-
ing 200 and fabricated under ambient conditions provided
improved electron mobility of 0.43 cm2 /V s by compari-
son with the non-fluorinated polymer, while maintaining
high hole mobility up to 1.85 cm2 /V s [474]. Substituting
the benzene in isoindigo with thiophene produces another
new acceptor, namely thienoisoindigo (A47). It has been
copolymerized with many donor units (201) as displayed in
Scheme 2.4.5. The FET performances from these polymers,
however, were moderate compared with the isoindigo-
based analogs, reaching hole mobilities between 10−4 and
10−2 cm2 /V s [475,476].
2.4.2.3. D–A polymers containing dual acceptors. We note
that apart from the alternating copolymers between one
donor and one acceptor several D–A copolymers contain-
ing different acceptor units have also been reported. Such
polymers usually exhibit ambipolar or electron-dominant
transporting characteristics owing to the introduction
of two acceptors. A typical example is the copolymer
formed from A42TT and A6. Two polymers (202a and
202b Scheme 2.4.6) with the A42TT-A6 alternating con-
jugated backbone and minor difference in the length of the
alkyl chains were reported independently by two research
groups [477,478]. Polymer 202a afforded a HOMO level of
−5.2 eV and a LUMO level as low as −4.0 eV, which was
ideal for the formation of electron and hole accumula-
tion layers. The mobilities reached 0.35 cm2 /V s for holes
and 0.40 cm2 /V s for electrons, respectively, after anneal-
ing at 200 ◦ C [477]. Polymer 202b presented an ambipolar
transporting property as well, with balanced mobilities of
∼0.1 cm2 /V s for both charges [478].
Further work reported polymer 203 with one more BT
unit inserted into the backbone [479]. The consecutive BT
groups cause a strong twist in the polymer main chains,
which led to an amorphous microstructure. This poly-
mer exhibited n-channel FET characteristics with electron
mobility of 10−3 cm2 /V s, one order of magnitude higher
than the hole mobility. Another modification for 202 is to
replace the thiophene units with selenophenes. The result-
ing polymer 204 exhibited a more red-shifted absorption
than 202a, and high hole and electron mobilities of 0.46
and 0.84 cm2 /V s for spin-coated polymer films annealed
at 200 ◦ C [466].
Another A42TT and A6-containing polymer 205 was
studied in relation to polymers 206a and 206b with a
stronger acceptor A20 replacing A6 [480]. Compared with
the A42TT-A6 polymers, the integration of A20 typically
resulted in polymers having very narrow band gaps of
around 0.65 eV. These polymers exhibited excellent tran-
sistor performance, with mobilities above 0.1 cm2 /V s, even
exceeding 1 cm2 /V s for 206b. The two strong acceptors
in the polymers 206a and 206b rendered them strongly
ambipolar.
1878 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 2.4.5. D–A polymers with isoindigo derivatives A45–A47.

Polymers 207 and 208 containing two acceptors A6 and
A7 in the backbone were synthesized by testing dipotas-
sium bis(trifluoroborate) derivative of A7 as a monomer
in this modified Suzuki polycondensations reactions [481].
The polymer 207 composed of all electron-accepting
units gave an electron mobility of 0.02 cm2 /V s. The good
electron-transport properties of the polymers let them be
tested as replacements of PCBM in preparing all-PSCs with
Voc larger than 1.2 V [482]. The new acceptor A47 (thio-
phene substituted isoindigo) was also copolymerized with
A6. The resulting polymer 209 exhibited a narrow opti-
cal band gap in the film of about 0.92 eV which is roughly
0.3 eV lower than that of DPP-BT copolymer (202). The FETs
exhibited excellent ambipolar behavior, with both hole and
electron mobilities recorded over 0.1 cm2 /V s [483].
Polymers containing dual acceptors were also used as
donor materials in PSCs. A polymer 210, which contained
alkoxylated A6 and quinacridone A52 in the main chains,
possessed an optical band gap of 1.92 eV and a LUMO level
of −3.32 eV. When blending with PC71BM in a 1:1 weight
ratio, a PSC afforded the PCE of 2.5% [484]. Another polymer,
211, containing A49 and A50 as acceptors and BDT (D33)
as a donor was applied in an inverted PSC, yielding a PCE of
7.0%. Further modifications on the fabrication of the devices
could improve the performance of PSCs up to an ultimately
high PCE value of 7.9% [485].
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 2.4.6. D–A polymers containing dual acceptors.
In this section, we have reviewed the broad scope of the
reported donor and acceptor units and typical D–A poly-
mers derived thereof. By summarizing the performances
of these polymers in the OFETs and PSCs, we could make
an attempt at highlighting some guidelines to design D–A
polymers for two kinds of applications. General require-
ments for the D–A polymers include (1) sufficient solubility
for ease of processing, (2) high molecular weights, (3)
proper positioning of solubilizing side chains to not hin-
der the conjugation but also for tuning the intermolecular
interactions and microstructure in the film, and (4) care-
ful selection of donors and acceptors strength provided by
their HOMO and LUMO energy levels to control the absorp-
tion behavior and band gap. Optimizations on the active
layer morphology and the device processing conditions are
equally important for improving the performances of D–A
polymers, which should be considered in more depth from
the perspective of device physics.
1879
In addition, two topics are worthy of being emphasized
again. First, we have proposed a concept of “dual-acceptor
polymers” and discussed some examples. This concept can
be employed to design ambipolar or electron-transporting
polymers, as well as the acceptor materials to replace
fullerene derivatives for realizing all-polymer solar cells.
It can be predicted that more and more polymers of this
kind will be reported in the near future by combining dif-
ferent acceptors, in particular, A6, A15, A21, A36, A40, A41,
A42, and A45, as depicted in Fig. 8.
Secondly, special attention should be put on inverted
PSCs for the device setup. The PCEs of state-of-the-art
PSCs around 8–9% discussed above were all obtained from
such a device structure [7,8,485]. The inverted PSCs have
several advantages over the conventional ones: (1) avoid
the use of the corrosive and hygroscopic hole-transporting
PEDOT:PSS, facilitating better long-term ambient stability
[7]; (2) use air-stable metals such as Ag or Au as top
1880 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
electrodes, which are more resistant toward degradation
[485]; (3) take advantage of the vertical phase separation
and concentration gradient in the active layer [7]. These
inverted PSCs are currently attracting more attention and
will be compared in more detail for their efficiencies and
durability with the standard ones for appealing polymers.
3. Two-dimensional (2D) conjugated polymers
In the previous sections, linear conjugated polymers
for organic electronics have been presented. These lin-
ear polymer systems could be widely extended to higher
dimensionalities and sophisticated topologies. So far,
however, there is no commonly accepted definition for
two-dimensional (2D) polymers, although the term has
been widely used [10]. Several approaches have been
applied to realize 2D polymers, such as covalent synthe-
sis, H-bonded networks, and supramolecular self-assembly
leading to layered structures [10]. In the part of 2D con-
jugated polymers, the focus is limited those attained by
covalent chemistry.
Various molecular architectures having such 2D con-
jugated structures and sophisticated topologies have
emerged and currently represent a quickly spreading field
of research [270]. The increase of dimensionality in ␲-
conjugated systems can lead to different superstructures
in the solid state and to multidirectional charge trans-
port. Conjugated macrocycles with fully ␲-conjugated and
shape-persistent nature are able to self-assemble into 2D
supramolecular structures thanks to ␲-stacking interac-
tions and show unique optical and electronic behaviors
[486]. Graphene, an individual atomically thick sheet of
graphite, is a most desired 2D polymer. The extraordinary
electronic, thermal, and mechanical properties of graphene
tend to be considered highly useful for manifold applica-
tions [11].
D–A polymers, on the other hand, with 2D extension,
i.e. additional conjugation at the direction perpendicular
to the conjugated polymer backbone have also been pro-
posed (see Fig. 18) [12]. Such polymers were synthesized
and investigated as OPV materials and quite recently an
extremely high PCE of near to 9% has been achieved [8]. This
section is divided up into three parts to describe aforesaid
three classes of macromolecular systems with 2D conju-
gated structures, namely (i) conjugated macrocycles, (ii)
graphene, and (iii) extended D–A polymers.
3.1. Conjugated macrocycles
Macrocycles with rigid, shape-persistent, non-
collapsible, and fully ␲-conjugated backbones have
attracted great interest in the past two decades, owing
to their unique properties and their role as building
blocks of discotic liquid crystals, columnar nanotubes,
guest–host complexes, porous surface networks, and three
dimensional nanostructures [257]. Moreover, macrocycles
as discrete molecular entities possess unique optical and
electronic properties with high potential for applications
in organic electronics [486]. A wide variety of building
blocks, including benzene, thiophene, pyridine, acetylene,
and even large-size PAHs and porphyrins have been
employed to synthesize shape-persistent conjugated
macrocycles [486]. Herein some macrocycles composed of
carbazole, fluorene, PAHs, and thiophene, with interesting
self-assembled structures and potential applications in
OLEDs and OFETs will be discussed.
3.1.1. Carbazole and fluorene-based macrocycles
While 2,7-fluorene- and 2,7-carbazole-containing con-
jugated polymers have been widely studied and applied in
organic electronics the corresponding macrocycles with-
out any end group-defects should also be of great interest
as perfect polymer models. Furthermore they are capa-
ble of forming ordered columnar structures with porous
cavities. Such macrocycles can be synthesized both by
choice of proper geometries for ring closure and by
template-assisted reactions. Often meta-phenylene units
were applied for macrocycles since they facilitate the
ring formation, but they also interrupt the conjugation.
For instance, 3,6-linked carbazole was used to synthesize
square carbazole-ethynylene macrocycles with a diameter
of 1.25 nm, which can form nanofibrils [254]. Thus, a new
approach toward cyclic conjugated oligomers was devel-
oped using even para-phenylene units.
A monodisperse fully conjugated 2,7-carbazole-based
macrocyclic dodecamer 212 (Scheme 3.1.1) has been
synthesized using a porphyrin template-assisted method
[487]. The 2D-WAXS studies on extruded filaments of 212
demonstrated that the molecules self-assemble into hexag-
onal arrays of columns with a packing parameter of 4.7 nm
between the columns. Within the columns the stacking dis-
tance was found to be 0.4 nm, and a correlation between
every four molecules along the column was found, i.e.
each macrocycle was rotated by ∼22.5 degrees toward
each other in agreement with the molecular structure
where every third carbazole unit carried a hydroxyalkyl
chain. Additionally, mono-layers of the macrocycles could
be visualized (Fig. 11) by scanning tunneling microscopy
(STM) on highly oriented pyrolitic graphite (HOPG), which
provided a well-ordered hexagonal packing of “face-on”
structures.
Another 2,7-carbazole-based macrocycle 213 contain-
ing diethynyls in between triscarbazoles was achieved by
elaborate functional design via the same porphyrin tem-
plate, where the sterically demanding solubilizing alkyl
side chains pointed to the outside of the giant ring. A 2D
supramolecular structure of the host–guest complexes was
obtained by physisorption of 213 on HOPG followed by gas-
phase deposition of hexabenzocoronene (HBC) molecules
under high vacuum leading to an inclusion of the HBCs in
the hollow macrocycles. The formation of such a host–guest
complex of 213 with HBC was visible by STM, as depicted
in Fig. 12. Assuming that the guest molecule would also be
able to form columnar stacks, this new type of self organiza-
tion enabled columnar assemblies consisting of conjugated
macrocycles with discotic pillars inside their channels.
These supramolecular structures have a high potential for
electronic devices, such as light amplification using cascade
energy transfer [488].
Similar to 2,7-carbazole-based macrocycle 212, a
monodisperse, completely ␲-conjugated, cyclododeca-
2,7-fluorene macrocycle 214 (Scheme 3.1.2) has been
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1881

Scheme 3.1.1. 2,7-Carbazole-based macrocycles. For 213, an HBC molecule is trapped in the macrocycle.

synthesized using the same method. Since oligo- and
polyfluorenes represent efficient blue-emitting materi-
als for OLEDs, such a monodisperse macrocycle serves
as an attractive model compound in order to gain
a better understanding of related linear architectures,
e.g. to study the impact of end groups on the opto-
electronic properties of linear polyfluorenes. STM mea-
surements indicate that macrocycle 214 self-organizes
on HOPG, forming a well-defined hexagonal pattern
[489].

Fig. 11. STM images of 212 as (a) a monolayer with hexagonal packing, (b) individual macrocycles, and (c) a single macrocycle on an HOPG surface. Ref.
[487], Copyright 2006.
Adapted from with permission from Wiley-VCH Verlag GmbH Co.
1882 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Fig. 12. STM images of 213 as a monolayer with hexagonal packing (a) before and (b) after deposition of HBC molecules on an HOPG surface. Ref. [488],
Copyright 2009.
Adapted from with permission from Wiley-VCH Verlag GmbH Co.

In addition, several smaller carbazole-based macro-
cycles 215–217 (Scheme 3.1.3) were synthesized using
1,8-linked carbazole as a building block [490,491]. They
were designed to form a cavity similar to that of a
porphyrin combined with the ability to bind metal
ions. Since porphyrins are by far the most intensively
studied nitrogen-containing macrocycles, due to their bio-
logical importance as well as their ability to function
as efficient metal complexing ligands, porphyrin-related
macrocycles have attracted tremendous research inter-
ests. They could be applied in broad areas, ranging from
catalysis, nonlinear optics and photodynamic therapy
to organic electronics [490]. Therefore, a large amount
of research has been devoted to porphyrins, expanded
porphyrins, and porphyrin nanorings [492–496]. Related
systems such as the triangular porphyrinoid (218a–e), not
only demonstrated the closest distance between three
cavities in plane, but also showed high catalytic activity
toward oxygen reduction after complexation with three
cobalt (II) ions [493,494]. More details on modified and
expanded porphyrins can be found in recent reviews
[486,497].

Scheme 3.1.2. Macrocycle of 2,7-fluorene.

 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 3.1.3. Porphyrin-related macrocycles.
3.1.2. PAHs-based macrocycles
Some larger-sized PAHs and their nitrogen-containing
derivatives could also be used as building blocks to con-
struct macrocycles. Phenanthrene, one of the simplest
PAHs, which can be polymerized at 3,6-positions to form
deep blue EL polymers as discussed above, was also
employed to synthesize a trimeric macrocycle by the same
way of linkage. A stiff phenanthrene-based macrocycle
219 (Scheme 3.1.4) formed well-oriented columnar super-
structures with a striking thermal stability. Additionally it
demonstrated strong ␲-stacking, resulting in a pronounced
intermolecular interaction. Therefore, mesophase forma-
tion with a large transition window ranging from 148 to
500 ◦ C was found [498].
Triphenanthroline macrocycles 220a–c were reported
with 3 different alkoxyl groups, varying from octyloxy
to hexadecyloxy, in order to compare the discotic self-
assembly behavior [499]. The variation of the length of the
alkyl chains led to severe changes of column formation
with a ␲-stacking distance of 0.37 nm for 220a. As antic-
ipated the inter-columnar distances increased from 3.32
over 3.75 up to 4.22 nm for 220a–c reflecting nicely the
distance dependence between columns on the length of
the alkoxy side chains with overall hexagonal arrangement
of the macrocycles. The interior is slightly larger than the
one in standard porphyrin or phthalocyanine-based mac-
rocycles, reaching opposite N N distances of 0.55 nm. Thus
a number of rather large alkali (Na+ , K+ ) and transition
1883
metal ions (Ag+ , Pb2+ , Cd2+ , Zn2+ , and Cu2+ ) could be incor-
porated into the cycle. The replacement of sodium in the
macrocycle upon addition of silver triflate was also proven
by optical absorption, leading to a red shift from 444 nm to
474 nm for the silver macrocycle.
Triphenylene can be applied for the buildup of
triangular-shaped macrocycles by covalently linking three
triphenylene units through the 7- and 10-positions. A
set of such molecules 221a–d was synthesized, indicating
pronounced self-assembly behaviors and unique optoelec-
tronic properties [500,501]. The self-assembly of 221a
produced oligomers in solution and fibers in the solid
state. The 1:3 charge transfer (CT) complex between 221a
and 2,4,7-trinitrofluorenone resulted in a microball struc-
ture [500]. With long alkoxy side chains, macrocycle 221b
exhibited strong self-assembly and liquid crystallinity as
studied by means of 2D-WAXS techniques. The highly
organized columnar superstructures adopted by this fully
planarized discotic molecule could be applied as charge-
carrier pathways in OFET devices. Compounds 221b–d
provided deep-blue emission in solution and a ten-fold
increase in the fluorescence quantum yield with respect
to parent triphenylene as a result of conjugation along
the cyclic backbone. The macrocycles were tested success-
fully as active materials in OLEDs with promising emissive
properties and device stabilities. A two-layer, solution-
processed OLED using 221d as an active layer and TPBI as an
electron-transport layer exhibited an onset voltage of 3.9 V,
1884 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Scheme 3.1.4. Examples of PAH and N-containing PAH macrocycles.
a maximum luminance of 200 cd/m2 at 6.5 V, and a narrow
deep blue emission similar to PL with CIE coordinates of
(0.16, 0.07). These results demonstrated the great poten-
tial of this new class of triphenylene-based macrocycles
for solution-processed, small-molecule OLED applications
[501].
A pyrene-based macrocycle 222 was synthesized and
investigated in solution by comparison with a linear
pyrene hexamer. This macrocycle displayed blue emission
with a maximum at 439 nm, which is slightly red-shifted
compared to the linear hexamer, suggesting additional
intermolecular interactions in the macrocycle [257].
A triphenylamine derivative, dimethylmethylene-
bridged triphenylamine (heterotriangulene), has been
recently used to construct macrocycles [502]. A tribromi-
nated heterotriangulene could self-organize to form
surface-supported molecular-thin 2D polymer films via
a surface-mediated synthesis (read more in next sec-
tion: graphene nanoribbons). Depending on activation
temperature, 2D porous metal-coordination or covalent
networks were obtained. A heterotriangulene macro-
cycle 223 was prepared using traditional solution-based
Yamamoto coupling and the results compared to those
materials obtained via surface-mediated synthesis [503].
The macroscopic quantities obtained from solution
chemistry allowed single-crystal X-ray analysis and a
characterization of optical and electrochemical properties
of this macrocycle. Due to high symmetry with few pre-
dicted active vibrational modes, this heterotriangulene is
a promising candidate for hole-transport applications in
optoelectronic devices with low power loss.
3.1.3. Thiophene-based macrocycles
Several kinds of macrocyclic oligothiophenes and
their ␲-extended derivatives exhibiting unusual elec-
tronic properties have been reported, and some of
them have also been used as semiconductor materi-
als for OFETs. Octathio[8]circulene 224a, a so-called
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1885

“sulflower” and its selenium-containing derivative 224b

were reported (Scheme 3.1.5), demonstrating coplanar
structures with a columnar stacking. OFETs based on
224a-b exhibited hole mobilities of about 9 × 10−3 and
1 × 10−3 cm2 /V s, respectively [504,505]. Recently, neutral
meso-substituted tetrathia[22]annulene[1,1,2,2] aromatic
macrocycles 225a–c were prepared, which displayed
porphyrin-like Soret and Q bands in the absorption spec-
tra. A high hole mobility of up to 0.63 cm2 /V s was achieved
from highly crystalline thin films of these macrocycles
[506]. A benzothiophene-cornered rectangular thiophene-
ethynylene macrocycle 226a with diameter of up to 2 nm
was synthesized and tested in OFETs. A film fabricated
by spin-coating exhibited a hole mobility with a max-
imum value of 7.3 × 10−3 cm2 /V s [507]. In fact, there
was reported an enormous number of macrocyclic thio-
phenes which have been synthesized and characterized
as interesting candidates for various future perspectives
and applications in organic and molecular electronics
also with respect to host–guest interaction, aggregation,
and self-assembly on surfaces. For example, the first
fully conjugated oligothiophene macrocycles 226b were
found to form well-ordered 2D monolayers at the solu-
tion/HOPG interface or two-component donor/acceptor
complexes with C60 presenting a 3D supramolecular
assembly [508]. Further information regarding macrocyclic
oligothiophenes can be found in related reviews [270,486].

3.2. Graphene nanoribbons from polyphenylene

precursors

Graphene, an individual sheet of graphite forming a 2D

honeycomb lattice, is composed of a hexagonal network
of sp2 -hybridized carbon atoms. Thus, it holds poten-
tials for a manifold of applications in catalysis, sensing,
energy storage, as well as optoelectronic devices grounded
on its extraordinary electronic, thermal, and mechani-
cal properties [11]. These properties of graphenes are
strongly dependent on three factors: size, shape and
edge structures. Therefore we start with the discussion
of the implication of the size. Here it is necessary to
clarify the correlation between size and desired applica-
tions of graphene-type molecules because there are several
terminologies such as graphene molecules, graphene
nanoribbons, nanographenes, and graphene sheets, which
sometimes are confusing. As defined recently (Fig. 13)
[11], a length of 100 nm can be considered as a cut-
off point between graphene and nanographene. Graphene
should have sizes exceeding 100 nm in both longitudi-
nal and lateral directions, while graphene fragments with
length smaller than 100 nm are defined as nanographenes.
The small graphene segments that are smaller than
5 nm can be called extended PAHs instead of graphene
molecules. The most interesting graphene-type molecules
are graphene nanoribbons (GNRs), which are defined as
graphene strips with a width of 10–50 nm while main-
taining an aspect ratio of larger than 10. Obviously, these
graphene species with different sizes should exhibit dis- Scheme 3.1.5. Examples of thiophene-containing macrocycles for OFETs.
tinct optical and electronic properties, in particular, GNRs
present ribbon length dependent band gaps and charge car-
rier mobilities [509,510]. Concerning the shape, a graphene
1886 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Fig. 13. Schematic illustration of graphene terminology defined according to their size scale. Ref. [11], Copyright 2012.
Adapted from with permission from Wiley-VCH Verlag GmbH Co.

sheet can be regarded as an infinitely large PAH, main-
taining 2D planar geometry. However, specific to the
graphene molecules and GNRs, various types of derivatives
which appear with linear, triangular, hexagonal, zigzag,
and chevron (V-shaped) geometries have been prepared
[253,511–513] and showed different optoelectronic behav-
iors as well.
Finally one has to consider the edge structures. There
are two types of achiral edges in GNRs, namely, zigzag and
armchair edges, defined by the orientation of the hexagons
relative to the ribbon extension, as presented in Fig. 14.
The edge structure and the row number of carbon atoms
normal to the ribbon axis determine the electronic struc-
ture and ribbon properties [514]. Thus, producing GNRs
with defined edge structures is of great interest for many
chemists and materials scientists. Unfortunately, GNRs fab-
ricated to date usually suffer from disordered edges that
make the band gap poorly defined, which in turn results in
a dramatical degradation of carrier mobility [515]. In addi-
tion, GNRs with pure zigzag edges remain rare relative to
those with armchair ones. They have been predicated to
possess metallic features and to be useful for spin electron-
ics [516].
Therefore, to obtain graphenes in particular GNRs
with well-defined size, shape, and edge structures is the
most important challenge for the application in electronic
devices. Toward this end, two types of protocols have
been explored for the synthesis of graphene and GNRs.

Fig. 14. Armchair (top) and zigzag (bottom) edges in monolayer GNRs. Ref. [517], Copyright 2009.
Reproduced from the American Institute of Physics.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
One is top-down exfoliating graphite toward graphene;
the other is a bottom-up building up of graphene from
molecular building blocks. The top-down approaches for
graphene synthesis comprise of mechanical exfoliation of
highly oriented pyrolyzed graphite (HOPG) [518], liquid-
phase exfoliation of graphite intercalation compounds
[519], and chemical oxidation/exfoliation of graphite fol-
lowed by reduction of graphene oxide (GO) [520,521].
Those examples for GNRs synthesis typically include the
cutting or etching of graphene or graphite precursors into
narrow graphene strips [515,522,523], and the longitu-
dinal unzipping of carbon nanotubes to corresponding
GNRs [524,525]. Two typical bottom-up methods include
epitaxial growth on metallic substrates by means of chem-
ical vapor deposition (CVD) for production of large-area
graphene film [526,527] and organic synthesis based on
precursor molecules for preparation of nanographenes and
GNRs [512,513,528].
Although the top-down methods mentioned above
were widely applied for synthesis of graphene and GNRs,
they suffer from drawbacks such as uncontrollable sizes
and irregular edge structures. In stark contrast, the bottom-
up chemical approaches offer a great opportunity to create
structurally defined graphenes. Nanographenes and GNRs
of various sizes and shapes have been obtained by atom-
ically precise syntheses. Initially, some extended PAHs
were synthesized via intramolecular cyclodehydrogena-
tion as small nanographene molecules with sizes between
1 and 5 nm and various molecular geometries [529–531].
The limited conjugation length of graphene molecules
lies outside the scope of this review, and for a more
detailed discussion on synthetic strategies, as well as
issues of solubility and partial cyclodehydrogenation the
reader is referred to more specialized literature [11,253].
Thus, we herein highlight the bottom-up synthesis of 2D
nanographenes using 1D linear polyphenylenes as precur-
sors both in solution and on surfaces.
3.2.1. Solution synthesis of GNRs using polyphenylene
precursors
As noted above, a graphene sheet can be considered as
an infinite PAH built from benzene, therefore the bottom-
up protocols were considered to include high-molecular-
weight, well soluble polyphenylene precursors which later
on undergo cyclodehydrogenation [512,513,528,532,533].
Thus soluble branched polyphenylene precursor 227
(Scheme 3.2.1) can be converted to a GNR 228 by
intramolecular oxidative cyclodehydrogenation [532].
High-resolution TEM images of GNR 228 disclosed two dif-
ferent solid-state domains: an ordered layer structure with
a layer distance of ca. 3.8 Å, and another disordered one
due to the existence of “kinks” in the obtained graphene-
type polymers and/or random stacking of GNRs. Standard
spectroscopic characterizations in solution, however, were
not possible. Thus GNRs 230 with larger number of side
chains even though extended linearly, to provide bet-
ter solubility were developed [513]. The polyphenylene
precursor 229, which was prepared by Suzuki–Miyaura
coupling reaction between diboronic ester of hexaphenyl-
benzene and 1,4-diiodo-2,3,5,6-tetraphenylbenzene, with
Mn of 14 kg/mol and low polydispersity of 1.2, was soluble
1887
in common organic solvents. Subsequent intramolecular
oxidative cyclodehydrogenation with FeCl3 provided GNRs
230, which was still soluble owing to the presence of
branched alkyl chains. Comparison of the MALDI-TOF spec-
tra of the precursor 229 and product 230 demonstrated
that the intramolecular cyclodehydrogenation proceeded
smoothly. These soluble nanoribbons were fully charac-
terized by UV–vis absorption (max = 485 nm) and STM
techniques [513]. The latter showed that the nanoribbons
230 had lengths of up to 12 nm (Fig. 15).
Another series of five monodisperse GNRs 232a–e were
prepared from precursor 231 by the bottom-up solution
synthesis. The obtained GNRs contain increasing number
of carbon atoms ranging from 132 (232a, n = 1) to 372
(232e, n = 5) along with the increase of the ribbon length.
The smallest representative 232a was still sufficiently sol-
uble exhibiting a maximum absorption at 644 nm [528].
STM images (Fig. 16) of self-assembled monolayers of this
homologue revealed the formation of extended lamellar
structures when adsorbed on HOPG, thus rendering it an
attractive candidate for applications in organic electronic
devices. Unfortunately, the larger homologues of this series
of GNRs were poorly soluble, hampering further investiga-
tions.
In order to obtain longer ribbons, high-molecular-
weight polyphenylene precursors with good solubility
were required. However, the rigidity of polyphenylene
backbones normally induces a strong aggregation result-
ing in poor solubility of the precursors. To overcome this
obstacle, polyphenylene precursors 233a and b with a flex-
ible kinked backbone were designed and synthesized [512].
Benefiting from such a molecular design, the precursor
with solubilizing dodecyl chains had a molecular weight
of up to 20 kg/mol as detected by MALDI-TOF MS. The GPC
analysis with PS as a standard indicated a relatively low
Mn of 9.9 kg/mol, however, with a PDI of 1.4. This made a
graphene nanoribbon 234b achievable after an oxidative
cyclodehydrogenation with FeCl3 . These GNRs had good
solubility that allowed for further structural characteriza-
tions and solution processing, an important requirement
for large-scale preparation of electronic devices.
The aforementioned GNRs fabricated by bottom-up
chemical approaches are limited to those with lateral
dimensions smaller than 1 nm, with absorption only up to
670 nm and calculated band gap larger than 1.6 eV. Quite
recently, a structurally defined and laterally extended GNR
236 with an unprecedented width of close to 2 nm was
synthesized, exhibiting a broad absorption extending into
the NIR region with an optical band gap as low as 1.12 eV
[533]. It should be noted that the precursor 235 was
prepared via a Yamamoto polycondensation using one
dihalogenated monomer. This reaction was believed to
yield high-molecular-weight polymers as compared to a
commonly used Suzuki–Miyaura cross-coupling because
of the intrinsic sensitivity of the latter to stoichiometry.
As a result, MALDI-TOF MS characterization of the pre-
cursor 235 indicated the presence of a regular pattern
with molecular weight up to 35–40 kg/mol. On this basis,
the number of repeating units in 235 was 21–24, which
corresponded to approximately 30 nm of the resulting
GNRs.
1888 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 3.2.1. GNRs synthesized using polyphenylene precursors in solution.

 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1889

Fig. 15. STM images of 230 at the solid/liquid interface on HOPG. Ref. [513], Copyright 2008.
Adapted with permission from the American Chemical Society.

Fig. 16. STM images of 232a on HOPG and corresponding model of molecular arrangement of the aromatic core. The values of intracolumnar (0.4 nm) and
intercolumnar (5 nm) spacing are obtained from STM measurements. Ref. [528], Copyright 2009.
Adapted with permission from the American Chemical Society.

Despite the great achievements in the bottom-up
organic synthesis of graphenes one clearly faces a trade-off
between ribbon size and solubility of the GNRs. The sol-
ubility issue also hampers the solution processing of the
graphenes for electronic devices. To obtain even larger, but
still soluble GNRs with different aspect ratios remains a
challenge for materials chemistry. Another issue for the
solution synthesis of graphenes concerns the efficiency of
the cyclization during the final step under Scholl reaction
conditions, which often suffers from intrinsic problems of
incomplete dehydrogenation and side reactions such as
chlorination. Nevertheless, the power of these synthetic
protocols to create structurally defined graphenes, and the
encouraging results achieved to date should undoubtedly
promote more research.
3.2.2. Surface-mediated synthesis of GNRs using
polyphenylene precursors
Different from the cyclodehydrogenation reactions for
graphene synthesis in solution, the surface-mediated
synthesis of graphenes is carried out under ultrahigh vac-
uum conditions by first depositing halogen substituted
oligophenylene monomers onto a suitable metallic sur-
face, then finishing the thermal-assisted polycondensation
on the surface, and eventually producing the desired
GNRs with shapes and edge structures dependant upon
1890 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Fig. 17. GNRs synthesized using polyphenylene precursors on surface and their STM images. (a) Overview STM image of straight GNR 239 after cyclode-
hydrogenation at 400 ◦ C. Inset: a higher-resolution STM image. (b) STM image taken after surface-assisted C–C coupling at 200 ◦ C before the final
cyclodehydrogenation showing a chain of the polyanthrylene precursor 238, and DFT-based simulation of the STM image with partially overlaid model
of the polymer. (c) High-resolution STM image with partly overlaid molecular model (blue) and a DFT-based STM simulation (greyscale) of GNR 239. (d)
Overview STM image of chevron-type GNR 242 fabricated on a Au(1 1 1) surface. Inset: a higher-resolution STM image and DFT-based simulation of the
STM image (greyscale) with partly overlaid molecular model of the ribbon. (e) STM image of coexisting straight and chevron-type GNR 245 sequentially
grown on Ag(1 1 1). Inset: model of the colligated and dehydrogenated molecules forming the threefold junction overlaid on the STM image. Ref. [511],
Copyright 2010.
Images (a–e) reproduced with permission from the Nature publishing group.

the selected monomers. Several representative examples
have been reported based on such a surface synthesis for
graphenes [511].
A linear-type nanoribbon 239 with armchair edges was
prepared from a monomer of dibrominated bianthryl 237
using the surface-mediated synthesis [511]. The steps for
fabricating such a nanoribbon are illustrated in Fig. 17. First,
an assembled monolayer of monomer 237 is deposited
onto Ag(1 1 1) or Au(1 1 1) surfaces; then a dehalogenat-
ion occurs at 200 ◦ C forming surface-stabilized biradical
species, which couple in a kind of Ullmann reaction to
yield the linear polyanthrylene precursor 238. Finally, the
sample is heated up to 400 ◦ C, enabling intramolecular
cyclodehydrogenation of the precursor polymer chains to
produce GNR 239. STM images before (Fig. 17b) and after
(Fig. 17c) cyclodehydrogenation reveal the formation of
atomically precise GNRs with fully hydrogen-terminated
armchair edges. A transfer method of GNR 239 from the
gold surface to silicon dioxide substrate has also been
demonstrated by a polydimethylsiloxane (PDMS) stamp
transfer process with subsequent etching of the gold layer
in KI solution.
An advantage of this method is that the topology of the
GNRs produced is determined by the halogen substituted
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1891

Table 5
PSC performances of 2D D–A polymers.

Polymer:acceptor (w:w) Jsc (mA/cm2 ) Voc (V) FF PCE (%) Ref.

246a:PCBM (1:4) 9.62 0.99 0.50 4.7 [12]

247b:PCBM (1:4) 6.22 0.90 0.45 3.2 [547]
248a:PCBM (1:4) 8.94 0.91 0.51 4.2 [539]
254:PCBM (1:2) 10.7 0.92 0.58 5.7 [543]
255a:PCBM (1:2) 12.1 0.86 0.60 6.2 [415]
257:PCBM (1:1) 11.7 0.80 0.61 6.0 [427]
260a:PCBM (1:2) 14.6 0.68 0.63 6.2 [391]
260b:PCBM (1:1.5) 17.5 0.74 0.59 7.6 [391]
260c:PCBM (1:1) 16.4 0.69 0.66 7.8 [448]
262a:PCBM (1:2) 14.0 0.73 0.65 6.6 [8]
262a:PCBM (1:2) ∼8.5 ∼1.6 0.60 8.8 [8]
Inverted tandem solar cell

monomers, GNRs with different architectures could thus
be prepared using different oligophenylene precursors.
On this basis, tetraphenyl-substituted dibromotripheny-
lene 240 was further selected as a monomer to produce
a chevron-type GNR 242 with a periodicity of 1.70 nm and
pure armchair edge structures. The temperatures for sur-
face polymerization to yield precursor polymer 241 and
for intramolecular cyclodehydrogenation are both higher
than those in the above case, as shown in Fig. 17. Most
of the GNRs exhibited a length of 20–30 nm and in a few
cases up to 100 nm [511]. This approach can be expanded
to binary-monomer systems, allowing for heteromolecular
coupling to form GNRs 245 with more complex shapes, as
e.g. a threefold GNR junction was clearly visible in the STM
image (Fig. 17e) [511].
Besides rigid graphene nanoribbons, porous graphene
networks with periodical order can be built up
using the bottom-up surface-mediated synthesis. By
thermally annealing precursor monomers, such as
hexaiodo-cyclohexa-m-phenylene and tribrominated
dimethylmethylene-bridged triphenylamine, regularly
porous 2D polymer networks were established [502,534].
For the first case, the domain size of the porous graphene
is about 50 nm × 50 nm with pore spacing of 7.4 Å, while
the second one shows pore spacing from 2.08 to 1.74 nm.
The bottom-up synthesis in solution and on surface
has successfully produced GNRs with defined size, shape,
and edge structures. These chemical strategies are, in our
opinion, the most promising way toward the controlled
synthesis of graphene-type materials. Further research
should focus on their structural characterization and the
understanding of their electronic properties, in particular,
charge transport through single GNRs. Theoretical research
has also demonstrated that GNRs with properly designed
edge structures fulfill the requirements in terms of elec-
tronic level alignment with common acceptors (PC60BM),
solar light harvesting, and singlet–triplet exchange energy
to be used as low band gap semiconductors for OPVs [535].
Therefore, it can be expected that the synthesis and appli-
cation of nanographenes and graphene nanoribbons will be
one of the more popular research directions in the future.
3.3. Two dimensional donor–acceptor polymers
Besides linear D–A polymers as discussed above, a con-
cept of two-dimensional (2D) D–A polymers with extended
conjugation at the direction perpendicular to the polymer
backbone has been proposed to design narrow-band gap
polymers for PSC applications [12]. Their performances in
the PSCs are listed in Table 5. So far there exist two types
of 2D D–A polymers which have been synthesized and
investigated. One is the so-called main-chain donor and
side-chain acceptor (mD–sA) polymers, a concept corre-
sponding to main-chain donor and main-chain acceptor
(mD–mA) polymers. In the mD–sA polymers, a conjugated
backbone serving as an electron-rich donor component is
grafted with a conjugated pendant chain containing an
electron-withdrawing acceptor at the terminus. The other
polymer still has both donor and acceptor in the poly-
mer main chains, similar to the linear D–A polymers, but
the donor or acceptor part contains aromatic substituents
remaining in conjugation with the backbone, forming a 2D
extended architecture. Structural differences between lin-
ear D–A polymers and both types of 2D D–A polymers are
schematically illustrated in Fig. 18.
3.3.1. 2D mD–sA polymers
Compared with the traditional 1D mD–mA copolymers,
2D mD–sA polymers have several interesting features,
such as high hole transporting properties of the main
chains, isotropic charge transport and internal charge
transfer (ICT) (from main chain to side chain). The first two
mD–sA polymers (246a and b, Scheme 3.3.1) were reported
in 2009, in which a fluorene-triarylamine copolymer
backbone was attached with styrylthiophene ␲-bridged
malononitrile or diethylthiobarbituric acid as electron-
accepting pendant groups [12]. Both polymers exhibited
two obvious absorption peaks, with the ␲–␲* transition of
main chains at 385 nm and the strong ICT of side chains
at 600 nm. Their HOMO levels were similar to that of the
fluorene-triarylamine copolymer backbone, while LUMO
levels were lowered down to −3.43 and −3.50 eV, respec-
tively, owing to the strong electron affinity of the side
chains. Theoretical studies also indicate that the HOMO and
LUMO energy levels were separately controlled by main-
chain donor and side-chain acceptor in this type of D–A
polymers [373,536]. PSC devices exhibited PCEs of 4.7%
and 4.4% for 246a and b, respectively, when blending with
PC71BM [12].
Afterwards, studies on 2D mD–sA polymers focused
on the replacement of either the fluorene segment by
other hole transporting units attached with solubilizing
1892 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
Fig. 18. Schematic illustrations of the architectures of 1D and 2D D–A polymers.
alkyl chains or the triphenylene segment by other electron
donors. Dibenzosilole, polymers 247a and b were reported
to exhibit similar band gaps as 246a and b due to the
same polymer main chains but lower PCEs of 2.5% and
3.2%, respectively [537]. A series of 2,7-carbazole-based
2D mD–sA polymers 248–250 have also been synthe-
sized [538,539]. These polymers have similar optical and
electrochemical properties as 246a and b, including two
absorption bands stemming from the ␲–␲* transition of
the main chains, a strong ICT between side and main
chains, and identical HOMO levels because of the identi-
cal polymer backbones. Among them, polymers 250a and b
possess broader absorption bands and stronger absorption
intensities than the other ones because of extended length
of conjugation along the main chains. Another feature of
these polymers is that their hole mobilities strongly rely
on the length of alkyl chains linked at the nitrogen atom of
carbazole. The hole mobilities of 2-ethylhexyl-substituted
polymers 248a and b were measured to be 2.4 × 10−4
and 1.1 × 10−3 cm2 /V s, respectively, higher than those of
polymers 249 and 250 with long branched side chains.
A PCE of 4.2% was obtained from blended 248a:PC71BM
devices. Other hole transporting units used to replace fluo-
rene include cyclopentadithiophene [540], dithienopyrrole
[541], and phenothiazine [541], but their performances in
PSC are moderate with PCEs below 1.5%. Thus, polymers
251a and c exhibited broad absorption bands ranging from
400 to 900 nm, and narrow optical band gaps of 1.34 eV,
however their solar cells yielded PCEs of only about 1.2%
[540].
There are also some reports on replacing the triph-
enylene with other electron-donating units in the mD–sA
polymers. Polymers 252 and 253 were synthesized
containing thiophene in the polymer backbone as an alter-
native to triphenylene, aiming at improving the planarity
of the polymer main chain [373,542]. For both series
of polymers, those with malononitrile as acceptor side
chains showed better performance than other counter-
parts, regardless of the fluorene or carbazole in the main
chains. The device based on 253a/PC71BM demonstrated
the highest PCE of 2.2% with a high Voc of 1.03 V in these
polymers.
For all 2D mD–sA polymers reported to date, only a
few examples (246a, 246b, 247b, and 248a) displayed rela-
tively high PCEs between 3 and 5%. Most of these polymers
provided moderate PCEs with low FF values, probably due
to the poor packing of the polymer chains. Although this
strategy allows for the design of new D–A polymer archi-
tectures showing some interesting properties, more efforts
have to be made to improve the performances in PSC when
compared with conventional D–A polymers.
3.3.2. Benzo[1,2-b:4,5-b ]dithiophene-containing 2D
D–A polymers
Another type of 2D D–A polymers maintain the donor
and acceptor moieties in the polymer main chains, but
forms a 2D structure by attaching conjugated side chains
with the polymer main chains. This design was real-
ized by using benzo[1,2-b:4,5-b ]dithiophene (BDT) as a
donor unit, whose central benzene can be substituted
with two additional aromatic groups bearing solubilizing
alkyl chains, leading to 2D conjugated polymers with
good solubility. Unlike the insulating alkyl chains, these
aromatic substituents can potentially assist the charge
transport. Moreover, the attached aromatic side chains
afford a more electron-rich donor to lower the HOMO
levels, which could be expected to provide a higher
Voc . Typical BDT-based 2D D–A polymers are shown in
Scheme 3.3.2.
Polymer 254 was the first BDT-based 2D D–A polymer
with dialkyl substituted thiophene attached to the cen-
tral benzene of BDT [543]. This polymer exhibited three
absorption bands in the range 300–700 nm both in chloro-
form and in the thin film. PCEs up to 5.66% were obtained
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908 1893

Scheme 3.3.1. Examples of 2D mD-sA polymers.

from the 254-based device, with a Voc of 0.92 V, a Jsc of
10.7 mA/cm2 , and an FF of 57.5% The high Voc and Jsc
were attributed to the low HOMO level of the polymer,
the higher IQE (above 80%), and the EQE response value
beyond 50% in a wide spectral range, respectively. By sub-
stituting the BT unit in polymer 254 with fluoro groups
as acceptors and changing the alkyl chains attached at the
side-chain thiophenes, copolymers 255a and b were syn-
thesized [415]. They provided the desired deep HOMO and
LUMO energy levels providing high Voc and Jsc . The solar
cells prepared from these two polymers were fabricated
using PC71BM as the acceptor, achieving PCEs of 6.21% and
5.64% for 255a and b, respectively. Besides BT, several other
electron-deficient units, such as thiazolothiazole [544],
1894 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908

Scheme 3.3.2. Benzodithiphene-containing 2D D–A copolymers.

 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
naphtho[1,2-c:5,6-c]bis[1,2,5]-thiadiazole [427], benzotri-
azole [447], and 5,5 -bibenzo[c]-[1,2,5]thiadiazole [545],
surrounded by two thiophenes have also been used
as acceptors in a copolymerization with alkylthienyl-
substituted BDT to make 2D D–A polymers (256–258). Most
of them exhibited excellent PCEs of 5–6% with high Voc and
Jsc . A recently reported polymer 258c had a hole mobility of
6 × 10−3 cm2 /V s and was applied in a phototransistor, but
its performance in PSC was not mentioned.
Bithienyl substituted BDT as a donor with extended con-
jugation along the side chains has also been reported. By
using BT and 5-hexylthieno[3,4-c]pyrrole-4,6-dione with-
out additional thiophenes as acceptors, polymers 259a
and b were synthesized [546]. The use of bithienyl sub-
stituents allowed six alkyl substituents per BDT repeating
unit, resulting in relatively high molecular weight of the
polymers but their performances in PSC were modest.
The advantage of BDT-based D–A polymers over 1D D–A
polymers was demonstrated by a comparative study on
alkylthienyl-substituted BDT and alkoxyl-substituted BDT,
respectively, as a donor. Polymers 260a and b exhibited
better thermal stability, red-shifted absorption spectra,
lower HOMO and LUMO energy levels, higher hole mobil-
ity, and improved photovoltaic properties, in comparison
with their corresponding alkoxy-substituted analogs. PCEs
as high as 6.21% and 7.59% were achieved from 260a and
b, respectively [391]. Another polymer 260c containing a
bulky sulfonyl side group at the thieno[3,4-b]thiophene as
an acceptor unit was synthesized [448]. The PCE of 260c
was as high as 7.81%, indicating nearly a 25% increase rela-
tive to an alkoxy-substituted analog.
Apart from thienyl-based conjugated side chains,
decylphenylethynyl substituents were also introduced at
the benzene ring of BDT donors combined with several
acceptors to produce 2D D–A polymers 261a–d [547].
These polymers were comparatively investigated by exper-
imental and theoretical methods but the photovoltaic
properties were not discussed.
Quite recently, a series of low band gap polymers
262a–d having a backbone based on BDT and DPP units
have been synthesized. These polymers exhibited low
energy band gap (1.4–1.5 eV), deep HOMO energy levels,
and high hole mobility. Single junction PSC devices exhib-
ited PCEs of 3–6% by morphology optimization. Higher
efficiencies exceeding 8% were realized in tandem PSCs [8].
Additionally, two D–A polymers containing
tris(thienylenevinylene) side chains with extended
length of conjugation have been reported recently, yield-
ing significant improvement of PCEs in comparison to
the analogs without conjugated side chains. An Isc of
22.6 mA/cm2 is the record for OPV devices so far. These
polymers hold promise to establish a new class of 2D D–A
materials [548].
4. Conclusions and outlook
Herein, several categories of conjugated polymers have
been highlighted, as classified by molecular topology.
1D and 2D conjugated polymers including five material
systems and a molecular design strategy for D–A poly-
mers have been outlined. Without getting into significant
1895
synthetic details, we focused on their performances in elec-
tronics, such as in PLEDs, OFETs, and PSCs.
Among these material systems, conjugated
polyphenylenes are a large family with PFs and PCz
as the most important members. PFs have been widely
studied as versatile semiconductors for various opto-
electronic applications, in particular as light-emitting
materials for red-green-blue (RGB) basic-color and white
electroluminescence. Earlier carbazole-based polymers
were used as light-emitting and host materials, but
have also shown promising performance in PSCs. Other
stepladder conjugated polymers containing carbon or
heteroatom bridges have been applied in optoelectronic
devices, but after first consideration, did not become the
leading materials for further applications. PAH-based
polymers were investigated as semiconductors, enriching
the materials basis for PLEDs and PSCs. The thiophene-
containing polymers have attracted extensive research
interest for organic electronic devices. We first discussed
the thiophene- and fused thiophene-based polymers with-
out additional electron-withdrawing units, which were
mainly applied as p-type semiconductors in the OFETs.
Fully ␲-conjugated and shape-persistent macrocycles
exhibit self-assembled supramolecular structures and
potential applications in OLEDs and OFETs. Graphene is a
unique case of a 2D polymer, and is considered promising
as a candidate for organic electronics. The bottom-up
approach in solution and on surfaces for the synthesis of
graphene nanoribbons with defined size, shape, and edge
structures was discussed. The chemical strategies suffer
from obstacles that need to be circumvented in the future
but are regarded as the most promising way toward the
graphene materials with defined structure.
The D–A strategy has appeared to be most promising
for obtaining high-performance conjugated polymers for
OFETs and PSCs. All aforementioned electron-rich building
blocks can serve as donor units for designing D–A poly-
mers when combining with appropriate acceptor units. We
have listed the known donor and acceptor units and sepa-
rately discussed the performances of typical D–A polymers
with 1D and 2D architectures. Several important guidelines
for designing D–A polymers could then be proposed. To
date the highest FET mobilities and PCEs of PSCs are both
obtained from D–A copolymers.
The D–A polymers should take the leading role in the
research of conjugated polymers for organic electronics.
Thiophene-containing building blocks will probably attract
more research interest than pure hydrocarbons. In addi-
tion, new donor and acceptor units will be continuously
designed and synthesized. Unprecedented structure types
may become rare in view of the large number of already
existing donors and acceptors (see Figs. 6–8). Access to new
building blocks will include the modification of already
existing ones for example, by attaching fluoro or cyano
groups to acceptors. Recent reports on A25 (derived from
A24) [433,434] and A46 (derived from A45) [474] point in
this direction. More research will probably focus on the
elaborate selection of existing donor and acceptor units
and their proper combination in polymers. Thereby, the
optimization of molecular weights and polydispersities as
well as more rigorous purification of established polymers
1896 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
will demand a greater part to further improve their per-
formances. It can also be predicted that the dual-acceptor
polymers will receive more attention owing to their
potential in producing ambipolar or electron-transporting
polymers, and as a possible replacement of fullerene accep-
tors. Another popular research direction comprises the
synthesis and application of nanographenes and graphene
nanoribbons. Chemically synthesizing graphene nanorib-
bons with large lateral dimensions and defined structures
will remain an ongoing target of materials chemists.
The focus, thereby, will be on the structural character-
ization, understanding of electronic properties, charge
transport, and applications in electronic devices of GNRs. It
is believed that further research into conjugated polymers
for organic electronics will continue to furnish excellent
achievements in succession to the rapid progress in the
past decade.
This review has laid an emphasis on the design of
conjugated polymers for optimizing their performance
in electronic devices. It did not focus on the detailed
methods of synthesis. Even if a satisfying laboratory-scale
synthesis of such a polymer has been established, there
remain critical issues, such as costs, upscaling, or the
avoidance of chlorinated solvents for processing. How-
ever, there are many factors influencing the performance
of devices beyond the molecular structure of a conju-
gated polymer as active component. While these are
beyond the scope of the present text, the formation of
supramolecular order (and the related defects) or of phase-
separated morphologies together with the role of the
interfaces should be carefully considered. Organic electron-
ics is thus a multidisciplinary research field requiring the
interaction between synthetic chemists, on the one hand,
and physicists and device engineers, on the other hand.
This review is intended to summarize current research
progress and is hoped to inspire future developments in
the research of ␲-conjugated polymers for organic elec-
tronics.
Acknowledgements
We thank Dr. Brenton Hammer for language polishing.
This work was financially supported by the European Com-
munity EC-ITN-SUPERIOR (GA-2009-238177), the Nano
Sci-E SENSORS, and the ERC Advanced Grant NANOGRAPH
(AdG-2010-267160). X.G. gratefully acknowledges the
Alexander von Humboldt Stiftung for granting a research
fellowship. Portions of this review are repeated from our
previous publications (Refs. [13,31b]).
References
[1] Bian LY, Zhu EW, Tang J, Tang WH, Zhang FJ. Recent progress in the
design of narrow bandgap conjugated polymers for high-efficiency
organic solar cells. Prog Polym Sci 2012;37:1292–331.
[2] Kola S, Sinha J, Katz HE. Organic transistors in the new decade:
toward n-channel, printed, and stabilized devices. J Polym Sci Part
B Polym Phys 2012;50:1090–120.
[3] Burroughes JH, Bradley DDC, Brown AR, Marks RN, Mackay K, Friend
RH, Burns PL, Holmes AB. Light-emitting diodes based on conju-
gated polymer. Nature 1990;347:539–41.
[4] Guo X, Puniredd SR, Baumgarten M, Pisula W, Müllen K.
Benzotrithiophene-based donor–acceptor copolymers with
distinct supramolecular organizations. J Am Chem Soc 2012;134:
8404–7.
[5] Chen HJ, Guo YL, Yu G, Zhao Y, Zhang J, Gao D, Liu HT, Liu YQ.
Highly p-extended copolymers with diketopyrrolopyrrole moi-
eties for high-performance field-effect transistors. Adv Mater
2012;24:4618–22.
[6] Kanimozhi C, Yaacobi-Gross N, Chou KW, Amassian A, Anthopou-
los TD, Patil S. Diketopyrrolopyrrole-diketopyrrolopyrrole-based
conjugated copolymer for high-mobility organic field-effect tran-
sistors. J Am Chem Soc 2012;134:16532–5.
[7] He ZC, Zhong CM, Su SJ, Xu M, Wu HB, Cao Y. Enhanced power-
conversion efficiency in polymer solar cells using an inverted device
structure. Nat Photon 2012;6:591–5.
[8] Dou LT, Gao J, Richard E, You JB, Chen CC, Cha KC, He YJ, Li
G, Yang Y. Systematic investigation of benzodithiophene- and
diketopyrrolopyrrole-based low-bandgap polymers designed for
single junction and tandem polymer solar cells. J Am Chem Soc
2012;134:10071–9.
[9] Rohr S. Neuer Weltrekord für organische Solarzellen: Heliatek
behauptet sich mit 12% Zelleffizienz als Technologieführer.
http://www.heliatek.com/newscenter/latest news/neuer-
weltrekord-fur-organische-solarzellen-heliatek-behauptet-sich-
mit-12-zelleffizienz-als-technologiefuhrer/?lang=en [accessed
March 2013]. 3 pp.
[10] Sakamoto J, van Heijst J, Lukin O, Schlüter AD. Two-dimensional
polymers: just a dream of synthetic chemists? Angew Chem Int Ed
2009;48:1030–69.
[11] Chen L, Hernandez Y, Feng X, Müllen K. From nanographene and
graphene nanoribbons to graphene sheets: chemical synthesis.
Angew Chem Int Ed 2012;51:7640–54.
[12] Huang F, Chen KS, Yip HL, Hau SK, Acton O, Zhang Y, Luo JD, Jen AKY.
Development of new conjugated polymers with donor-pi-bridge-
acceptor side chains for high performance solar cells. J Am Chem
Soc 2009;131:13886–7.
[13] Grimsdale AC, Müllen K. Oligomers and polymers based on bridged
phenylenes as electronic materials. Macromol Rapid Commun
2007;28:1676–702.
[14] Mainthia SB, Kronick PL, Ur H, Chapman EF, Labes MM. Electronic
conductivity of complexes of poly-p-phenylene. Polym Prepr Am
Chem Soc 1963;4(1):208–12.
[15] Akiyama M, Iwakura Y, Shiraishi S, Imai YJ. Poly-p-phenylene-
1,2,4-oxadiazole from p-cyanobenzonitrile oxide by a solid-state
cycloaddition polymerization. J Polym Sci Part B Polym Lett
1966;4:305–8.
[16] Vahlenkamp T, Wegner G. Poly(2,5-dialkoxy-p-phenylene)s-
synthesis and properties. Macromol Chem Phys 1994;195:
1933–52.
[17] Yang Y, Pei Q, Heeger AJ. Efficient blue polymer light-emitting
diodes from a series of soluble poly(para-phenylene)s. J Appl Phys
1996;79:934–9.
[18] Grem G, Leditzky G, Ullrich B, Leising G. Realization of a blue-light-
emitting device using poly(p-phenylene). Adv Mater 1992;4:36–7.
[19] Scherf U, Müllen K. Polyarylnes and poly(arylenevinylenes).
7. A soluble ladder polymer via bridging functionalized
poly(para-phenylene)-precursors. Makromol Chem Rapid
Commun 1991;12:489–97.
[20] Scherf U, Müllen K. Poly(arylene)s and poly(arylenevinylene)s. II.
A modified two-step route to soluble phenylene-type ladder poly-
mers. Macromolecules 1992;25:3546–8.
[21] Grem G, Paar C, Stampfl J, Leising G, Huber J, Scherf U. Soluble
segmented stepladder poly(p-phenylenes) for blue-light-emitting
diodes. Chem Mater 1995;7:2–4.
[22] Romaner L, Heimel G, Wiesenhofer H, Freitas PSd, Scherf U,
Brédas JL, Zojer E, List EJW. Ketonic defects in ladder-type poly(p-
phenylene)s. Chem Mater 2004;16:4667–74.
[23] Grüner J, Hamer PJ, Friend RH, Huber HJ, Scherf U, Holmes AB. A high
efficiency blue-light-emitting diode based on novel ladder poly(p-
phenylene)s. Adv Mater 1994;6:748–52.
[24] Wu Y, Zhang J, Fei Z, Bo Z. Spiro-bridged ladder-type poly(p-
phenylene)s: towards structurally perfect light-emitting materials.
J Am Chem Soc 2008;130:7192–3.
[25] Gilch HG, Wheelwright WL. Polymerization of ␣-halogenated p-
xylenes with base. J Polym Sci Part A-1 1966;4:1337–49.
[26] Sariciftci NS, Smilowitz L, Heeger AJ, Wudl F. Photoinduced elec-
tron transfer from a conducting polymer to buckminsterfullerene.
Science 1992;258:1474–6.
[27] Gustafsson G, Cao Y, Treacy GM, Klavetter F, Colaneri N, Heeger
AJ. Flexible light-emitting diodes made from soluble conducting
polymers. Nature 1992;357:477–9.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[28] Greenham NC, Moratti SC, Bradley DDC, Friend RH, Holmes AB. Effi-
cient light-emitting diodes based on polymers with high electron
affinities. Nature 1993;365:628–30.
[29] Granström M, Petritsch K, Arias AC, Lux A, Andersson MR, Friend
RH. Laminated fabrication of polymeric photovoltaic diodes. Nature
1998;395:257–60.
[30] Laquai F, Mishra AK, Ribas MR, Petrozza A, Jacob J, Akcelrud
L, Müllen K, Friend RH, Wegner G. Photophysical properties
of a series of poly(ladder-type phenylene)s. Adv Funct Mater
2007;17:3231–40.
[31] (a) Xie LH, Yin CR, Lai WY, Fan QL, Huang W. Polyfluorene-based
semiconductors combined with various periodic table elements for
organic electronics. Prog Polym Sci 2012;37:1192–264;
(b) Li C, Liu MY, Pschirer NG, Baumgarten M, Müllen K.
Polyphenylene-based materials for organic photovoltaics. Chem
Rev 2010;110:6817–55.
[32] Neher D. Polyfluorene homopolymers: conjugated liquid-
crystalline polymers for bright blue emission and
polarized electroluminescence. Macromol Rapid Commun
2001;22:1365–85.
[33] Janietz S, Bradley DDC, Grell M, Giebeler C, Inbasekaran M, Woo
EP. Electrochemical determination of the ionization potential
and electron affinity of poly(9,9-dioctylfluorene). Appl Phys Lett
1998;73:2453–5.
[34] Redecker M, Bradley DDC, Inbasekaran M, Woo EP. Nondispersive
hole transport in an electroluminescent polyfluorene. Appl Phys
Lett 1998;73:1565–7.
[35] Ego C, Grimsdale AC, Uckert F, Yu G, Srdanov G, Müllen K.
Triphenylamine-substituted polyfluorene—a stable blue-emitter
with improved charge injection for light-emitting diodes. Adv
Mater 2002;14:809–11.
[36] Miteva T, Meisel A, Knoll W, Nothofer HG, Scherf U, Müller DC,
Meerholz K, Yasuda A, Neher D. Improving the performance of
polyfluorene-based organic light-emitting diodes via end-capping.
Adv Mater 2001;13:565–70.
[37] Redecker M, Bradley DDC, Inbasekaran M, Wu WW, Woo EP. High
mobility hole transport fluorene-triarylamine copolymers. Adv
Mater 1999;11:241–6.
[38] Inbasekaran M, Woo E, Wu W, Bernius M, Wujkowski
L. Fluorene homopolymers and copolymers. Synth Met
2000;111–112:397–401.
[39] Li YN, Ding JF, Day M, Tao Y, Lu JP, D’iorio M. Synthesis and proper-
ties of random and alternating fluorene/carbazole copolymers for
use in blue light-emitting devices. Chem Mater 2004;16:2165–73.
[40] Lu JP, Tao Y, D’iorio M, Li YN, Ding JF, Day M. Pure deep blue
light-emitting diodes from alternating fluorene/carbazole copoly-
mers by using suitable hole-blocking materials. Macromolecules
2004;37:2442–9.
[41] Horii T, Shinnai T, Tsuchiya K, Mori T, Kijima M. Synthesis
and properties of conjugated copolycondensates consisting of
carbazole-2,7-diyl and fluorene-2,7-diyl. J Polym Sci Part A Polym
Chem 2012;50:4557–62.
[42] Wu FI, Reddy DS, Shu CF, Liu MS, Jen AKY. Novel oxadiazole-
containing polyfluorene with efficient blue electroluminescence.
Chem Mater 2003;15:269–74.
[43] Ding J, Day M, Robertson G, Roovers J. Synthesis and charac-
terization of alternating copolymers of fluorene and oxadiazole.
Macromolecules 2002;35:3474–83.
[44] Sung HH, Lin HC. Novel alternating fluorene-based conjugated
polymers containing oxadiazole pendants with various terminal
groups. Macromolecules 2004;37:7945–54.
[45] Hung MC, Liao JL, Chen SA, Chen SH, Su AC. Fine tuning the purity
of blue emission from polydioctylfluorene by end-capping with
electron-deficient moieties. J Am Chem Soc 2005;127:14576–7.
[46] Kulkarni AP, Zhu Y, Jenekhe SA. Quinoxaline-containing polyflu-
orenes: synthesis, photophysics, and stable blue electrolumines-
cence. Macromolecules 2005;38:1553–63.
[47] Liu MS, Jiang XZ, Liu S, Herguth P, Jen AKY. Effect of cyano sub-
stituents on electron affinity and electron-transporting properties
of conjugated polymers. Macromolecules 2002;35:3532–8.
[48] Liu MS, Jiang XZ, Herguth P, Jen AKY. Efficient cyano-containing
electron-transporting polymers for light-emitting diodes. Chem
Mater 2001;13:3820–2.
[49] Peng Q, Peng JB, Kang ET, Neoh KG, Cao Y. Synthesis and
electroluminescent properties of copolymers based on fluorene
and 2,5-di(2-hexyloxyphenyl)thiazolothiazole. Macromolecules
2005;38:7292–8.
[50] Shu CF, Dodda R, Wu FI. Highly efficient blue-light-emitting diodes
from polyfluorene containing bipolar pendant groups. Macro-
molecules 2003;36:6698–703.
1897
[51] Lemmer U, Heun S, Mahrt RF, Scherf U, Hopmeier M, Siegner U,
Göbel EO, Müllen K, Bässler H. Aggregate fluorescence in conju-
gated polymers. Chem Phys Lett 1995;240:373–8.
[52] Bliznyuk VN, Carter SA, Scott JC, Klaerner G, Miller RD, Miller DC.
Electrical and photoinduced degradation of polyfluorene based on
films and light emitting devices. Macromolecules 1999;32:361–9.
[53] Herz LM, Phillips RT. Effects of interchain interactions, polarization
anisotropy, and photo-oxidation on the ultrafast photoluminesce-
nce decay from a polyfluorene. Phys Rev B 2000;61:13691–7.
[54] Prieto I, Teetsov J, Fox MA, Bout DA, Bard AJ. A study of excimer
emission in solutions of poly(9,9-dioctyl-fluorene) using electro-
generated chemiluminescence. J Phys Chem A 2001;105:520–3.
[55] Grimsdale AC, Leclère P, Lazzaroni R, MacKenzie JD, Mur-
phy C, Setayesh S, Silva C, Friend RH, Müllen K. Correlation
between molecular structure, microscopic morphology, and opti-
cal propertiesof poly(tetraalkylindenofluorene)s. Adv Funct Mater
2002;12:729–33.
[56] Haugeneder A, Lemmer U, Scherf U. Exciton dissociation dynamics
in a conjugated polymer containing aggregate states. Chem Phys
Lett 2002;351:354–8.
[57] Panozzo S, Vial JC, Kervella Y, Stéphan O. Fluorene-fluorenone
copolymer: stable and efficient yellow-emitting material for elec-
troluminescent devices. J Appl Phys 2002;92:3495–502.
[58] Zeng G, Yu WL, Chua SJ, Huang W. Spectral and thermal spectral
stability study for fluorene-based conjugated polymers. Macro-
molecules 2002;35:6907–14.
[59] Montilla F, Mallavia R. On the origin of green emission
bands in fluorene-based conjugated polymers. Adv Funct Mater
2007;17:71–8.
[60] Lupton JM, Craig MR, Meijer EW. On-chain defect emission in elec-
troluminescent polyfluorenes. Appl Phys Lett 2002;80:4489–91.
[61] Becker K, Lupton JM, Feldmann J, Nehls BS, Galbrecht F, Gao D,
Scherf U. On-chain fluorenone defect emission from single poly-
fluorene molecules in the absence of intermolecular interactions.
Adv Funct Mater 2006;16:364–70.
[62] List EJW, Guentner R, Freitas PSd, Scherf U. The effect of keto defect
sites on the emission properties of polyfluorene-type materials.
Adv Mater 2002;14:374–8.
[63] List EJW, Gaal M, Guentner R, Freitas PSd, Scherf U. The role of
keto defect sites for the emission properties of polyfluorene-type
materials. Synth Met 2003;39:759–63.
[64] Gong X, Moses D, Heeger AJ, Xiao S. Excitation energy transfer from
polyfluorene to fluorenone defects. Synth Met 2004;141:17–20.
[65] Romaner L, Pogantsch A, Freitas PS, Scherf U, Gaal M, Zojer E, List
EJM. The origin of green emission in polyfluorene-based conju-
gated polymers: on-chain defect fluorescence. Adv Funct Mater
2003;13:597–601.
[66] Gamerith S, Gadermaier C, Scherf U, List EJW. Emission properties
of pristine and oxidatively degraded polyfluorene type polymers.
Phys Stat Sol 2004;201:1132–51.
[67] Gaal M, List EJW, Scherf U. Excimers or emissive on-chain defects?
Macromolecules 2003;36:4236–7.
[68] Kulkarni AP, Kong X, Jenekhe SA. Fluorenone-containing polyflu-
orenes and oligofluorenes: photophysics, origin of the green
emission and efficient green electroluminescence. J Phys Chem B
2004;108:8689–701.
[69] Weinfurtner KH, Fujikawa H, Tokito S, Taga Y. Highly efficient
pure blue electroluminescence from polyfluorene Influence of the
molecular weight distribution on the aggregation tendency. Appl
Phys Lett 2000;76:2502–4.
[70] Craig MR, Kok MMd, Hofstraat JW, Schenning APHJ, Meijer EW.
Improving color purity and stability in a blue emitting polyfluorene
by monomer purification. J Mater Chem 2003;13:2861–2.
[71] Marsitzky D, Murray J, Scott JC, Carter KR. Amorphous poly-2,7-
fluorene networks. Chem Mater 2001;13:4285–9.
[72] Klärner G, Lee JI, Lee VY, Chan E, Chen JP, Nelson A, Markiewicz D,
Siemens R, Scott JC, Miller RD. Cross-linkable polymers based on
dialkylfluorenes. Chem Mater 1999;11:1800–5.
[73] Setayesh S, Grimsdale AC, Weil T, Enkelmann V, Müllen K, Megh-
dadi F, List EJW, Leising G. Polyfluorenes with polyphenylene
dendron side chains: toward non-aggregating, light-emitting poly-
mers. J Am Chem Soc 2001;123:946–53.
[74] Pogantsch A, Wenzl FP, List EJW, Leising G, Grimsdale AC, Müllen
K. Polyfluorenes with dendron side chains as the active materials
for polymer light-emitting devices. Adv Mater 2002;14:1061–4.
[75] Marsitzky D, Vestberg R, Blainey P, Tang BT, Hawker CJ, Carter KR.
Self-encapsulation of poly-2,7-fluorenes in a dendrimer matrix. J
Am Chem Soc 2001;123:6965–72.
[76] Chou CH, Shu CF. Synthesis and characterization of dendronized
polyfluorenes. Macromolecules 2002;35:9673–7.
1898 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[77] Fu Y, Li Y, Li J, Yan S, Bo Z. High molecular weight dendronized
poly(fluorene)s with peripheral carbazole groups: synthesis, char-
acterization, and properties. Macromolecules 2004;37:6395–400.
[78] Lee JH, Hwang DH. Alkoxyphenyl-substituted polyfluorene a sta-
ble blue-light-emitting polymer with good solution processability.
Chem Commun 2003:2836–7.
[79] Hwang DH, Park MJ, Lee JH. EL properties of stable blue light-
emitting polyfluorene copolymers. Mater Sci Eng C 2004;24:201–4.
[80] Yu WL, Pei J, Huang W, Heeger AJ. Spiro-functionalized poly-
fluorene derivatives as blue light-emitting materials. Adv Mater
2000;12:828–31.
[81] Lee JI, Lee H, Oh J, Chu HY, Kim SH, Yang YS, Kim GH, Do LM, Zyung
T. Organic blue light emitting materials based on spirobifluorene.
Curr Appl Phys 2003;3:469–71.
[82] Wu Y, Li J, Fu Y, Bo Z. Synthesis of extremely stable blue light emit-
ting poly(spirobifluorene)s with suzuki polycondensation. Org Lett
2004;6:3485–7.
[83] Vak D, Chun C, Lee CL, Kim JJ, Kim DY. A novel spiro-functionalized
polyfluorene derivative with solubilizing side chains. J Mater Chem
2004;14:1342–6.
[84] Tseng YH, Shih PI, Chien CH, Dixit AK, Shu CF. Stable organic
blue-light-emitting devices prepared from poly[spiro(fluorene-
9,9 -xanthene)]. Macromolecules 2005;38:10055–60.
[85] Pogantsch A, Wenzl FP, Scherf U, Grimsdale AC, Müllen K, List EJW.
Long lived photoexcitation dynamics in a dendronically substituted
poly(fluorene). J Chem Phys 2003;119:6904–10.
[86] Lupton JM, Schouwink P, Keivanidis PE, Grimsdale AC, Müllen K.
Influence of dendronization on spectral diffusion and aggregation
in conjugated polymers. Adv Funct Mater 2003;13:154–8.
[87] Klärner G, Davey MH, Chen WD, Scott JC, Miller RD. Col-
orfast blue-light-emitting random copolymers derived from
di-n-hexylfluorene and anthracene. Adv Mater 1998;10:993–7.
[88] Lim LS, Friend RH, Rees ID, Li J, Ma YG, Robinson K, Holmes AB, Hen-
nebicq E, Beljonne D, Cacialli F. Suppression of green emission in a
new class of blue-emitting polyfluorene copolymers with twisted
biphenyl moieties. Adv Funct Mater 2005;15:981–8.
[89] Xia C, Advincula RC. Decreased aggregation phenomena in polyflu-
orenes by introducing carbazole copolymer units. Macromolecules
2001;34:5854–9.
[90] Peng Q, Xie M, Huang Y, Lu Z, Xiao D. New series of highly phenyl-
substituted polyfluorene derivatives for polymer light-emitting
diodes. J Polym Sci Part A Polym Chem 2004;42:2985–93.
[91] Liu XM, He CB, Hao XT, Tan LW, Li YQ, Ong KS. Hyper-
branched blue-light-emitting alternating copolymers of tetra-
bromoarylmethane/silane and 9,9-dihexylfluorene-2,7-diboronic
acid. Macromolecules 2004;37:5965–70.
[92] Xiao S, Nguyen M, Gong X, Cao Y, Wu H, Moses D, Heeger AJ. Sta-
bilization of semiconducting polymers with silsesquioxane. Adv
Funct Mater 2003;12:25–9.
[93] Setayesh S, Marsitzky D, llen KM. Bridging the gap between
polyfluorene and ladder-poly-p-phenylene: synthesis and
characterization of poly-2,8-indenofluorene. Macromolecules
2000;33:2016–20.
[94] Jacob J, Sax S, Piok T, List EJW, Grimsdale AC, Müllen K. Ladder-type
pentaphenylenes and their polymers: efficient blue-light emitters
and electron-accepting materials via a common intermediate. J Am
Chem Soc 2004;126:6987–95.
[95] Catin PC. Eye Sensitivity. http://miac.unibas.ch/SIP/02-
Fundamentals-media/figs/eyeSensitivity.png [accessed April
2013]; 2012.
[96] Su HJ, Wu FI, Shu CF. Tuning wavelength: synthesis and
characterization of spiro-DPVF-containing polyfluorenes and
applications in organic light-emitting diodes. Macromolecules
2004;37:7197–202.
[97] Su HJ, Wu FI, Tseng YH, Shu CF. Color tuning of a light-emitting
polymer: polyfluorene-containing pendant amino-substituted dis-
tyrylarylene units. Adv Funct Mater 2005;15:1209–16.
[98] Liu J, Min C, Zhou Q, Cheng Y, Wang L, Ma D, Jing X, Wang F. Blue
light-emitting polymer with polyfluorene as the host and highly
fluorescent 4-dimethylamino-1,8-naphthalimide as the dopant in
the sidechain. Appl Phys Lett 2006;88, 083505/1–3.
[99] Sun M, Niu Q, Yang R, Du B, Liu R, Yang W, Peng J, Cao Y. Fluorene-
based copolymers for color-stable blue light-emitting diodes. Eur
Polym J 2007;43:1916–22.
[100] Huang F, Zhang Y, Liu MS, Cheng YJ, Jen AKY. High-efficiency and
color stable blue-light-emitting polymers and devices. Adv Funct
Mater 2007;17:3808–15.
[101] Guo X, Cheng Y, Xie Z, Geng Y, Wang L, Jing X, Wang F.
Fluorene-based copolymers containing dinaphtho-s-indacene as
new building blocks for high-efficiency and color-stable blue LEDs.
Macromol Rapid Commun 2009;30:816–25.
[102] Ego C, Marsitzky D, Becker S, Zhang J, Grimsdale AC, Müllen K,
MacKenzie JD, Silva C, Friend RH. Attaching perylene dyes to poly-
fluorene: three simple, efficient methods for facile color tuning of
light-emitting polymers. J Am Chem Soc 2003;125:437–43.
[103] Wu WS, Inbasekaran M, Hudack M, Welsh D, Yu WL, Cheng
Y, Wang C, Kram S, Tacey M, Bernius M, Fletcher R, Kiszka K,
Munger S, O’brein J. Recent development of polyfluorene-based
RGB materials for light emitting diodes. Microelectronics J 2004;35:
343–8.
[104] Herguth P, Jiang X, Liu MS, Jen AKY. Highly efficient fluorene- and
benzothiadiazole-based conjugated copolymers for polymer light-
emitting diodes. Macromolecules 2002;35:6094–100.
[105] Liu J, Tu GL, Zhou QG, Cheng YX, Geng YH, Wang LX, Ma DG,
BJing X, Wang FS. Highly efficient green light emitting polyfluorene
incorporated with 4-diphenylamino-1,8-naphthalimide as green
dopant. J Mater Chem 2006;16:1431–8.
[106] Lim E, Jung BJ, Shim HK. Synthesis and characterization of a new
light-emitting fluorene-thieno[3,2-b]thiophene-based conjugated
copolymer. Macromolecules 2003;36:4288–93.
[107] Pei J, Yu WL, Huang W, Heeger AJ. The synthesis and characteriza-
tion of an efficient green electroluminescent conjugated polymer:
poly[2,7-bis(4-hexylthienyl)-9,9-dihexylfluorene]. Chem Commun
2000:1631–2.
[108] Hou Q, Xu YS, Yang W, Yuan M, Peng JB, Cao Y. Novel red-emitting
fluorene-based copolymers. J Mater Chem 2002;12:2887–92.
[109] Hou Q, Zhou QM, Zhang Y, Yang W, Yang RQ, Cao Y. Syn-
thesis and electroluminescent properties of high efficiency
saturated red emitter based on copolymers from fluorine and 4,7-
di(4-hexylthien-2-yl)-2,1,3-benzothiadiazole. Macromolecules
2004;37:6299–305.
[110] Yang R, Tian R, Yan J, Zhang Y, Yang J, Hou Q, Yang W, Zhang
C, Cao Y. Deep-red electroluminescent polymers: synthesis and
characterization of new low-band-gap conjugated copolymers for
light-emitting diodes and photovoltaic devices. Macromolecules
2005;38:244–53.
[111] Yang J, Jiang C, Zhang Y, Yang R, Yang W, Hou Q, Cao Y. High-
efficiency saturated red emitting polymers derived from fluorene
and naphthoselenadiazole. Macromolecules 2004;37:1211–8.
[112] Yang R, Tian R, Hou Q, Yang W, Cao Y. Synthesis and optical
and electroluminescent properties of novel conjugated copolymers
derived from fluorene and benzoselenadiazole. Macromolecules
2003;36:7453–60.
[113] Chen X, Liao JL, Liang YM, Ahmed MO, Tseng HE, Chen SA.
High-efficiency red-light emission from polyfluorenes grafted with
cyclometalated iridium complexes and charge transport moiety. J
Am Chem Soc 2003;125:636–7.
[114] Jiang JX, Jiang CY, Yang W, Zhen HG, Huang F, Cao Y. High-
efficiency electrophosphorescent fluorene-alt-carbazole copoly-
mers n-grafted with cyclometalated Ir complexes. Macromolecules
2005;38:4072–80.
[115] Zhen HY, Jiang CY, Yang W, Jiang JX, Huang F, Cao Y. Synthe-
sis and properties of electrophosphorescent chelating polymers
with iridium complexes in the conjugated backbone. Chem Eur J
2005:5007–16.
[116] Ma Z, Ding J, Zhang B, Mei C, Cheng Y, Xie Z, Wang L, Jing X, Wang F.
Red-emitting polyfluorenes grafted with quinoline-based iridium
complex: “simple polymeric chain, unexpected high efficiency”.
Adv Funct Mater 2010;20:138–46.
[117] Gong X, Wang S, Moses D, Bazan GC, Heeger AJ. Multilayer polymer
light-emitting diodes: white-light emission with high efficiency.
Adv Mater 2005;17:2053–8.
[118] Xu Y, Peng J, Mo Y, Hou Q, Cao Y. Efficient polymer white-light-
emitting diodes. Appl Phys Lett 2005;86, 163502/1–3.
[119] Zhou Y, Sun Q, Tan Za, Zhong H, Yang C, Li Y. Double-layer struc-
tured WPLEDs based on three primary RGB luminescent polymers:
toward high luminous efficiency, color purity, and stability. J Phys
Chem C 2007;111:6862–7.
[120] Gong X, Ma W, Ostrowski JC, Bazan GC, Moses D, Heeger AJ. White
electrophosphorescence from semiconducting polymer blends.
Adv Mater 2004;16:615–9.
[121] Huang J, Hou WJ, Li JH, Li G, Yang Y. Improving the power efficiency
of white light-emitting diode by doping electron transport material.
Appl Phys Lett 2006;89, 133509/1–3.
[122] Huang J, Li G, Wu E, Xu Q, Yang Y. Achieving high-efficiency polymer
white-light-emitting devices. Adv Mater 2006;18:114–7.
[123] Kim TH, Lee HK, Park OO, Chin BD, Lee SH, Kim JK. White-
light-emitting diodes based on iridium complexes via efficient
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
energy transfer from a conjugated polymer. Adv Funct Mater
2006;16:611–7.
[124] Shih PI, Tseng YH, Wu FI, Dixit AK, Shu CF. Stable and efficient
white electroluminescent devices based on a single emitting layer
of polymer blends. Adv Funct Mater 2006;16:1582–9.
[125] Tu G, Zhou Q, Cheng Y, Wang L, Ma D, Jing X, Wang F. White
electroluminescence from polyfluorene chemically doped with 1,8-
napthalimide moieties. Appl Phys Lett 2004;85:2172–4.
[126] Liu J, Zhou Q, Cheng Y, Geng Y, Wang L, Ma D, Jing X, Wang F. White
electroluminescence from a single-polymer system with simulta-
neous two-color emission: polyfluorene as the blue host and a
2,1,3-benzothiadiazole derivative as the orange dopant on the main
chain. Adv Funct Mater 2006;16:957–65.
[127] Tu G, Mei C, Zhou Q, Cheng Y, Geng Y, Wang L, Ma D, Jing X, Wang
F. Highly efficient pure-white-light-emitting diodes from a sin-
gle polymer: polyfluorene with naphthalimide moieties. Adv Funct
Mater 2006;106:101–6.
[128] Liu J, Guo X, Bu L, Xie Z, Cheng Y, Geng Y, Wang L, Jing X, Wang
F. White electroluminescence from a single-polymer system with
simultaneous two-color emission: polyfluorene as blue host and
2,1,3-benzothiadiazole derivatives as orange dopants on the side
chain. Adv Funct Mater 2007;17:1917–25.
[129] Liu J, Shao S, Chen L, Xie Z, Cheng Y, Geng Y, Wang L, Jing X,
Wang F. White electroluminescence from a single polymer system:
improved performance by means of enhanced efficiency and red-
shifted luminescence of the blue-light-emitting species. Adv Mater
2007;19:1859–63.
[130] Chien CH, Shih PI, Shu CF. White electroluminescence from a single
polymer: a blue-emitting polyfluorene incorporating orange-
emitting benzoselenadiazole segments on its main chain. J Polym
Sci Part A Polym Chem 2007;45:2938–46.
[131] Lee SK, Jung BJ, Ahn T, Jung YK, Lee JI, Kang IN, Lee J, Park JH, Shim HK.
White electroluminescence from a single polyfluorene containing
bis-DCM units. J Polym Sci Part A Polym Chem 2007;45:3380–90.
[132] Mei C, Ding J, Yao B, Cheng Y, Xie Z, Geng Y, Wang L. Synthesis and
characterization of white-light-emitting polyfluorenes containing
orange phosphorescent moieties in the side chain. J Polym Sci Part
A Polym Chem 2007;45:1746–57.
[133] Kappaun S, Eder S, Sax S, Saf R, Mereiter K, List EJW, Slugovc
C. WPLEDs prepared from main-chain fluorene–iridium(III) poly-
mers. J Mater Chem 2006;16:4389–92.
[134] Liu J, Cheng Y, Xie Z, Geng Y, Wang L, Jing X, Wang F. White elec-
troluminescence from a star-like polymer with an orange emissive
core and four blue emissive arms. Adv Mater 2008;20:1357–62.
[135] Chen L, Li P, Cheng Y, Xie Z, Wang L, Jing X, Wang F. White
electroluminescence from star-like single polymer systems: 2,1,3-
benzothiadiazole derivatives dopant as orange cores and polyfl
uorene host as six blue arms. Adv Mater 2011;23:2986–90.
[136] Liu J, Xie Z, Cheng Y, Geng Y, Wang L, Jing X, Wang F. Molecular
design on highly efficient white electroluminescence from a single-
polymer system with simultaneous blue, green, and red emission.
Adv Mater 2007;19:531–5.
[137] Liu J, Zhou Q, Cheng Y, Geng Y, Wang L, Ma D, Jing X, Wang F. The first
single polymer with simultaneous blue, green, and red emission for
white electroluminescence. Adv Mater 2005;17:2974–8.
[138] Lee PI, Hsu SLC, Lee RF. White-light-emitting diodes from single
polymer systems based on polyfluorene copolymers end-capped
with a dye. Polymer 2007;48:110–5.
[139] Chuang CY, Shih PI, Chien CH, Wu FI, Shu CF. Bright-white
light-emitting devices based on a single polymer exhibiting
simultaneous blue, green, and red emissions. Macromolecules
2007;40:247–52.
[140] Luo J, Li X, Hou Q, Peng J, Yang W, Cao Y. High-efficiency white-
light emission from a single copolymer: fluorescent blue, green, and
red chromophores on a conjugated polymer backbone. Adv Mater
2007;19:1113–7.
[141] Wu WC, Lee WY, Chen WC. New fluorene-acceptor random copoly-
mers: towards pure white light emission from a single polymer.
Macromol Chem Phys 2006;207:1131–8.
[142] Lee SK, Hwang DH, Jung BJ, Cho NS, Lee J, Lee JD, Shim HK.
Fabrication and characterization of single-component polymeric
white-light-emitting diodes. Adv Funct Mater 2005;15:1647–55.
[143] Wu FI, Yang XH, Neher D, Dodda R, Tseng YH, Shu CF. Efficient
white-electrophosphorescent devices based on a single polyfluo-
rene copolymer. Adv Funct Mater 2007;17:1085–92.
[144] Jiang J, Xu Y, Yang W, Guan R, Liu Z, Zhen H, Cao Y. High-efficiency
white-light-emitting devices from a single polymer by mixing sin-
glet and triplet emission. Adv Mater 2006;18:1769–73.
[145] Zhen H, Xu W, Yang W, Chen Q, Xu Y, Jiang J, Peng J, Cao Y.
White-light emission from a single polymer with singlet and
1899
triplet chromophores on the backbone. Macromol Rapid Commun
2006;27:2095–100.
[146] Guo X, Qin C, Cheng Y, Xie Z, Geng Y, Jing X, Wang F, Wang
L. White electroluminescence from a phosphonate-functionalized
single-polymer system with electron-trapping effect. Adv Mater
2009;21:3682–8.
[147] Svensson M, Zhang FL, Veenstra SC, Verhees WJH, Hummelen JC,
Kroon JM, Inganas O, Andersson MR. High-performance polymer
solar cells of an alternating polyfluorene copolymer and a fullerene
derivative. Adv Mater 2003;15:988–91.
[148] Inganäs O, Svensson M, Zhang F, Gadisa A, Persson NK, Wang
X, Andersson MR. Low bandgap alternating polyfluorene copoly-
mers in plastic photodiodes and solar cells. Appl Phys A 2004;79:
31–5.
[149] Zhang FL, Gadisa A, Inganäs O, Svensson M, Andersson MR. Influ-
ence of buffer layers on the performance of polymer solar cells. Appl
Phys Lett 2004;84:3906–8.
[150] Gadisa A, Zhang FL, Sharma D, Svensson M, Andersson MR, Inganäs
O. Improvements of fill factor in solar cells based on blends
of polyfluorene copolymers as electron donors. Thin Solid Films
2007;515:3126–31.
[151] Zhang FL, Perzon E, Wang XJ, Mammo W, Andersson MR, Inganäs
O. Polymer solar cells based on a low-bandgap fluorene copolymer
and a fullerene derivative with photocurrent extended to 850 nm.
Adv Funct Mater 2005;15:745–50.
[152] Perzon E, Wang XJ, Zhang FL, Mammo W, Delgado JL, de la Cruz P,
Inganäs O, Langa F, Andersson MR. Design, synthesis and properties
of low band gap polyfluorenes for photovoltaic devices. Synth Met
2005;154:53–6.
[153] Perzon E, Wang XJ, Admassie S, Inganäs O, Andersson MR. An
alternating low band-gap polyfluorene for optoelectronic devices.
Polymer 2006;47:4261–8.
[154] Wang XJ, Perzon E, Mammo W, Oswald F, Admassie S, Persson NK,
Langa F, Andersson MR, Inganäs O. Polymer solar cells with low-
bandgap polymers blended with C-70-derivative give photocurrent
at 1 ␮m. Thin Solid Films 2006;511:576–80.
[155] Zhang FL, Mammo W, Andersson LM, Admassie S, Anders-
son MR, Inganäs L, Admassie S, Andersson MR, Ingands O.
Low-bandgap alternating fluorene copolymer/methanofullerene
heterojunctions in efficient near-infrared polymer solar cells. Adv
Mater 2006;18:2169–73.
[156] Gadisa A, Mammo W, Andersson LM, Admassie S, Zhang F, Ander-
sson MR, Inganäs O. A new donor–acceptor–donor polyfluorene
copolymer with balanced electron and hole mobility. Adv Funct
Mater 2007;17:3836–42.
[157] Mammo W, Admassie S, Gadisa A, Zhang FL, Inganäs O, Andersson
MR. New low band gap alternating polyfluorene copolymer-based
photovoltaic cells. Sol Energy Mater Sol Cells 2007;91:1010–8.
[158] Zhang FL, Bijleveld J, Perzon E, Tvingstedt K, Barrau S, Inganas O,
Andersson MR. High photovoltage achieved in low band gap poly-
mer solar cells by adjusting energy levels of a polymer with the
LUMOs of fullerene derivatives. J Mater Chem 2008;18:5468–74.
[159] Zhou EJ, Yamakawa SP, Tajima K, Yang CH, Hashimoto K. Syn-
thesis and photovoltaic properties of diketopyrrolopyrrole-based
donor–acceptor copolymers. Chem Mater 2009;21:4055–61.
[160] Huo LJ, Hou JH, Chen HY, Zhang SQ, Jiang Y, Chen TL, Yang
Y. Bandgap and molecular level control of the low-bandgap
polymers based on 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-
c]pyrrole-1,4-dione toward highly efficient polymer solar cells.
Macromolecules 2009;42:6564–71.
[161] Zhang FL, Jespersen KG, Bjorstrom C, Svensson M, Andersson MR,
Sundstrom V, Magnusson K, Moons E, Yartsev A, Inganas O. Influ-
ence of solvent mixing on the morphology and performance of solar
cells based on polyfluorene copolymer/fullerene blends. Adv Funct
Mater 2006;16:667–74.
[162] Becerril HA, Miyaki N, Tang ML, Mondal R, Sun YS, Mayer AC,
Parmer JE, McGehee MD, Bao ZA. Transistor and solar cell per-
formance of donor–acceptor low bandgap copolymers bearing
an acenaphtho[1,2-b]thieno[3,4-e]pyrazine (ACTP) motif. J Mater
Chem 2009;19:591–3.
[163] Wang F, Luo J, Yang KX, Chen JW, Huang F, Cao Y. Conjugated fluo-
rene and silole copolymers: synthesis, characterization, electronic
transition, light emission, photovoltaic cell, and field effect hole
mobility. Macromolecules 2005;38:2253–60.
[164] Wang F, Luo J, Chen JW, Huang F, Cao Y. Conjugated ran-
dom and alternating 2,3,4,5-tetraphenylsilole-containing polyflu-
orenes: synthesis, characterization, strong solution photolumine-
scence, and light-emitting diodes. Polymer 2005;46:8422–9.
[165] Okamoto T, Jiang Y, Qu F, Mayer AC, Parmer JE, McGehee
MD, Bao ZN. Synthesis and characterization of pentacene- and
1900 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
anthradithiophene-fluorene conjugated copolymers synthesized
by Suzuki reactions. Macromolecules 2008;41:6977–80.
[166] Liu L, Ho CL, Wong WY, Cheung KY, Fung MK, Lam WT, Djurišić AB,
Chan WK. Effect of oligothienyl chain length on tuning the solar cell
performance in fluorene-based polyplatinynes. Adv Funct Mater
2008;18:2824–33.
[167] Redecker M, Bradley DDC, Inbasekaran M, Woo EP. Mobility
enhancement through homogeneous nematic alignment of a
liquid-crystalline polyfluorene. Appl Phys Lett 1999;74:1400–2.
[168] Heeney M, Bailey C, Giles M, Shkunov M, Sparrowe D, Tierney
S, Zhang WM, McCulloch I. Alkylidene fluorene liquid crystalline
semiconducting polymers for organic field effect transistor devices.
Macromolecules 2004;37:5250–6.
[169] Kreouzis T, Bradley DDC, Campbell AJ. Hole and electron trans-
port in poly(9,9-dioctylfluorene) and poly(9,9-dioctylfluorene-co-
benzothiadiazole). Proc SPIE 2004;5214:141–9.
[170] Donley CL, Zaumseil J, Andreasen JW, Nielsen MM, Sirringhaus H,
Friend RH, Kim JS. Effects of packing structure on the optoelectronic
and charge transport properties in poly(9,9-di-n-octylfluorene-alt-
benzothiadiazole). J Am Chem Soc 2005;127:12890–9.
[171] Chen MX, Perzon E, Robisson N, Jonsson SKM, Andersson MR,
Fahlman M, Berggren M. Low band gap donor–acceptor–donor
polymers for infra-red electroluminescence and transistors. Synth
Met 2004;146:233–6.
[172] Chen MX, Crispin X, Perzon E, Andersson MR, Pullerits T, Anders-
son M, Inganas O, Berggren M. High carrier mobility in low band
gap polymer-based field-effect transistors. Appl Phys Lett 2005;87,
252105/1–3.
[173] Sirringhaus H, Wilson RJ, Friend RH, Inbasekaran M, Wu W, Woo
EP, Grell M, Bradley DDC. Mobility enhancement in conjugated
polymer field-effect transistors through chain alignment in a
liquid-crystalline phase. Appl Phys Lett 2000;77:406–8.
[174] Gather MC, Bradley DDC. An improved optical method for deter-
mining the order parameter in thin oriented molecular films
and demonstration of a highly axial dipole moment for the
lowest energy pi-pi optical transition in poly(9,9-dioctylfluorene-
co-bithiophene). Adv Funct Mater 2007;17:479–85.
[175] Sirringhaus H, Kawase T, Friend RH, Shimoda T, Inbasekaran M, Wu
W, Woo EP. High-resolution inkjet printing of all-polymer transis-
tor circuits. Science 2000;290:2123–6.
[176] Tang WH, Chellappan V, Liu MH, Chen ZK, Ke L. Hole transport
in poly[2,7-(9,9-dihexylfluorene)-alt-bithiophene] high-efficiency
polymer solar cells from its blends with PCBM. ACS Appl Mater
Interfaces 2009;1:1467–73.
[177] Kim YM, Lim E, Kang IN, Jung BJ, Lee J, Koo BW, Do LM, Shim HK.
Solution-processable field-effect transistor using a fluorene- and
selenophene-based copolymer as an active layer. Macromolecules
2006;39:4081–5.
[178] Lim E, Jung BJ, Lee J, Shim HK, Lee JI, Yang YS, Do LM. Thin-
film morphologies and solution-processable field-effect transistor
behavior of a fluorene-thieno[3,2-b]thiophene-based conjugated
copolymer. Macromolecules 2005;38:4531–5.
[179] Ma WL, Iyer PK, Gong X, Liu B, Moses D, Bazan GC, Heeger AJ.
Water/methanol-soluble conjugated copolymer as an electron-
transport layer in polymer light-emitting diodes. Adv Mater
2005;17:274–7.
[180] Huang F, Wu H, Wang D, Yang W, Cao Y. Novel electroluminescent
conjugated polyelectrolytes based on polyfluorene. Chem Mater
2004;16:708–16.
[181] Oh SH, Vak D, Na SI, Lee TW, Kim DY. Water-soluble polyfluorenes
as an electron injecting layer in PLEDs for extremely high quantum
efficiency. Adv Mater 2008;20:1624–9.
[182] Wu H, Huang F, Mo Y, Yang W, Wang D, Peng J, Cao Y. Effi-
cient electron injection from a bilayer cathode consisting of
aluminum and alcohol-/water-soluble conjugated polymers. Adv
Mater 2004;16:1826–30.
[183] Huang F, Niu YH, Zhang Y, Ka JW, Liu MS, Jen AKY. A conjugated,
neutral surfactant as electron-injection material for high-efficiency
polymer light-emitting diodes. Adv Mater 2007;19:2010–4.
[184] Huang F, Zhang Y, Liu MS, Jen AKY. Electron-rich alcohol-soluble
neutral conjugated polymers as highly efficient electron-injecting
materials for polymer light-emitting diodes. Adv Funct Mater
2009;19:2457–66.
[185] Huang F, Shih PI, Shu CF, Chi Y, Jen AKY. Highly efficient polymer
white-light-emitting diodes based on lithium salts doped electron
transporting layer. Adv Mater 2009;21:361–5.
[186] Zhou G, Qian G, Ma L, Cheng Y, Xie Z, Wang L, Jing X, Wang
F. Polyfluorenes with phosphonate groups in the side chains as
chemosensors and electroluminescent materials. Macromolecules
2005;38:5416–24.
[187] Meerholz K. Device physics – enlightening solutions. Nature
2005;437:327–8.
[188] Yang RQ, Wu HB, Cao Y, Bazan GC. Control of cationic conjugated
polymer performance in light emitting diodes by choice of coun-
terion. J Am Chem Soc 2006;128:14422–3.
[189] Zhou G, Geng Y, Cheng Y, Xie Z, Wang L, Jing X, Wang F. Efficient blue
electroluminescence from neutral alcohol-soluble polyfluorenes
with aluminum cathode. Appl Phys Lett 2006;89, 233501/1–3.
[190] Wu XF, Xu BW, Tong H, Wang LX. Phosphonate-functionalized poly-
fluorene film sensors for sensitive detection of iron(III) in both
organic and aqueous media. Macromolecules 2010;43:8917–23.
[191] Huang F, Hou L, Shen H, Jiang J, Wang F, Zhen H, Cao
Y. Synthesis, photophysics, and electroluminescence of high-
efficiency saturated red light-emitting polyfluorene-based poly-
electrolytes and their neutral precursors. J Mater Chem 2005;15:
2499–507.
[192] Deng XY, Lau WM, Wonga KY. High efficiency low operating voltage
polymer light-emitting diodes with aluminum cathode. Appl Phys
Lett 2004;84:3522–4.
[193] Huang F, Hou L, Wu H, Wang X, Shen H, Wei Cao, Yang W, Cao
Y. High-efficiency, environment-friendly electroluminescent poly-
mers with stable high work function metal as a cathode: green-
and yellow-emitting conjugated polyfluorene polyelectrolytes and
their neutral precursors. J Am Chem Soc 2004;126:9845–53.
[194] Jiang H, Taranekar P, Reynolds JR, Schanze KS. Conjugated polyelec-
trolytes: synthesis, photophysics, and applications. Angew Chem
Int Ed 2009;48:4300–16.
[195] Keivanidis PE, Jacob J, Oldridge L, Sonar P, Carbonnier B, Baluschev
S, Grimsdale AC, Müllen K, Wegner G. Photophysical character-
ization of light-emitting poly(indenofluorene)s. ChemPhysChem
2005;6:1650–60.
[196] Marsitzky D, Scott JC, Chen JP, Lee VY, Miller RD, Setayesh S, Müllen
K. Poly-2,8-(indenofluorene-co-anthracene)—a colorfast blue-
light-emitting random copolymer. Adv Mater 2001;13:1096–9.
[197] Jacob J, Zhang J, Grimsdale AC, Müllen K.
Poly(tetraarylindenofluorene)s: new stable blue-emitting
polymers. Macromolecules 2003;36:8240–5.
[198] Vak D, Lim B, Lee SH, Kim DY. Synthesis of a double spiro-
polyindenofluorene with a stable blue emission. Org Lett
2005;7:4229–32.
[199] Surin M, Sonar P, Grimsdale AC, Müllen K, Lazzaroni R, Leclere
P. Supramolecular organization in fluorene/indenofluorene-
oligothiophene alternating conjugated copolymers. Adv Funct
Mater 2005;15:1426–34.
[200] Sonar P, Oldridge L, Grimsdale AC, Müllen K, Surin M, Lazza-
roni R, Leclere P, Pinto J, Chua LL, Sirringhaus H, Friend RH.
Synthesis, characterization and comparative OFET behaviour of
indenofluorene-bithiophene and terthiophene alternating copoly-
mers. Synth Met 2010;160:468–74.
[201] Kim J, Kim SH, Jung IH, Jeong E, Xia Y, Cho SN, Hwang IW, Lee K, Suh
H, Shim HK, Woo HY. Synthesis and characterization of indeno[1,2-
b]fluorene-based low bandgap copolymers for photovoltaic cells. J
Mater Chem 2010;20:1577–86.
[202] Zheng QD, Jung BJ, Sun J, Katz HE. Ladder-type oligo-p-phenylene-
containing copolymers with high open-circuit voltages and
ambient photovoltaic activity. J Am Chem Soc 2010;132:5394–404.
[203] Sonar P, Zhang J, Grimsdale AC, Müllen K, Surin M, Lazzaroni R,
Leclère P, Tierney S, Heeney M, McCulloch I. 4-Hexylbithieno[3,2-
b:2 3 -e]pyridine: an efficient electron-accepting unit in fluorene
and indenofluorene copolymers for light-emitting devices. Macro-
molecules 2004;37:709–15.
[204] Jeong E, Kim SH, Jung IH, Xia Y, Lee K, Suh H, Shim HK, Woo
HY. Synthesis and characterization of indeno[1,2-b]fluorene-based
white light-emitting copolymer. J Polym Sci Part A Polym Chem
2009;47:3467–79.
[205] Usta H, Facchetti A, Marks TJ. Air-stable, solution-processable n-
channel and ambipolar semiconductors for thin-film transistors
based on the indenofluorenebis(dicyanovinylene) core. J Am Chem
Soc 2008;130:8580–1.
[206] Mishra AK, Graf M, Grasse F, Jacob J, List EJW, Müllen K.
Blue-emitting carbon- and nitrogen-bridged poly(ladder-type
tetraphenylene)s. Chem Mater 2006;18:2879–85.
[207] Jacob J, Sax S, Gaal M, List EJW, Grimsdale AC, Müllen K. A fully aryl-
substituted poly(ladder-type pentaphenylene) a remarkably stable
blue-light-emitting polymer. Macromolecules 2005;38:9933–8.
[208] Morin JF, Leclerc M, Adès D, Siove A. Polycarbazoles: 25 years of
progress. Macromol Rapid Commun 2005;26:761–78.
[209] Li YN, Wu YL, Ong BS. Polyindolo[3,2-b]carbazoles: a new class of p-
channel semiconductor polymers for organic thin-film transistors.
Macromolecules 2006;39:6521–7.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[210] Boudreault PLT, Beaupré S, Leclerc M. Polycarbazoles for plastic
electronics. Polym Chem 2010;1:127–36.
[211] Lmimouni K, Legrand C, Chapoton A. Optical and electrical
characterizations of poly(N-alkylcarbazole) light-emitting diodes.
Interpretation of electrical behaviour. Synth Met 1998;97:151–5.
[212] Ying L, Zou JH, Zhang AQ, Chen B, Yang W, Cao Y. Novel orange-
red light-emitting polymers with cyclometaled iridium complex
grafted in alkyl chain. J Organomet Chem 2009;694:2727–34.
[213] Cho HJ, Hwang DH, Lee JD, Cho NS, Lee SK, Lee J, Jung YK, Shim
HK. Synthesis and characterization of novel germanium-containing
poly(p-phenylenevinylene) derivatives. J Polym Sci Part A Polym
Chem 2008;46:979–88.
[214] Brihaye O, Legrand C, Chapoton A, Chevrot C, Siove A. Wide
frequency and temperature-range conductivity measurements
of chemically doped carbazole and poly(N-Butylcarbazole) –
thin-films elaboration for electronic components. Synth Met
1993;57:5075–80.
[215] van Dijken A, Bastiaansen JJAM, Kiggen NMM, Langeveld BMW,
Rothe C, Monkman A, Bach I, Stossel P, Brunner K. Carbazole
compounds as host materials for triplet emitters in organic light-
emitting diodes: polymer hosts for high-efficiency light-emitting
diodes. J Am Chem Soc 2004;126:7718–27.
[216] Ma ZH, Chen LC, Ding JQ, Wang LX, Jing XB, Wang FS. Green
electrophosphorescent polymers with poly(3,6-Carbazole) as the
backbone: a linear structure does realize high efficiency. Adv Mater
2011;23:3726–9.
[217] Dierschke F, Grimsdale AC, Müllen K. Efficient synthesis of 2,7-
dibromocarbazoles as components for electroactive materials.
Synth Stuttgart 2003:2470–2.
[218] Morin JF, Leclerc M. Syntheses of conjugated polymers derived from
N-alkyl-2,7-carbazoles. Macromolecules 2001;34:4680–2.
[219] Morin JF, Leclerc M. 2,7-carbazole-based conjugated poly-
mers for blue, green, and red light emission. Macromolecules
2002;35:8413–7.
[220] Morin JF, Beaupre S, Leclerc M, Levesque I, D’Iorio M. Blue
light-emitting devices from new conjugated poly(N-substituted-
2,7-carbazole) derivatives. Appl Phys Lett 2002;80:341–3.
[221] Li JL, Dierschke F, Wu JS, Grimsdale AC, Müllen K. Poly(2,7-
carbazole) and perylene tetracarboxydiimide: a promising
donor/acceptor pair for polymer solar cells. J Mater Chem
2006;16:96–100.
[222] Ooi ZE, Tam TL, Shin RYC, Chen ZK, Kietzke T, Sellinger A,
Baumgarten M, Müllen K, Demello JC. Solution processable bulk-
heterojunction solar cells using a small molecule acceptor. J Mater
Chem 2008;18:4619–22.
[223] Leclerc N, Michaud A, Sirois K, Morin JF, Leclerc M. Synthesis of 2,7-
carbazolenevinylene-based copolymers and characterization of
their photovoltaic properties. Adv Funct Mater 2006;16:1694–704.
[224] Blouin N, Michaud A, Gendron D, Wakim S, Blair E, Neagu-Plesu R,
Belletete M, Durocher G, Tao Y, Leclerc M. Toward a rational design
of poly(2,7-carbazole) derivatives for solar cells. J Am Chem Soc
2008;130:732–42.
[225] Blouin N, Michaud A, Leclerc M. A low-bandgap poly(2,7-carbazole)
derivative for use in high-performance solar cells. Adv Mater
2007;19:2295–300.
[226] Wakim S, Beaupre S, Blouin N, Aich BR, Rodman S, Gaudiana R, Tao
Y, Leclerc M. Highly efficient organic solar cells based on a poly(2,7-
carbazole) derivative. J Mater Chem 2009;19:5351–8.
[227] Park SH, Roy A, Beaupre S, Cho S, Coates N, Moon JS, Moses
D, Leclerc M, Lee K, Heeger AJ. Bulk heterojunction solar cells
with internal quantum efficiency approaching 100%. Nat Photonics
2009;3:297–302.
[228] He ZC, Zhong CM, Huang X, Wong WY, Wu HB, Chen LW, Su SJ,
Cao Y. Simultaneous enhancement of open-circuit voltage, short-
circuit current density, and fill factor in polymer solar cells. Adv
Mater 2011;23:4636–43.
[229] Liu J, Shao S, Fang G, Meng B, Xie Z, Wang L. High-efficiency
inverted polymer solar cells with transparent and work-function
tunable MoO3 –Al composite film as cathode buffer layer. Adv Mater
2012;24:2774–9.
[230] Yi HN, Johnson RG, Iraqi A, Mohamad D, Royce R, Lidzey DG.
Narrow energy gap polymers with absorptions up to 1200 nm
and their photovoltaic properties. Macromol Rapid Commun
2008;29:1804–9.
[231] Zou YP, Gendron D, Neagu-Plesu R, Leclerc M. Synthesis and
characterization of new low-bandgap diketopyrrolopyrrole-based
copolymers. Macromolecules 2009;42:6361–5.
[232] Zou YP, Gendron D, Badrou-Aich R, Najari A, Tao Y, Leclerc M. A
high-mobility low-bandgap poly(2,7-carbazole) derivative for pho-
tovoltaic applications. Macromolecules 2009;42:2891–4.
1901
[233] Zhang M, Yang CD, Mishra AK, Pisula W, Zhou G, Schmaltz B, Baum-
garten M, Müllen K. Conjugated alternating copolymers containing
both donor and acceptor moieties in the main chain. Chem Com-
mun 2007:1704–6.
[234] Pisula W, Mishra AK, Li J, Baumgarten M, Müllen K. Carbazole-based
conjugated polymers as donor material for photovoltaic devices.
In: Brabec CJ, Dyakonov V, Scherf U, editors. Organic photovoltaics:
materials, device, physics, and manufacturing technologies. Wein-
heim: Wiley-VCH; 2008. p. 93–128.
[235] Blouin N, Michaud A, Wakim S, Boudreault PLT, Leclerc M, Ver-
celli B, Zecchin S, Zotti G. Optical, electrochemical, magnetic, and
conductive properties of new polyindolocarbazoles and polydiin-
dolocarbazoles. Macromol Chem Phys 2006;207:166–74.
[236] Boudreault PLT, Wakim S, Blouin N, Simard M, Tessier C,
Tao Y, Leclerc M. Synthesis, characterization, and applica-
tion of indolo[3,2-b]carbazole semiconductors. J Am Chem Soc
2007;129:9125–36.
[237] Zhou EJ, Yamakawa S, Zhang Y, Tajima K, Yang CH, Hashimoto K.
Indolo[3,2-b]carbazole-based alternating donor–acceptor copoly-
mers: synthesis, properties and photovoltaic application. J Mater
Chem 2009;19:7730–7.
[238] Lu JP, Liang FS, Drolet N, Ding JF, Tao Y, Movileanu R. Crystalline low
band-gap alternating indolocarbazole and benzothiadiazole-cored
oligothiophene copolymer for organic solar cell applications. Chem
Commun 2008:5315–7.
[239] Tsai JH, Chueh CC, Lai MH, Wang CF, Chen WC, Ko BT, Ting C.
Synthesis of new indolocarbazole-acceptor alternating conjugated
copolymers and their applications to thin film transistors and pho-
tovoltaic cells. Macromolecules 2009;42:1897–905.
[240] Chan KL, McKiernan MJ, Towns CR, Holmes AB. Poly(2,7-
dibenzosilole): a blue light emitting polymer. J Am Chem Soc
2005;127:7662–3.
[241] Mo YQ, Tian RY, Shi W, Cao Y. Ultraviolet-emitting conjugated
polymer poly(9,9 -alkyl-3,6-silafluorene) with a wide band gap of
4.0 eV. Chem Commun 2005:4925–6.
[242] Wang EG, Li C, Mo YQ, Zhang Y, Ma G, Shi W, Peng JB, Yang W, Cao Y.
Poly(3,6-silafluorene-co-2,7-fluorene)-based high-efficiency and
color-pure blue light-emitting polymers with extremely nar-
row band-width and high spectral stability. J Mater Chem
2006;16:4133–40.
[243] Chen RF, Fan QL, Liu SJ, Zhu R, Pu KY, Huang W. Fluorene and silaflu-
orene conjugated copolymer: a new blue light-emitting polymer.
Synth Met 2006;156:1161–7.
[244] Chen RF, Zhu R, Zheng C, Liu SJ, Fan QL, Huang W. Ger-
mafluorene conjugated copolymer-synthesis and applications in
blue-light-emitting diodes and host materials. Sci China B 2009;52:
212–8.
[245] Boudreault PLT, Michaud A, Leclerc M. A new poly(2,7-
dibenzosilole) derivative in polymer solar cells. Macromol Rapid
Commun 2007;28:2176–9.
[246] Wang EG, Wang L, Lan LF, Luo C, Zhuang WL, Peng JB, Cao
Y. High-performance polymer heterojunction solar cells of a
polysilafluorene derivative. Appl Phys Lett 2008;92, 033307/
1–3.
[247] Allard N, Aich RB, Gendron D, Boudreault PLT, Tessier C, Alem S, Tse
SC, Tao Y, Leclerc M. Germafluorenes: new heterocycles for plastic
electronics. Macromolecules 2010;43:2328–33.
[248] Yang W, Hou Q, Liu CZ, Niu YH, Huang J, Yang RQ, Cao
Y. Improvement of color purity in blue-emitting polyfluorene
by copolymerization with dibenzothiophene. J Mater Chem
2003;13:1351–5.
[249] King SM, Matheson R, Dias FB, Monkman AP. Enhanced triplet
formation by twisted intramolecular charge-transfer excited
states in conjugated oligomers and polymers. J Phys Chem B
2008;112:8010–6.
[250] Liu J, Hu SJ, Zhao W, Zou QH, Luo W, Yang W, Peng JBA, Cao Y. Novel
spectrally stable saturated blue-light-emitting poly[(fluorene)-co-
(dioctyldibenzothiophene-S,S-dioxide)]s. Macromol Rapid Com-
mun 2010;31:496–501.
[251] Baumgartner T, Reau R. Organophosphorus pi-conjugated materi-
als. Chem Rev 2006;106:4681–727.
[252] Chen RF, Zhu R, Fan QL, Huang W. Synthesis, structure, and opto-
electronic properties of phosphafluorene copolymers. Org Lett
2008;10:2913–6.
[253] Feng XL, Pisula W, Müllen K. Large polycyclic aromatic hydro-
carbons: synthesis and discotic organization. Pure Appl Chem
2009;81:2203–24.
[254] Balakrishnan K, Datar A, Zhang W, Yang XM, Naddo T, Huang JL, Zuo
JM, Yen M, Moore JS, Zang L. Nanofibril self-assembly of an arylene
ethynylene macrocycle. J Am Chem Soc 2006;128:6576–7.
1902 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[255] Saleh M, Baumgarten M, Mavrinskiy A, Schafer T, Müllen K.
Triphenylene-based polymers for blue polymeric light emitting
diodes. Macromolecules 2010;43:137–43.
[256] Saleh M, Park YS, Baumgarten M, Kim JJ, Müllen K. Conjugated triph-
enylene polymers for blue OLED devices. Macromol Rapid Commun
2009;30:1279–83.
[257] Figueira-Duarte TM, Müllen K. Pyrene-based materials for organic
electronics. Chem Rev 2011;111:7260–314.
[258] Kawano SI, Yang C, Ribas M, Baluschev S, Baumgarten M, Müllen K.
Blue-emitting poly(2,7-pyrenylene)s: synthesis and optical prop-
erties. Macromolecules 2008;41:7933–7.
[259] Kawano SI, Baumgarten M, Müllen K, Schäfer T, Murer P, Saleh M.
Novel polymers. PCT/EP 2009/057126. Wo: BASF SE, DE and Max-
Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V., De.;
2010.
[260] Mikroyannidis JA. Luminescent monomer of substituted
tetrastyrylpyrene and poly (p-phenylenevinylene) derivative
with pyrene segments: synthesis and photophysics. Synth Met
2005;155:125–9.
[261] Mikroyannidis JA, Fenenko L, Yahiro M, Adachi C. Alternating
copolyfluorenevinyles with polynuclear aromatic moieties: syn-
thesis, photophysics, and electroluminescence. J Polym Sci Part A
Polym Chem 2007;45:4661–70.
[262] Figueira-Duarte TM, Del Rosso PG, Trattnig R, Sax S, List EJW,
Müllen K. Designed suppression of aggregation in polypyrene:
toward high-performance blue-light-emitting diodes. Adv Mater
2010;22:990–3.
[263] Suh H, Jin Y, Park SH, Kim D, Kim J, Kim C, Kim JY, Lee K. Stabilized
blue emission from organic light-emitting diodes using poly(2,6-
(4,4-bis(2-ethylhexyl)-4H-cyclopenta[def]phenanthrene)).
Macromolecules 2005;38:6285–9.
[264] Park SH, Jin Y, Kim JY, Kim SH, Kim J, Suh H, Lee K. A blue-
light-emitting polymer with a rigid backbone for enhanced color
stability. Adv Funct Mater 2007;17:3063–8.
[265] Jin Y, Kim Y, Kim SH, Song S, Woo HY, Lee K, Suh H. Novel green-
light-emitting polymers based on cyclopenta[def]phenanthrene.
Macromolecules 2008;41:5548–54.
[266] Kim J, Park SH, Cho S, Jin Y, Kim J, Kim I, Lee JS, Kim JH, Woo HY, Lee
K, Suh H. Low-bandgap poly(4H-cyclopenta[def]phenanthrene)
derivatives with 4,7-dithienyl-2,1,3-benzothiadiazole unit for pho-
tovoltaic cells. Polymer 2010;51:390–6.
[267] Guo X, Yao B, Jiang GX, Cheng YX, Xie ZY, Wang LX, Ing XB, Wang FS.
Synthesis and characterization of color-stable electroluminescent
polymers: poly(dinaphtho[1,2-a:1 ,2 -g]-s-indacene)s. J Polym Sci
Part A Polym Chem 2008;46:4866–78.
[268] Yang C, Jacob J, Müllen K. Synthesis and photochromic properties
of ladderized poly(p-phenylene-alt-9,10-anthrylene)s. Macro-
molecules 2006;39:5696–704.
[269] Song S, Jin Y, Kim SH, Moon J, Kim K, Kim JY, Park SH, Lee K,
Suh H. Stabilized polymers with novel indenoindene backbone
against photodegradation for LEDs and solar cells. Macromolecules
2008;41:7296–305.
[270] Mishra A, Ma CQ, Bäuerle P. Functional oligothiophenes: molecular
design for multidimensional nanoarchitectures and their applica-
tions. Chem Rev 2009;109:1141–276.
[271] Tsumura A, Koezuka H, Ando T. Macromolecular electronic device
– field-effect transistor with a polythiophene thin-film. Appl Phys
Lett 1986;49:1210–2.
[272] Sirringhaus H, Brown PJ, Friend RH, Nielsen MM, Bechgaard
K, Langeveld-Voss BMW, Spiering AJH, Janssen RAJ, Meijer EW,
Herwig P, de Leeuw DM. Two-dimensional charge transport
in self-organized, high-mobility conjugated polymers. Nature
1999;401:685–8.
[273] Chang JF, Sun BQ, Breiby DW, Nielsen MM, Solling TI, Giles
M, McCulloch I, Sirringhaus H. Enhanced mobility of poly(3-
hexylthiophene) transistors by spin-coating from high-boiling-
point solvents. Chem Mater 2004;16:4772–6.
[274] Zhao GJ, He YJ, Li YF. 6.5% efficiency of polymer solar cells based
on poly(3-hexylthiophene) and Indene-C-60 Bisadduct by device
optimization. Adv Mater 2010;22:4355–8.
[275] Ong BS, Wu YL, Liu P, Gardner S. High-performance semiconducting
polythiophenes for organic thin-film transistors. J Am Chem Soc
2004;126:3378–9.
[276] Kong H, Chung DS, Kang IN, Park JH, Park MJ, Jung IH, Park CE,
Shim HK. New selenophene-based semiconducting copolymers
for high performance organic thin-film transistors. J Mater Chem
2009;19:3490–9.
[277] Chen ZY, Lemke H, Albert-Seifried S, Caironi M, Nielsen MM,
Heeney M, Zhang WM, McCulloch I, Sirringhaus H. High mobility
ambipolar charge transport in polyselenophene conjugated poly-
mers. Adv Mater 2010;22:2371–5.
[278] Heeney M, Zhang W, Crouch DJ, Chabinyc ML, Gordeyev S, Hamil-
ton R, Higgins SJ, McCulloch I, Skabara PJ, Sparrowe D, Tierney S.
Regioregular poly(3-hexyl) selenophene: a low band gap organic
hole transporting polymer. Chem Commun 2007:5061–3.
[279] Chung DS, Park JW, Kim SO, Heo K, Park CE, Ree M, Kim YH,
Kwon SK. Alternating copolymers containing bithiophene and
dialkoxynaphthalene for the applications to field effect transis-
tor and photovoltaic cell: performance and stability. Chem Mater
2009;21:5499–507.
[280] Ko SW, Verploegen E, Hong S, Mondal R, Hoke ET, Toney MF,
McGehee MD, Bao ZN. 3,4-Disubstituted polyalkylthiophenes for
high-performance thin-film transistors and photovoltaics. J Am
Chem Soc 2011;133:16722–5.
[281] Osaka I, Akita M, Koganezawa T, Takimiya K. Quinacridone-based
semiconducting polymers: implication of electronic structure and
orientational order for charge transport property. Chem Mater
2012;24:1235–43.
[282] Mcculloch I, Heeney M, Bailey C, Genevicius K, Shkunov IM, Spar-
rowe M, Tierney D, Wagner S, Zhang R, Chabinyc WM, Kline
ML, Mcgehee RJ, Toney MDMF. Liquid-crystalline semiconducting
polymers with high charge-carrier mobility. Nat Mater 2006;5:
328–33.
[283] Chabinyc ML, Toney MF, Kline RJ, McCulloch I, Heeney M. X-ray
scattering study of thin films of poly(2,5-bis(3-alkylthiophen-
2-yl)thieno[3,2-b]thiophene). J Am Chem Soc 2007;129:
3226–37.
[284] Li YN, Wu YL, Liu P, Birau M, Pan HL, Ong BS. Poly(2,5-bis(2-
thienyl)-3,6-dialkylthieno[3,2-b]thiophene)s-high-mobility semi-
conductors for thin-film transistors. Adv Mater 2006;18:3029–32.
[285] Wang S, Kiersnowski A, Pisula W, Müllen K. Microstructure evo-
lution and device performance in solution-processed polymeric
field-effect transistors: the key role of the first monolayer. J Am
Chem Soc 2012;134:4015–8.
[286] Li J, Qin F, Li CM, Bao QL, Chan-Park MB, Zhang W, Qin JG, Ong BS.
High-performance thin-film transistors from solution-processed
dithienothiophene polymer semiconductor nanoparticles. Chem
Mater 2008;20:2057–9.
[287] He MQ, Li JF, Sorensen ML, Zhang FX, Hancock RR, Fong HH, Pozdin
VA, Smilgies DM, Malliaras GG. Alkylsubstituted thienothiophene
semiconducting materials: structure–property relationships. J Am
Chem Soc 2009;131:11930–8.
[288] Li J, Tan HS, Chen ZK, Goh WP, Wong HK, Ong KH, Liu WL, Li CM, Ong
BS. Dialkyl-substituted dithienothiophene copolymers as polymer
semiconductors for thin-film transistors and bulk heterojunction
solar cells. Macromolecules 2011;44:690–3.
[289] Fong HH, Pozdin VA, Amassian A, Malliaras GG, Smilgies DM, He
MQ, Gasper S, Zhang F, Sorensen M. Tetrathienoacene copolymers
as high mobility, soluble organic semiconductors. J Am Chem Soc
2008;130:13202–3.
[290] He MQ, Li JF, Tandia A, Sorensen M, Zhang FX, Fong HH, Pozdin VA,
Smilgies DM, Malliaras GG. Importance of C-2 symmetry for the
device performance of a newly synthesized family of fused-ring
thiophenes. Chem Mater 2010;22:2770–9.
[291] Liu JY, Zhang R, Sauve G, Kowalewski T, McCullough RD. Highly
disordered polymer field effect transistors: N-alkyl dithieno[3,2-
b: 2 ,3 -d]pyrrole-based copolymers with surprisingly high charge
carrier mobilities. J Am Chem Soc 2008;130:13167–76.
[292] Lu G, Usta H, Risko C, Wang L, Facchetti A, Ratner MA, Marks TJ. Syn-
thesis, characterization, and transistor response of semiconducting
silole polymers with substantial hole mobility and air stability.
Experiment and theory. J Am Chem Soc 2008;130:7670–85.
[293] Coppo P, Turner ML. Investigation of the electronic properties of
cyclopentadithiophene polymers and copolymers. MRS Symp Proc
2003;771:61–4.
[294] Jiang Y, Hong S, Oh JH, Mondal R, Okamoto T, Verploegen
E, Toney MF, McGehee MD, Bao ZN. Impact of regioregular-
ity on thin-film transistor and photovoltaic cell performances of
pentacene-containing polymers. J Mater Chem 2012;22:4356–63.
[295] Rieger R, Beckmann D, Mavrinskiy A, Kastler M, Müllen K. Backbone
curvature in polythiophenes. Chem Mater 2010;22:5314–8.
[296] Rieger R, Beckmann D, Pisula W, Steffen W, Kastler M, Müllen
K. Rational optimization of benzo[2,1-b;3,4-b ]dithilophene-
containing polymers for organic field-effect transistors. Adv Mater
2010;22:83–6.
[297] Huo LJ, Hou JH. Benzo[1,2-b:4,5-b ]dithiophene-based conjugated
polymers: band gap and energy level control and their application
in polymer solar cells. Polym Chem 2011;2:2453–61.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[298] Pan HL, Li YN, Wu YL, Liu P, Ong BS, Zhu SP, Xu G. Synthesis and
thin-film transistor performance of poly(4,8-didodcylenzo[1,2-
b:4,5-b ]dithiophene). Chem Mater 2006;18:3237–41.
[299] Pan HL, Li YN, Wu YL, Liu P, Ong BS, Zhu SP, Xu G. Low-temperature,
solution-processed, high-mobility polymer semiconductors for
thin-film transistors. J Am Chem Soc 2007;129:4112–3.
[300] Lee D, Hubijar E, Kalaw GJD, Ferraris JP. Enhanced and tunable open-
circuit voltage using dialkylthio benzo[1,2-b:4,5-b ]dithiophene in
polymer solar cells. Chem Mater 2012;24:2534–40.
[301] Sista P, Xue BF, Wilson M, Holmes N, Kularatne RS, Nguyen H,
Dastoor PC, Belcher W, Poole K, Janesko BG, Biewer MC, Ste-
fan MC. Influence of the alkyl substituents spacing on the solar
cell performance of benzodithiophene semiconducting polymers.
Macromolecules 2012;45:772–80.
[302] Osaka I, Abe T, Shinamura S, Miyazaki E, Takimiya K. High-mobility
semiconducting naphthodithiophene copolymers. J Am Chem Soc
2010;132:5000–1.
[303] Osaka I, Abe T, Shinamura S, Takimiya K. Impact of isomeric
structures on transistor performances in naphthodithiophene
semiconducting polymers. J Am Chem Soc 2011;133:6852–60.
[304] Hwang MC, Jang JW, An TK, Park CE, Kim YH, Kwon SK.
Synthesis and characterization of new thermally stable
poly(naphthodithiophene) derivatives and applications for
high-performance organic thin film transistors. Macromolecules
2012;45:4520–8.
[305] Zhang WM, Smith J, Watkins SE, Gysel R, McGehee M, Salleo A,
Kirkpatrick J, Ashraf S, Anthopoulos T, Heeney M, McCulloch I. Inda-
cenodithiophene semiconducting polymers for high-performance,
air-stable transistors. J Am Chem Soc 2010;132:11437–9.
[306] Chan SH, Chen CP, Chao TC, Ting C, Lin CS, Ko BT. Synthesis, char-
acterization, and photovoltaic properties of novel semiconducting
polymers with thiophene-phenylene-thiophene (TPT) as coplanar
units. Macromolecules 2008;41:5519–26.
[307] Rieger R, Beckmann D, Pisula W, Kastler M, Müllen K. Tetrathiahex-
acene as building block for solution-processable semiconducting
polymers: exploring the monomer size limit. Macromolecules
2010;43:6264–7.
[308] Zheng QD, Chen SC, Zhang B, Wang LX, Tang CQ, Katz HE. Highly
soluble heteroheptacene: a new building block for p-Type semi-
conducting polymers. Org Lett 2011;13:324–7.
[309] Cheedarala RK, Kim GH, Cho S, Lee J, Kim J, Song HK, Kim JY,
Yang C. Ladder-type heteroacene polymers bearing carbazole and
thiophene ring units and their use in field-effect transistors and
photovoltaic cells. J Mater Chem 2011;21:843–50.
[310] Chen YG, Tian HK, Yan DH, Geng YH, Wang FS. Conjugated poly-
mers based on a S- and N-containing heteroarene: synthesis,
characterization, and semiconducting properties. Macromolecules
2011;44:5178–85.
[311] Chen Y, Liu C, Tian H, Bao C, Zhang X, Yan D, Geng Y, Wang F. Novel
conjugated polymers based on dithieno[3,2-b:6,7-b] carbazole for
solution processed thin-film transistors. Macromol Rapid Commun
2012;33:1759–64.
[312] Schroeder BC, Nielsen CB, Kim YJ, Smith J, Huang Z, Durrant
J, Watkins SE, Song K, Anthopoulos TD, McCulloch I. Ben-
zotrithiophene Co-polymers with high charge carrier mobilities in
field-effect transistors. Chem Mater 2011;23:4025–31.
[313] Zhang ZG, Wang JZ. Structures and properties of conjugated
Donor–Acceptor copolymers for solar cell applications. J Mater
Chem 2012;22:4178–87.
[314] Boudreault PLT, Najari A, Leclerc M. Processable low-bandgap poly-
mers for photovoltaic applications. Chem Mater 2011;23:456–69.
[315] Zhou HX, Yang LQ, You W. Rational design of high performance
conjugated polymers for organic solar cells. Macromolecules
2012;45:607–32.
[316] Li YF. Molecular design of photovoltaic materials for polymer solar
cells: toward suitable electronic energy levels and broad absorp-
tion. Acc Chem Res 2012;45:723–33.
[317] Wang CL, Dong HL, Hu WP, Liu YQ, Zhu DB. Semiconducting pi-
conjugated systems in field-effect transistors: a material odyssey
of organic electronics. Chem Rev 2012;112:2208–67.
[318] Biniek L, Schroeder BC, Nielsen CB, McCulloch I. Recent advances in
high mobility donor–acceptor semiconducting polymers. J Mater
Chem 2012;22:14803–13.
[319] Facchetti A. pi-conjugated polymers for organic electronics and
photovoltaic cell applications. Chem Mater 2011;23:733–58.
[320] Lin Y, Fan H, Li Y, Zhan X. Thiazole-based organic semiconductors
for organic electronics. Adv Mater 2012;24:3087–106.
[321] Tieke B, Rabindranath AR, Zhang K, Zhu Y. Conjugated polymers
containing diketopyrrolopyrrole units in the main chain. Beilstein
J Org Chem 2010;6:830–45.
1903
[322] Nielsen CB, Turbiez M, McCulloch I. Recent advances in the devel-
opment of semiconducting DPP-containing polymers for transistor
applications. Adv Mater 2013;25:1859–80.
[323] Zhou HX, Yang LQ, Liu SB, You W. A tale of current and voltage
interplay of band gap and energy levels of conjugated polymers in
bulk heterojunction solar cells. Macromolecules 2010;43:10390–6.
[324] Price SC, Stuart AC, You W. Polycyclic aromatics with flank-
ing thiophenes: tuning energy level and band gap of conjugated
polymers for bulk heterojunction photovoltaics. Macromolecules
2010;43:797–804.
[325] Furukawa S, Kobayashi J, Kawashima T. Development of a sila-
friedel-crafts reaction and its application to the synthesis of
dibenzosilole derivatives. J Am Chem Soc 2009;131:14192–3.
[326] Ureshino T, Yoshida T, Kuninobu Y, Takai K. Rhodium-
catalyzed synthesis of silafluorene derivatives via cleavage
of silicon–hydrogen and carbon–hydrogen bonds. J Am Chem Soc
2010;132:14324–6.
[327] Shintani R, Otomo H, Ota K, Hayashi T. Palladium-catalyzed
asymmetric synthesis of silicon-stereogenic dibenzosiloles via
enantioselective C H bond functionalization. J Am Chem Soc
2012;134:7305–8.
[328] Zhang GQ, Liu K, Li Y, Yang MJ. Novel poly(phenylene ethynylene)-
type conjugated polymers containing diketopyrrolopyrrole or
triphenylpyrazoline units in the main chain: synthesis, characteri-
zation and photophysical properties. Polym Int 2009;58:665–73.
[329] Gao P, Beckmann D, Tsao HN, Feng XL, Enkelmann V, Pisula
W, Müllen K. Benzo[1,2-b: 4,5-b ]bis[b]benzothiophene as solu-
tion processible organic semiconductor for field-effect transistors.
Chem Commun 2008:1548–50.
[330] Perzon E, Zhang FL, Andersson M, Mammo W, Inganas O, Ander-
sson MR. A conjugated polymer for near infrared optoelectronic
applications. Adv Mater 2007;19:3308–11.
[331] Tsao HN, Cho D, Andreasen JW, Rouhanipour A, Breiby DW, Pisula
W, Müllen K. The influence of morphology on high-performance
polymer field-effect transistors. Adv Mater 2009;21:209–12.
[332] Tsao HN, Cho DM, Park I, Hansen MR, Mavrinskiy A, Yoon DY, Graf R,
Pisula W, Spiess HW, Müllen K. Ultrahigh mobility in polymer field-
effect transistors by design. J Am Chem Soc 2011;133:2605–12.
[333] Wang SH, Kappl M, Liebewirth I, Müller M, Kirchhoff K, Pisula W,
Müllen K. Organic field-effect transistors based on highly ordered
single polymer fibers. Adv Mater 2012;24:417–20.
[334] Mühlbacher D, Scharber M, Morana M, Zhu ZG, Waller D, Gaudi-
ana R, Brabec C. High photovoltaic performance of a low-bandgap
polymer. Adv Mater 2006;18:2884–9.
[335] Zhu Z, Waller D, Gaudiana R, Morana M, Muhlbacher D, Schar-
ber M, Brabec C. Panchromatic conjugated polymers containing
alternating donor/acceptor units for photovoltaic applications.
Macromolecules 2007;40:1981–6.
[336] Peet J, Kim JY, Coates NE, Ma WL, Moses D, Heeger AJ, Bazan GC.
Efficiency enhancement in low-bandgap polymer solar cells by
processing with alkane dithiols. Nat Mater 2007;6:497–500.
[337] Lee JK, Ma WL, Brabec CJ, Yuen J, Moon JS, Kim JY, Lee K, Bazan GC,
Heeger AJ. Processing additives for improved efficiency from bulk
heterojunction solar cells. J Am Chem Soc 2008;130:3619–23.
[338] Li KC, Huang JH, Hsu YC, Huang PJ, Chu CW, Lin JT, Ho KC, Wei
KH, Lin HC. Tunable novel cyclopentadithiophene-based copoly-
mers containing various numbers of bithiazole and thienyl units for
organic photovoltaic cell applications. Macromolecules 2009;42:
3681–93.
[339] Van Mierloo S, Hadipour A, Spijkman MJ, Van den Brande
N, Ruttens B, Kesters J, D’Haen J, Van Assche G, de Leeuw
DM, Aernouts T, Manca J, Lutsen L, Vanderzande DJ, Maes
W. Improved photovoltaic performance of a semicrystalline
narrow bandgap copolymer based on 4H-cyclopenta[2,1-b:3,4-
b ]dithiophene donor and thiazolo[5,4-d]thiazole acceptor units.
Chem Mater 2012;24:587–93.
[340] Moulé AJ, Tsami A, Buennagel TW, Forster M, Kronenberg NM,
Scharber M, Koppe M, Morana M, Brabec CJ, Meerholz K, Scherf
U. Two novel cyclopentadithiophene-based alternating copoly-
mers as potential donor components for high-efficiency bulk-
heterojunction-type solar cells. Chem Mater 2008;20:4045–50.
[341] Guo XG, Xin H, Kim FS, Liyanage ADT, Jenekhe SA, Watson MD.
Thieno[3,4-c]pyrrole-4,6-dione-based donor–acceptor conjugated
polymers for solar cells. Macromolecules 2011;44:269–77.
[342] Li Z, Ding JF, Song NH, Du XM, Zhou JY, Lu JP, Tao Y. Alternating
copolymers of dithienyl-s-tetrazine and cyclopentadithiophene for
organic photovoltaic applications. Chem Mater 2011;23:1977–84.
[343] Li Z, Ding JF, Song NH, Lu JP, Tao Y. Development of a new s-
tetrazine-based copolymer for efficient solar cells. J Am Chem Soc
2010;132:13160–1.
1904 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[344] Chen GY, Chiang CM, Kekuda D, Lan SC, Chu CW, Wei KH.
Synthesis and characterization of a narrow-bandgap polymer
containing alternating cyclopentadithiophene and diketo-pyrrolo-
pyrrole units for solar cell applications. J Polym Sci Part A Polym
Chem 2010;48:1669–75.
[345] Yue W, Zhao Y, Shao SY, Tian HK, Xie ZY, Geng YH, Wang FS.
Novel NIR-absorbing conjugated polymers for efficient polymer
solar cells: effect of alkyl chain length on device performance. J
Mater Chem 2009;19:2199–206.
[346] Zhou EJ, Nakamura M, Nishizawa T, Zhang Y, Wei QS, Tajima K, Yang
CH, Hashimoto K. Synthesis and photovoltaic properties of a novel
low band gap polymer based on N-substituted dithieno[3,2-b:2 ,3 -
d]pyrrole. Macromolecules 2008;41:8302–5.
[347] Yang LQ, Zhou HX, You W. Quantitatively analyzing the influence of
side chains on photovoltaic properties of polymer-fullerene solar
cells. J Phys Chem C 2010;114:16793–800.
[348] Hu XL, Shi MM, Zuo LJ, Nan YX, Liu YJ, Fu L, Chen HZ. Synthesis, char-
acterization, and photovoltaic property of a low band gap polymer
alternating dithienopyrrole and thienopyrroledione units. Polymer
2011;52:2559–64.
[349] Zhou EJ, Cong JZ, Tajima K, Yang CH, Hashimoto K. Synthesis
and photovoltaic properties of donor–acceptor copolymer based
on dithienopyrrole and thienopyrroledione. Macromol Chem Phys
2011;212:305–10.
[350] Steckler TT, Zhang X, Hwang J, Honeyager R, Ohira S, Zhang
XH, Grant A, Ellinger S, Odom SA, Sweat D, Tanner DB, Rinzler
AG, Barlow S, Bredas JL, Kippelen B, Marder SR, Reynolds JR. A
spray-processable, low bandgap, and ambipolar donor–acceptor
conjugated polymer. J Am Chem Soc 2009;131:2824–6.
[351] Hou JH, Chen HY, Zhang SQ, Li G, Yang Y. Synthesis, characterization,
and photovoltaic properties of a low band gap polymer based on
silole-containing polythiophenes and 2,1,3-benzothiadiazole. J Am
Chem Soc 2008;130:16144–5.
[352] Chu TY, Lu JP, Beaupre S, Zhang YG, Pouliot JR, Wakim S, Zhou
JY, Leclerc M, Li Z, Ding JF, Tao Y. Bulk heterojunction solar
cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno[3,2-b:2 ,3 -
d]silole copolymer with a power conversion efficiency of 7.3%. J Am
Chem Soc 2011;133:4250–3.
[353] Zhang MJ, Fan HJ, Cuo X, He YJ, Zhang ZG, Min J, Zhang J,
Zhao GJ, Zhan XW, Li YF. Synthesis and photovoltaic properties
of bithiazole-based donor–acceptor copolymers. Macromolecules
2010;43:5706–12.
[354] Zhang MJ, Guo X, Li YF. Synthesis and characterization of a copoly-
mer based on thiazolothiazole and dithienosilole for polymer solar
cells. Adv Energy Mater 2011;1:557–60.
[355] Zhang Y, Zou JY, Yip HL, Sun Y, Davies JA, Chen KS, Acton O,
Jen AKY. Conjugated polymers based on C, Si and N-bridged
dithiophene and thienopyrroledione units: synthesis, field-effect
transistors and bulk heterojunction polymer solar cells. J Mater
Chem 2011;21:3895–902.
[356] Coffin RC, Peet J, Rogers J, Bazan GC. Streamlined microwave-
assisted preparation of narrow-bandgap conjugated polymers
for high-performance bulk heterojunction solar cells. Nat Chem
2009;1:657–61.
[357] Patil AV, Lee WH, Lee E, Kim K, Kang IN, Lee SH. Synthesis
and photovoltaic properties of a low-band-gap copolymer of
dithieno[3,2-b:2 ,3 -d]thiophene and dithienylquinoxaline. Macro-
molecules 2011;44:1238–41.
[358] Ku SY, Liman CD, Burke DJ, Treat ND, Cochran JE, Amir
E, Perez LA, Chabinyc ML, Hawker CJ. A facile synthesis of
low-band-gap donor–acceptor copolymers based on dithieno[3,2-
b:2 ,3 -d]thiophene. Macromolecules 2011;44:9533–8.
[359] Patil AV, Lee WH, Kim K, Park H, Kang IN, Lee SH. Synthesis
and photovoltaic properties of narrow band gap copolymers of
dithieno[3,2-b:2 ,3 -d]thiophene and diketopyrrolopyrrole. Polym
Chem 2011;2:2907–16.
[360] Shahid M, Ashraf RS, Huang ZG, Kronemeijer AJ, McCarthy-Ward T,
McCulloch I, Durrant JR, Sirringhaus H, Heeney M. Photovoltaic and
field effect transistor performance of selenophene and thiophene
diketopyrrolopyrrole co-polymers with dithienothiophene. J Mater
Chem 2012;22:12817–23.
[361] Amb CM, Chen S, Graham KR, Subbiah J, Small CE, So F, Reynolds JR.
Dithienogermole as a fused electron donor in bulk heterojunction
solar cells. J Am Chem Soc 2011;133:10062–5.
[362] Small CE, Chen S, Subbiah J, Amb CM, Tsang SW, Lai TH,
Reynolds JR, So F. High-efficiency inverted dithienogermole-
thienopyrrolodione-based polymer solar cells. Nat Photonics
2012;6:115–20.
[363] Fei ZP, Shahid M, Yaacobi-Gross N, Rossbauer S, Zhong HL, Watkins
SE, Anthopoulos TD, Heeney M. Thiophene fluorination to enhance
photovoltaic performance in low band gap donor–acceptor poly-
mers. Chem Commun 2012;48:11130–2.
[364] Chen CP, Chan SH, Chao TC, Ting C, Ko BT. Low-bandgap
poly(thiophene-phenylene-thiophene) derivatives with
broaden absorption spectra for use in high-performance
bulk-heterojunction polymer solar cells. J Am Chem Soc
2008;130:12828–33.
[365] Bronstein H, Leem DS, Hamilton R, Woebkenberg P, King S, Zhang
WM, Ashraf RS, Heeney M, Anthopoulos TD, de Mello J, McCulloch
I. Indacenodithiophene-co-benzothiadiazole copolymers for high
performance solar cells or transistors via alkyl chain optimization.
Macromolecules 2011;44:6649–52.
[366] Zhang MJ, Guo X, Wang XC, Wang HQ, Li YF. Synthesis and pho-
tovoltaic properties of D–A copolymers based on alkyl-substituted
indacenodithiophene donor unit. Chem Mater 2011;23:4264–70.
[367] Zhang Y, Zou JY, Yip HL, Chen KS, Zeigler DF, Sun Y, Jen AKY. Inda-
cenodithiophene and quinoxaline-based conjugated polymers for
highly efficient polymer solar cells. Chem Mater 2011;23:2289–91.
[368] Zhang Y, Zou JY, Yip HL, Chen KS, Davies JA, Sun Y, Jen AKY. Synthe-
sis, characterization, charge transport, and photovoltaic properties
of dithienobenzoquinoxaline- and dithienobenzopyridopyrazine-
based conjugated polymers. Macromolecules 2011;44:4752–8.
[369] Guo X, Zhang M, Tan J, Zhang S, Huo L, Hu W, Li Y, Hou J. Influence of
D/A ratio on photovoltaic performance of a highly efficient polymer
solar cell system. Adv Mater 2012;24:6536–41.
[370] Donaghey JE, Ashraf RS, Kim Y, Huang ZG, Nielsen CB, Zhang WM,
Schroeder B, Grenier CRG, Brown CT, D’Angelo P, Smith J, Watkins
S, Song K, Anthopoulos TD, Durrant JR, Williams CK, McCulloch
I. Pyrroloindacenodithiophene containing polymers for organic
field effect transistors and organic photovoltaics. J Mater Chem
2011;21:18744–52.
[371] Ashraf RS, Chen ZY, Leem DS, Bronstein H, Zhang WM, Schroeder
B, Geerts Y, Smith J, Watkins S, Anthopoulos TD, Sirringhaus H, de
Mello JC, Heeney M, McCulloch I. Silaindacenodithiophene semi-
conducting polymers for efficient solar cells and high-mobility
ambipolar transistors. Chem Mater 2011;23:768–70.
[372] Schroeder BC, Huang ZG, Ashraf RS, Smith J, D’Angelo P,
Watkins SE, Anthopoulos TD, Durrant JR, McCulloch I.
Silaindacenodithiophene-based low band gap polymers –
the effect of fluorine substitution on device performances and film
morphologies. Adv Funct Mater 2012;22:1663–70.
[373] Wang JY, Hau SK, Yip HL, Davies JA, Chen KS, Zhang Y, Sun Y, Jen
AKY. Benzobis(silolothiophene)-based low bandgap polymers for
efficient polymer solar cells. Chem Mater 2011;23:765–7.
[374] Kim J, Han AR, Seo JH, Oh JH, Yang C. beta-Alkyl substituted
dithieno[2,3-d;2 ,3 -d ]benzo[1,2-b;4,5-b ]dithiophene semicon-
ducting materials and their application to solution-processed
organic transistors. Adv Mater 2012;24:3464–72.
[375] Fei ZP, Ashraf RS, Huang ZG, Smith J, Kline RJ, D’Angelo P,
Anthopoulos TD, Durrant JR, McCulloch I, Heeney M. Germainda-
cenodithiophene based low band gap polymers for organic solar
cells. Chem Commun 2012;48:2955–7.
[376] Kimoto A, Tajima Y. Donor–acceptor-type polymers based on
dithieno[2,3-b;7,6-b]carbazole unit for photovoltaic applications.
Org Lett 2012;14:2282–5.
[377] Deng Y, Chen Y, Zhang X, Tian H, Bao C, Yan D, Geng Y, Wang
F. Donor–acceptor conjugated polymers with dithienocarbazoles
as donor units: effect of structure on semiconducting properties.
Macromolecules 2012;45:8621–7.
[378] Bronstein H, Ashraf RS, Kim YJ, White AJP, Anthopoulos T,
Song K, James D, Zhang WM, McCulloch I. Synthesis of a
novel fused thiophene-thieno[3,2-b]thiophene-thiophene donor
monomer and co-polymer for use in OPV and OFETs. Macromol
Rapid Commun 2011;32:1664–8.
[379] Schroeder BC, Ashraf RS, Thomas S, White AJP, Biniek L, Nielsen
CB, Zhang WM, Huang ZG, Tuladhar PS, Watkins SE, Anthopoulos
TD, Durrant JR, McCulloch I. Synthesis of novel thieno[3,2-
b]thienobis(silolothiophene) based low bandgap polymers for
organic photovoltaics. Chem Commun 2012;48:7699–701.
[380] Cheng YJ, Wu JS, Shih PI, Chang CY, Jwo PC, Kao WS, Hsu CS.
Carbazole-based ladder-type heptacylic arene with aliphatic side
chains leading to enhanced efficiency of organic photovoltaics.
Chem Mater 2011;23:2361–9.
[381] Yuan MJ, Yang PY, Durban MM, Luscombe CK. Low bandgap poly-
mers based on silafluorene containing multifused heptacylic arenes
for photovoltaic applications. Macromolecules 2012;45:5934–40.
[382] Dai GL, Chang JJ, Wu JS, Chi CY. Dithieno-naphthalimide
based copolymers for air-stable field effect transistors: syn-
thesis, characterization and device performance. J Mater Chem
2012;22:21201–9.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[383] Chen YL, Chang CY, Cheng YJ, Hsu CS. Synthesis of a new ladder-type
benzodi(cyclopentadithiophene) arene with forced planarization
leading to an enhanced efficiency of organic photovoltaics. Chem
Mater 2012;24:3964–71.
[384] Chang HH, Tsai CE, Lai YY, Chiou DY, Hsu SL, Hsu CS,
Cheng YJ. Synthesis, molecular and photovoltaic properties of
donor–acceptor conjugated polymers incorporating a new hep-
tacylic indacenodithieno[3,2-b]thiophene arene. Macromolecules
2012;45:9282–91.
[385] Xu YX, Chueh CC, Yip HL, Ding FZ, Li YX, Li CZ, Li X, Chen
WC, Jen AKY. Improved charge transport and absorption coef-
ficient in indacenodithieno[3,2-b]thiophene-based ladder-type
polymer leading to highly efficient polymer solar cells. Adv Mater
2012;24:6356–61.
[386] Liang YY, Wu Y, Feng DQ, Tsai ST, Son HJ, Li G, Yu LP. Development
of new semiconducting polymers for high performance solar cells.
J Am Chem Soc 2009;131:56–7.
[387] Price SC, Stuart AC, Yang LQ, Zhou HX, You W. Fluorine substituted
conjugated polymer of medium band gap yields 7% efficiency in
polymer-fullerene solar cells. J Am Chem Soc 2011;133:4625–31.
[388] Liang YY, Feng DQ, Wu Y, Tsai ST, Li G, Ray C, Yu LP. Highly effi-
cient solar cell polymers developed via fine-tuning of structural
and electronic properties. J Am Chem Soc 2009;131:7792–9.
[389] Hou JH, Chen HY, Zhang SQ, Chen RI, Yang Y, Wu Y, Li G. Synthesis
of a low band gap polymer and its application in highly efficient
polymer solar cells. J Am Chem Soc 2009;131:15586–7.
[390] Liang YY, Yu LP. A new class of semiconducting polymers for bulk
heterojunction solar cells with exceptionally high performance. Acc
Chem Res 2010;43:1227–36.
[391] Huo LJ, Zhang SQ, Guo X, Xu F, Li YF, Hou JH. Replacing alkoxy
groups with alkylthienyl groups: a feasible approach to improve
the properties of photovoltaic polymers. Angew Chem Int Ed
2011;50:9697–702.
[392] Huo LJ, Guo X, Li YF, Hou JH. Synthesis of a polythieno[3,4-
b]thiophene derivative with a low-lying HOMO level and its
application in polymer solar cells. Chem Commun 2011;47:8850–2.
[393] Zhang MJ, Sun YP, Guo X, Cui CH, He YJ, Li YF. Synthesis and
characterization of dioctyloxybenzo[1,2-b:4,3-b ]-dithiophene-
containing copolymers for polymer solar cells. Macromolecules
2011;44:7625–31.
[394] Hart H, Sasaoka M. Exocyclic benzenes. Synthesis and properties
of benzo[1,2-c:3,4-c :5,6-c ]trithiophene, a Tristhiahexaradialene.
J Am Chem Soc 1978;100:4326–7.
[395] Patra A, Wijsboom YH, Shimon LJW, Bendikov M. Planar
[6]radialenes: structure, synthesis, and aromaticity of ben-
zotriselenophene and benzotrithiophene. Angew Chem Int Ed
2007;46:8814–8.
[396] Kashiki T, Shinamura S, Kohara M, Miyazaki E, Takimiya K, Ikeda
M, Kuwabara H. One-pot synthesis of benzo[b]thiophenes and
benzo[b]selenophenes from o-halo-substituted ethynylbenzenes:
convenient approach to mono-, bis-, and tris-chalcogenophene-
annulated benzenes. Org Lett 2009;11:2473–5.
[397] Kashiki T, Kohara M, Osaka I, Miyazaki E, Takimiya K. Synthe-
sis and characterization of benzo[1,2-b:3,4-b :5,6-b ]trithiophene
(BTT) oligomers. J Org Chem 2011;76:4061–70.
[398] Nielsen CB, Schroeder BC, Hadipour A, Rand BP, Watkins SE,
McCulloch I. A benzotrithiophene-based low band gap polymer for
polymer solar cells with high open-circuit voltage. J Mater Chem
2011;21:17642–5.
[399] McCulloch I, Ashraf RS, Biniek L, Bronstein H, Combe C, Donaghey
JE, James DI, Nielsen CB, Schroeder BC, Zhang WM. Design of semi-
conducting indacenodithiophene polymers for high performance
transistors and solar cells. Acc Chem Res 2012;45:714–22.
[400] Zhao X, Yang D, Lv H, Yin L, Yang X. New benzotrithiophene deriva-
tive with a broad band gap for high performance polymer solar
cells. Polym Chem 2013;4:57–60.
[401] Lan SC, Yang PA, Zhu MJ, Yu CM, Jiang JM, Wei KH. Thio-
phene spacers impart crystallinity and enhance the efficiency of
benzotrithiophene-based conjugated polymers for bulk hetero-
junction photovoltaics. Polym Chem 2013;4:1132–40.
[402] Guo X, Wang SH, Enkelmann V, Baumgarten M, Müllen K.
Making benzotrithiophene a stronger electron donor. Org Lett
2011;13:6062–5.
[403] Yang L, Tumbleston JR, Zhou H, Ade H, You W. Disentangling the
impact of side chains and fluorine substituents of conjugated donor
polymers on the performance of photovoltaic blends. Energy Envi-
ron Sci 2013;6:316–26.
[404] Zhou HX, Yang LQ, Price SC, Knight KJ, You W. Enhanced photo-
voltaic performance of low-bandgap polymers with deep LUMO
levels. Angew Chem Int Ed 2010;49:7992–5.
1905
[405] Osaka I, Abe T, Shimawaki M, Koganezawa T, Takimiya K.
Naphthodithiophene-based donor–acceptor polymers: ver-
satile semiconductors for OFETs and OPVs. ACS Macro Lett
2012;1:437–40.
[406] Sanjaykumar SR, Badgujar S, Song CE, Shin WS, Moon SJ, Kang
IN, Lee J, Cho S, Lee SK, Lee JC. Synthesis and characterization of
a novel naphthodithiophene-based copolymer for use in polymer
solar cells. Macromolecules 2012;45:6938–45.
[407] Peng Q, Huang Q, Hou XB, Chang PP, Xu J, Deng SJ. Enhanced
solar cell performance by replacing benzodithiophene with naph-
thodithiophene in diketopyrrolopyrrole-based copolymers. Chem
Commun 2012;48:11452–4.
[408] He F, Wang W, Chen W, Xu T, Darling SB, Strzalka J, Liu Y, Yu LP.
Tetrathienoanthracene-based copolymers for efficient solar cells. J
Am Chem Soc 2011;133:3284–7.
[409] Jiang Y, Mei JG, Ayzner AL, Toney MF, Bao ZA. 5,11-Conjugation-
extended low-bandgap anthradithiophene-containing polymer
exhibiting enhanced thin-film order and field-effect mobility.
Chem Commun 2012;48:7286–8.
[410] Wu JS, Lin CT, Wang CL, Cheng YJ, Hsu CS. New angular-shaped
and isomerically pure anthradithiophene with lateral aliphatic side
chains for conjugated polymers: synthesis, characterization, and
implications for solution-prossessed organic field-effect transistors
and photovoltaics. Adv Mater 2012;24:2391–9.
[411] Zhou WY, Wen YG, Ma LC, Liu YQ, Zhan XW. Conjugated polymers of
rylene diimide and phenothiazine for n-channel organic field-effect
transistors. Macromolecules 2012;45:4115–21.
[412] Kim G, Yeom HR, Cho S, Seo JH, Kim JY, Yang C. Easily attainable
phenothiazine-based polymers for polymer solar cells: advantage
of insertion of S,S-dioxides into its polymer for inverted structure
solar cells. Macromolecules 2012;45:1847–57.
[413] Nie WY, MacNeill CM, Li Y, Noftle RE, Carroll DL, Coffin
RC. A soluble high molecular weight copolymer of benzo[1,2-
b:4,5-b ]dithiophene and benzoxadiazole for efficient organic
photovoltaics. Macromol Rapid Commun 2011;32:1163–8.
[414] Gibson GL, McCormick TM, Seferos DS. Atomistic band gap
engineering in donor–acceptor polymers. J Am Chem Soc
2012;134:539–47.
[415] Peng Q, Liu XJ, Su D, Fu GW, Xu J, Dai LM. Novel benzo[1,2-b:4,5-
b ]dithiophene-benzothiadiazole derivatives with variable
side chains for high-performance solar cells. Adv Mater
2011;23:4554–8.
[416] Zhou HX, Yang LQ, Stuart AC, Price SC, Liu SB, You W. Development
of fluorinated benzothiadiazole as a structural unit for a polymer
solar cell of 7% efficiency. Angew Chem Int Ed 2011;50:2995–8.
[417] Ying L, Hsu BBY, Zhan HM, Welch GC, Zalar P, Perez LA, Kramer
EJ, Nguyen TQ, Heeger AJ, Wong WY, Bazan GC. Regioregular pyri-
dal[2,1,3]thiadiazole pi-conjugated copolymers. J Am Chem Soc
2011;133:18538–41.
[418] Henson ZB, Müllen K, Bazan GC. Design strategies for organic
semiconductors beyond the molecular formula. Nat Chem
2012;4:699–704.
[419] Hwang YJ, Kim FS, Xin H, Jenekhe SA. New thienothiadiazole-based
conjugated copolymers for electronics and optoelectronics. Macro-
molecules 2012;45:3732–9.
[420] Cimrová V, Kmínek I, Pavlačková P, Výprachtický D. Low-bandgap
donor–acceptor copolymers with 4,6-bis(3 -(2-ethylhexyl)thien-
2 -yl)thieno[3,4-c][1,2,5]thiadiazole: synthesis, optical, electro-
chemical, and photovoltaic properties. J Polym Sci Part A Polym
Chem 2011;49:3426–36.
[421] Song S, Park S, Kwon S, Lee BH, Shim JY, Lee J, Park SH, Jin Y, Kim I,
Lee K, Suh H. Synthesis and photovoltaic property of copolymers
with phenanthrothiadiazole moiety. Sol Energy Mater Sol Cells
2012;105:229–36.
[422] Kim J, Yun MH, Anant P, Cho S, Jacob J, Kim JY, Yang C. Copolymers
comprising 2,7-carbazole and bis-benzothiadiazole units for bulk-
heterojunction solar cells. Chem Eur J 2011;17:14681–8.
[423] Wang HF, Cheng P, Liu Y, Chen JM, Zhan XW, Hu WP, Shuai
ZG, Li YF, Zhu DB. A conjugated polymer based on 5,5 -
bibenzo[c][1,2,5]thiadiazole for high-performance solar cells. J
Mater Chem 2012;22:3432–9.
[424] Oh HS, Kim TD, Koh YH, Lee KS, Cho S, Cartwright A, Prasad PN.
Synthesis and characterization of dithienylbenzobis(thiadiazole)-
based low band-gap polymers for organic electronics. Chem
Commun 2011;47:8931–3.
[425] Yuen JD, Kumar R, Zakhidov D, Seifter J, Lim B, Heeger AJ, Wudl F.
Ambipolarity in benzobisthiadiazole-based donor–acceptor conju-
gated polymers. Adv Mater 2011;23:3780–5.
[426] Osaka I, Shimawaki M, Mori H, Doi I, Miyazaki E, Koganezawa T,
Takimiya K. Synthesis, characterization, and transistor and solar
1906 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
cell applications of a naphthobisthiadiazole-based semiconducting
polymer. J Am Chem Soc 2012;134:3498–507.
[427] Wang M, Hu XW, Liu P, Li W, Gong X, Huang F, Cao Y.
Donor acceptor conjugated polymer based on naphtho[1,2-c:5,6-
c]bis[1,2,5]thiadiazole for high-performance polymer solar cells. J
Am Chem Soc 2011;133:9638–41.
[428] Zoombelt AP, Fonrodona M, Wienk MM, Sieval AB, Hummelen JC,
Janssen RAJ. Photovoltaic performance of an ultrasmall band gap
polymer. Org Lett 2009;11:903–6.
[429] Dallos T, Beckmann D, Brunklaus G, Baumgarten M.
Thiadiazoloquinoxaline-acetylene containing polymers as
semiconductors in ambipolar field effect transistors. J Am Chem
Soc 2011;133:13898–901.
[430] An C, Guo X, Puniredd SR, Zhao Y, Pisula W, Baumgarten
M. Benzodithiophene-thiadiazoloquinoxaline as an acceptor for
ambipolar copolymers with deep LUMO level and distinct linkage
pattern. Macromolecules 2013 (submitted).
[431] He ZC, Zhang C, Xu XF, Zhang LJ, Huang L, Chen JW, Wu HB, Cao
Y. Largely enhanced efficiency with a PFN/Al bilayer cathode in
high efficiency bulk heterojunction photovoltaic cells with a low
bandgap polycarbazole donor. Adv Mater 2011;23:3086–9.
[432] Duan R, Ye L, Guo X, Huang Y, Wang P, Zhang S, Zhang J, Huo
L, Hou J. Application of two-dimensional conjugated benzo[1,2-
b:4,5-b ]dithiophene in quinoxaline-based photovoltaic polymers.
Macromolecules 2012;45:3032–8.
[433] Iyer A, Bjorgaard J, Anderson T, Kose ME. Quinoxaline-based
semiconducting polymers: effect of fluorination on the photophys-
ical, thermal, and charge transport properties. Macromolecules
2012;45:6380–9.
[434] Chen HC, Chen YH, Liu CC, Chien YC, Chou SW, Chou PT. Prominent
short-circuit currents of fluorinated quinoxaline-based copolymer
solar cells with a power conversion efficiency of 8.0%. Chem Mater
2012;24:4766–72.
[435] Mondal R, Miyaki N, Becerril HA, Norton JE, Parmer J, Mayer
AC, Tang ML, Bredas JL, McGehee MD, Bao ZA. Synthesis of ace-
naphthyl and phenanthrene based fused-aromatic thienopyrazine
co-polymers for photovoltaic and thin film transistor applications.
Chem Mater 2009;21:3618–28.
[436] Guo XG, Kim FS, Jenekhe SA, Watson MD. Phthalimide-based poly-
mers for high performance organic thin-film transistors. J Am Chem
Soc 2009;131:7206–7.
[437] Kola S, Tremblay NJ, Yeh ML, Katz HE, Kirschner SB, Reich DH.
Synthesis and characterization of a pyromellitic diimide-based
polymer with C- and N-main chain links: matrix for solution-
processable n-channel field-effect transistors. ACS Macro Lett
2012;1:136–40.
[438] Guo X, Watson MD. Pyromellitic diimide-based donor–acceptor
poly(phenylene ethynylene)s. Macromolecules 2011;44:6711–6.
[439] Wang HF, Shi QQ, Lin YZ, Fan HJ, Cheng P, Zhan XW, Li YF, Zhu DB.
Conjugated polymers based on a new building block: dithienoph-
thalimide. Macromolecules 2011;44:4213–21.
[440] Zhou NJ, Guo XG, Ortiz RP, Li SQ, Zhang SM, Chang RPH, Facchetti
A, Marks TJ. Bithiophene imide and benzodithiophene copoly-
mers for efficient inverted polymer solar cells. Mater Sci Eng C
2012;24:2242–8.
[441] Guo XG, Zhou NJ, Lou SJ, Hennek JW, Ortiz RP, Butler MR, Boudreault
PLT, Strzalka J, Morin PO, Leclerc M, Navarrete JTL, Ratner MA,
Chen LX, Chang RPH, Facchetti A, Marks TJ. Bithiopheneimide-
dithienosilole/dithienogermole copolymers for efficient solar cells:
information from structure-property-device performance correla-
tions and comparison to thieno[3,4-c]pyrrole-4,6-dione analogues.
J Am Chem Soc 2012;134:18427–39.
[442] Guo XG, Ortiz RP, Zheng Y, Hu Y, Noh YY, Baeg KJ, Facchetti
A, Marks TJ. Bithiophene-imide-based polymeric semiconductors
for field-effect transistors: synthesis, structure-property correla-
tions, charge carrier polarity, and device stability. J Am Chem Soc
2011;133:1405–18.
[443] Cui WB, Yuen J, Wudl F. Benzodipyrrolidones and their polymers.
Macromolecules 2011;44:7869–73.
[444] Hong W, Sun B, Guo C, Yuen J, Li Y, Lu S, Huang C, Facchetti
A. Dipyrrolo[2,3-b:2 ,3 -e]pyrazine-2,6(1H,5H)-dione based conju-
gated polymers for ambipolar organic thin-film transistors. Chem
Commun 2013;49:484–6.
[445] Cui CH, Fan X, Zhang MJ, Zhang J, Min J, Li YF. A D–A copolymer
of dithienosilole and a new acceptor unit of naphtho[2,3-
c]thiophene-4,9-dione for efficient polymer solar cells. Chem
Commun 2011;47:11345–7.
[446] Yang C, Cho S, Chiechi RC, Walker W, Coates NE, Moses
D, Heeger AJ, Wudl F. Visible-near infrared absorbing
dithienylcyclopentadienone-thiophene copolymers for organic
thin-film transistors. J Am Chem Soc 2008;130:16524–6.
[447] Fei Z, Gao X, Smith J, Pattanasattayavong P, Domingo EB,
Stingelin N, Watkins SE, Anthopoulos TD, Kline RJ, Heeney
M. Near infrared absorbing soluble poly(cyclopenta[2,1-b:3,4-
b ]dithiophen-4-one)vinylene polymers exhibiting high hole and
electron mobilities in ambient air. Chem Mater 2013;25:59–68.
[448] Huang Y, Guo X, Liu F, Huo LJ, Chen YN, Russell TP, Han CC, Li YF, Hou
JH. Improving the ordering and photovoltaic properties by extend-
ing pi-conjugated area of electron-donating units in polymers with
D–A structure. Adv Mater 2012;24:3383–9.
[449] Cheng YJ, Ho YJ, Chen CH, Kao WS, Wu CE, Hsu SL, Hsu CS. Synthesis,
photophysical and photovoltaic properties of conjugated polymers
containing fused donor–acceptor dithienopyrrolobenzothiadia-
zole and dithienopyrroloquinoxaline arenes. Macromolecules
2012;45:2690–8.
[450] Guo XG, Watson MD. Conjugated polymers from naphthalene
bisimide. Org Lett 2008;10:5333–6.
[451] Durban MM, Kazarinoff PD, Luscombe CK. Synthesis and char-
acterization of thiophene-containing naphthalene diimide
n-type copolymers for OFET applications. Macromolecules
2010;43:6348–52.
[452] Yan H, Chen ZH, Zheng Y, Newman C, Quinn JR, Dotz F, Kastler
M, Facchetti A. A high-mobility electron-transporting polymer for
printed transistors. Nature 2009;457:679–87.
[453] Hwang YJ, Ren GQ, Murari NM, Jenekhe SA. n-Type naphthalene
diimide-biselenophene copolymer for all-polymer bulk hetero-
junction solar cells. Macromolecules 2012;45:9056–62.
[454] Nakabayashi K, Mori H. All-polymer solar cells based on fully con-
jugated block copolymers composed of poly(3-hexylthiophene)
and poly(naphthalene bisimide) segments. Macromolecules
2012;45:9618–25.
[455] Zhou EJ, Cong JZ, Zhao MX, Zhang LZ, Hashimoto K, Tajima K. Syn-
thesis and application of poly(fluorene-alt-naphthalene diimide)
as an n-type polymer for all-polymer solar cells. Chem Commun
2012;48:5283–5.
[456] Chen ZH, Zheng Y, Yan H, Facchetti A. Naphthalenedicarboximide-
vs perylenedicarboximide-based copolymers. Synthesis and semi-
conducting properties in bottom-gate N-channel organic transis-
tors. J Am Chem Soc 2009;131:8–9.
[457] Zhan XW, Tan ZA, Domercq B, An ZS, Zhang X, Barlow S, Li YF,
Zhu DB, Kippelen B, Marder SR. A high-mobility electron-transport
polymer with broad absorption and its use in field-effect transistors
and all-polymer solar cells. J Am Chem Soc 2007;129:7246–7.
[458] Zhou EJ, Cong JZ, Wei QS, Tajima K, Yang CH, Hashimoto K. All-
polymer solar cells from perylene diimide based copolymers:
material design and phase separation control. Angew Chem Int Ed
2011;50:2799–803.
[459] Kang I, An TK, Hong Ja, Yun HJ, Kim R, Chung DS, Park CE, Kim YH,
Kwon SK. Effect of selenophene in a DPP copolymer incorporating
a vinyl group for high-performance organic field-effect transistors.
Adv Mater 2013;25:524–8.
[460] Lee J, Han AR, Hong J, Seo JH, Oh JH, Yang C. Inversion of dominant
polarity in ambipolar polydiketopyrrolopyrrole with thermally
removable groups. Adv Funct Mater 2012;22:4128–38.
[461] Mei JG, Kim DH, Ayzner AL, Toney MF, Bao ZA. Siloxane-terminated
solubilizing side chains: bringing conjugated polymer backbones
closer and boosting hole mobilities in thin-film transistors. J Am
Chem Soc 2011;133:20130–3.
[462] Lee J, Han AR, Kim J, Kim Y, Oh JH, Yang C. Solution-
processable ambipolar diketopyrrolopyrrole-selenophene poly-
mer with unprecedentedly high hole and electron mobilities. J Am
Chem Soc 2012;134:20713–21.
[463] Bronstein H, Chen ZY, Ashraf RS, Zhang WM, Du JP, Durrant
JR, Tuladhar PS, Song K, Watkins SE, Geerts Y, Wienk MM,
Janssen RAJ, Anthopoulos T, Sirringhaus H, Heeney M, McCulloch
I. Thieno[3,2-b]thiophene-diketopyrrolopyrrole-containing poly-
mers for high-performance organic field-effect transistors and
organic photovoltaic devices. J Am Chem Soc 2011;133:3272–5.
[464] Woo CH, Beaujuge PM, Holcombe TW, Lee OP, Frechet JMJ. Incorpo-
ration of furan into low band-gap polymers for efficient solar cells.
J Am Chem Soc 2010;132:15547–9.
[465] Sonar P, Hab TJ, Dodabalapur A. A fluorenone based low band gap
solution processable copolymer for air stable and high mobility
organic field effect transistors. Chem Commun 2013;49:1588–90.
[466] Kronemeijer AJ, Gili E, Shahid M, Rivnay J, Salleo A, Heeney
M, Sirringhaus H. A selenophene-based low-bandgap
donor–acceptor polymer leading to fast ambipolar logic. Adv
Mater 2012;24:1558–65.
 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[467] Stalder R, Mei JG, Reynolds JR. Isoindigo-based donor–acceptor con-
jugated polymers. Macromolecules 2010;43:8348–52.
[468] Stalder R, Mei JG, Subbiah J, Grand C, Estrada LA, So F,
Reynolds JR. n-Type conjugated polyisoindigos. Macromolecules
2011;44:6303–10.
[469] Lei T, Cao Y, Fan YL, Liu CJ, Yuan SC, Pei J. High-performance air-
stable organic field-effect transistors: isoindigo-based conjugated
polymers. J Am Chem Soc 2011;133:6099–101.
[470] Wang EG, Ma ZF, Zhang Z, Vandewal K, Henriksson P, Inganäs
O, Zhang FL, Andersson MR. An easily accessible isoindigo-based
polymer for high-performance polymer solar cells. J Am Chem Soc
2011;133:14244–7.
[471] Stalder R, Grand C, Subbiah J, So F, Reynolds JR. An isoindigo
and dithieno[3,2-b:2 ,3 -d]silole copolymer for polymer solar cells.
Polym Chem 2012;3:89–92.
[472] Ma ZF, Wang EG, Jarvid ME, Henriksson P, Inganäs O,
Zhang FL, Andersson MR. Synthesis and characterization of
benzodithiophene-isoindigo polymers for solar cells. J Mater Chem
2012;22:2306–14.
[473] Lei T, Dou JH, Pei J. Influence of alkyl chain branching positions
on the hole mobilities of polymer thin-film transistors. Adv Mater
2012;24:6457–61.
[474] Lei T, Dou JH, Ma ZJ, Yao CH, Liu CJ, Wang JY, Pei J. Ambipo-
lar polymer field-effect transistors based on fluorinated isoindigo:
high performance and improved ambient stability. J Am Chem Soc
2012;134:20025–8.
[475] Van Pruissen GWP, Gholamrezaie F, Wienk MM, Janssen RAJ. Syn-
thesis and properties of small band gap thienoisoindigo based
conjugated polymers. J Mater Chem 2012;22:20387–93.
[476] Koizumi Y, Ide M, Saeki A, Vijayakumar C, Balan B, Kawamoto M,
Seki S. Thienoisoindigo-based low-band gap polymers for organic
electronic devices. Polym Chem 2013;4:484–94.
[477] Sonar P, Singh SP, Li Y, Soh MS, Dodabalapur A. A low-bandgap
diketopyrrolopyrrole-benzothiadiazole-based copolymer for high-
mobility ambipolar organic thin-film transistors. Adv Mater
2010;22:5409–13.
[478] Cho S, Lee J, Tong MH, Seo JH, Yang C. Poly(diketopyrrolopyrrole-
benzothiadiazole) with ambipolarity approaching 100% equiva-
lency. Adv Funct Mater 2011;21:1910–6.
[479] Lee J, Cho S, Seo JH, Anant P, Jacob J, Yang C. Swapping field-effect
transistor characteristics in polymeric diketopyrrolopyrrole semi-
conductors: debut of an electron dominant transporting polymer.
J Mater Chem 2012;22:1504–10.
[480] Yuen JD, Fan J, Seifter J, Lim B, Hufschmid R, Heeger AJ, Wudl
F. High performance weak donor–acceptor polymers in thin film
transistors: effect of the acceptor on electronic properties, ambipo-
lar conductivity, mobility, and thermal stability. J Am Chem Soc
2011;133:20799–807.
[481] Lee JK, Gwinner MC, Berger R, Newby C, Zentel R, Friend RH,
Sirringhaus H, Ober CK. High-performance electron-transporting
polymers derived from a heteroaryl bis(trifluoroborate). J Am Chem
Soc 2011;133:9949–51.
[482] Gwinner MC, Brenner TJK, Lee JK, Newby C, Ober CK, McNeill
CR, Sirringhaus H. Organic field-effect transistors and solar
cells using novel high electron-affinity conjugated copolymers
based on alkylbenzotriazole and benzothiadiazole. J Mater Chem
2012;22:4436–9.
[483] Ashraf RS, Kronemeijer AJ, James DI, Sirringhaus H, McCulloch I. A
new thiophene substituted isoindigo based copolymer for high per-
formance ambipolar transistors. Chem Commun 2012;48:3939–41.
[484] Song HJ, Kim DH, Lee EJ, Heo SW, Lee JY, Moon DK. Conjugated
polymer consisting of quinacridone and benzothiadiazole as donor
materials for organic photovoltaics: coplanar property of polymer
backbone. Macromolecules 2012;45:7815–22.
[485] Lim DC, Kim KD, Park SY, Hong EM, Seo HO, Lim JH, Lee KH, Jeong
Y, Song C, Lee E, Kim YD, Cho S. Towards fabrication of high-
performing organic photovoltaics: new donor–polymer, atomic
layer deposited thin buffer layer and plasmonic effects. Energy
Environ Sci 2012;5:9803–7.
[486] Iyoda M, Yamakawa J, Rahman MJ. Conjugated macrocycles: con-
cepts and applications. Angew Chem Int Ed 2011;50:10522–53.
[487] Jung SH, Pisula W, Rouhanipour A, Rader HJ, Jacob J, Müllen K. A
conjugated polycarbazole ring around a porphyrin. Angew Chem
Int Ed 2006;45:4685–90.
[488] Schmaltz B, Rouhanipour A, Rader HJ, Pisula W, Müllen K. Fill-
ing the cavity of conjugated carbazole macrocycles with graphene
molecules: monolayers formed by physisorption serve as a sur-
face for pulsed laser deposition. Angew Chem Int Ed 2009;48:
720–4.
1907
[489] Simon SC, Schmaltz B, Rouhanipour A, Rader HJ, Müllen K.
A macrocyclic model dodecamer for polyfluorenes. Adv Mater
2009;21:83–5.
[490] Arnold L, Norouzi-Arasi H, Wagner M, Enkelmann V, Müllen K. A
porphyrin-related macrocycle from carbazole and pyridine build-
ing blocks: synthesis and metal coordination. Chem Commun
2011;47:970–2.
[491] Arnold L, Baumgarten M, Müllen K. A carbazole-containing por-
phyrinoid: synthesis and oxidation to the porphyrin-state. Chem
Commun 2012;48:9640–2.
[492] Zhang Z, Lim JM, Ishida M, Roznyatovskiy VV, Lynch VM, Gong
HY, Yang XP, Kim D, Sesser JL. Cyclo[m]pyridine[n]pyrroles: hybrid
macrocycles that display expanded pi-conjugation upon protona-
tion. J Am Chem Soc 2012;134:4076–9.
[493] Arnold L, Puniredd SR, von Malotki C, Pisula W, Koshino
N, Higashimura H, Baumgarten M, Wagner M, Müllen K.
Fused pi-extended discotic triangular porphyrinoids. J Porphyrins
Phthalocyanines 2012;16:564–75.
[494] Liu RL, von Malotki C, Arnold L, Koshino N, Higashimura H, Baum-
garten M, Müllen K. Triangular trinuclear metal-N-4 complexes
with high electrocatalytic activity for oxygen reduction. J Am Chem
Soc 2011;133:10372–5.
[495] O’Sullivan MC, Sprafke JK, Kondratuk DV, Rinfray C, Claridge TDW,
Saywell A, Blunt MO, O’Shea JN, Beton PH, Malfois M, Anderson
HL. Vernier templating and synthesis of a 12-porphyrin nano-ring.
Nature 2011;469:72–5.
[496] Sprafke JK, Odell B, Claridge TDW, Anderson HL. All-or-nothing
cooperative self-assembly of an annulene sandwich. Angew Chem
Int Ed 2011;50:5572–5.
[497] Arnold L, Müllen K. Modifying the porphyrin core – a chemist’s
jigsaw. J Porphyrins Phthalocyanines 2011;15:757–79.
[498] Pisula W, Kastler M, Yang C, Enkelmann V, Müllen K. Columnar
mesophase formation of cyclohexa-m-phenylene-based macro-
cycles. Chem Asian J 2007;2:51–6.
[499] Baumgarten M, Müllen K. Functional polyphenylenes for
supramolecular ordering and application in organic electronics.
In: Samorí P, Cacialli FF, editors. Functional supramolecular
architectures. Weinheim: Wiley-VCH; 2011. p. 155–94.
[500] Hanai Y, Rahman MJ, Yamakawa J, Takase M, Nishinaga T, Hasegawa
M, Kamada K, Iyoda M. Synthesis and nanostructures of cyclic triph-
enylene trimers having long alkyl and alkoxy side-chains. Chem
Asian J 2011;6:2940–5.
[501] Schwab MG, Qin TS, Pisula W, Mavrinskiy A, Feng XL, Baum-
garten M, Kim H, Laquai F, Schuh S, Trattnig R, List EJW, Müllen
K. Molecular triangles: synthesis, self-assembly, and blue emis-
sion of cyclo-7,10-tris-triphenylenyl macrocycles. Chem Asian J
2011;6:3001–10.
[502] Bieri M, Blankenburg S, Kivala M, Pignedoli CA, Ruffieux P, Müllen K,
Fasel R. Surface-supported 2D heterotriangulene polymers. Chem
Commun 2011;47:10239–41.
[503] Schlütter F, Rossel F, Kivala M, Enkelmann V, Gisselbrecht JP,
Ruffieux P, Fasel R, Müllen K. ␲-Conjugated heterotriangulene
macrocycles by solution and surface-supported synthesis towards
honeycomb networks. J Am Chem Soc 2013;135:4550–7.
[504] Chernichenko KY, Sumerin VV, Shpanchenko RV, Balenkova ES,
Nenajdenko VG. “Sulflower”: a new form of carbon sulfide. Angew
Chem Int Ed 2006;45:7367–70.
[505] Dadvand A, Cicoira F, Chernichenko KY, Balenkova ES, Osuna RM,
Rosei F, Nenajdenko VG, Perepichka DF. Heterocirculenes as a new
class of organic semiconductors. Chem Commun 2008:5354–6.
[506] Singh K, Sharma A, Zhang J, Xu W, Zhu DB. New sulfur bridged
neutral annulenes. Structure, physical properties and applications
in organic field-effect transistors. Chem Commun 2011;47:905–7.
[507] Ie Y, Hirose T, Aso Y. Synthesis, properties, and FET performance of
rectangular oligothiophene. J Mater Chem 2009;19:8169–75.
[508] Krömer J, Rios-Carreras II, Fuhrmann G, Musch C, Wunderlin
M, Debaerdemaeker T, Mena-Osteritz E, Bäuerle P. Synthesis
of the first fully alpha-conjugated macrocyclic oligothiophenes:
cyclo[n]thiophenes with tunable cavities in the nanometer regime.
Angew Chem Int Ed 2000;39:3481–6.
[509] Yang Y, Murali R. Impact of size effect on graphene nanoribbon
transport. IEEE Electron Device Lett 2010;31:237–9.
[510] Nakada K, Fujita M, Dresselhaus G, Dresselhaus MS. Edge state in
graphene ribbons: nanometer size effect and edge shape depend-
ence. Phys Rev B 1996;54:17954–61.
[511] Cai JM, Ruffieux P, Jaafar R, Bieri M, Braun T, Blankenburg S, Muoth
M, Seitsonen AP, Saleh M, Feng XL, Müllen K, Fasel R. Atomically
precise bottom-up fabrication of graphene nanoribbons. Nature
2010;466:470–3.
1908 X. Guo et al. / Progress in Polymer Science 38 (2013) 1832–1908
[512] Dössel L, Gherghel L, Feng XL, Müllen K. Graphene nanoribbons by
chemists: nanometer-sized. Soluble, and defect-free. Angew Chem
Int Ed 2011;50:2540–3.
[513] Yang XY, Dou X, Rouhanipour A, Zhi LJ, Rader HJ, Müllen
K. Two-dimensional graphene nanoribbons. J Am Chem Soc
2008;130:4216–7.
[514] Jia XT, Campos-Delgado J, Terrones M, Meunier V, Dresselhaus MS.
Graphene edges: a review of their fabrication and characterization.
Nanoscale 2011;3:86–95.
[515] Han MY, Özyilmaz B, Zhang YB, Kim P. Energy band-gap engineering
of graphene nanoribbons. Phys Rev Lett 2007;98, 206805/1–4.
[516] Son YW, Cohen ML, Louie SG. Half-metallic graphene nanoribbons.
Nature 2006;444:347–9.
[517] Reddy CD, Ramasubramaniam A, Shenoy VB, Zhang YW. Edge elas-
tic properties of defect-free single-layer graphene sheets. Appl Phys
Lett 2009;94, 101904/1–3.
[518] Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos
SV, Grigorieva IV, Firsov AA. Electric field effect in atomically thin
carbon films. Science 2004;306:666–9.
[519] Li XL, Wang XR, Zhang L, Lee SW, Dai HJ. Chemically
derived, ultrasmooth graphene nanoribbon semiconductors. Sci-
ence 2008;319:1229–32.
[520] Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zimney EJ,
Stach EA, Piner RD, Nguyen ST, Ruoff RS. Graphene-based composite
materials. Nature 2006;442:282–6.
[521] Tung VC, Allen MJ, Yang Y, Kaner RB. High-throughput solution
processing of large-scale graphene. Nat Nanotechnol 2009;4:25–9.
[522] Xie LM, Jiao LY, Dai HJ. Selective etching of graphene edges by
hydrogen plasma. J Am Chem Soc 2010;132:14751–3.
[523] Pan ZH, Liu N, Fu L, Liu ZF. Wrinkle engineering: a new
approach to massive graphene nanoribbon arrays. J Am Chem Soc
2011;133:17578–81.
[524] Kosynkin DV, Higginbotham AL, Sinitskii A, Lomeda JR, Dimiev A,
Price BK, Tour JM. Longitudinal unzipping of carbon nanotubes to
form graphene nanoribbons. Nature 2009;458:872–6.
[525] Jiao LY, Zhang L, Wang XR, Diankov G, Dai HJ. Narrow graphene
nanoribbons from carbon nanotubes. Nature 2009;458:877–80.
[526] Berger C, Song ZM, Li XB, Wu XS, Brown N, Naud C, Mayou D, Li
TB, Hass J, Marchenkov AN, Conrad EH, First PN, de Heer WA. Elec-
tronic confinement and coherence in patterned epitaxial graphene.
Science 2006;312:1191–6.
[527] Sutter PW, Flege JI, Sutter EA. Epitaxial graphene on ruthenium. Nat
Mater 2008;7:406–11.
[528] Fogel Y, Zhi LJ, Rouhanipour A, Andrienko D, Rader HJ, Müllen K.
Graphitic nanoribbons with dibenzo[e,l]pyrene repeat units: syn-
thesis and self-assembly. Macromolecules 2009;42:6878–84.
[529] Simpson CD, Brand JD, Berresheim AJ, Przybilla L, Rader HJ, Müllen
K. Synthesis of a giant 222 carbon graphite sheet. Chem Eur J
2002;8:1424–9.
[530] Pisula W, Feng XL, Müllen K. Charge-carrier transporting graphene-
type molecules. Chem Mater 2011;23:554–67.
[531] Feng XL, Pisula W, Kudernac T, Wu DQ, Zhi LJ, De Feyter S,
Müllen K. Controlled self-assembly of C-3-symmetric hexa-peri-
hexabenzocoronenes with alternating hydrophilic and hydropho-
bic substituents in solution, in the bulk, and on a surface. J Am Chem
Soc 2009;131:4439–48.
[532] Wu JS, Gherghel L, Watson MD, Li JX, Wang ZH, Simpson CD, Kolb
U, Müllen K. From branched polyphenylenes to graphite ribbons.
Macromolecules 2003;36:7082–9.
[533] Schwab MG, Narita A, Hernandez Y, Balandina T, Mali KS, Feyter SD,
Feng X, Müllen K. Structurally defined graphene nanoribbons with
high lateral extension. J Am Chem Soc 2012;134:18169–72.
[534] Bieri M, Treier M, Cai JM, Ait-Mansour K, Ruffieux P, Gröning O,
Gröning P, Kastler M, Rieger R, Feng XL, Müllen K, Fasel R. Porous
graphenes: two-dimensional polymer synthesis with atomic pre-
cision. Chem Commun 2009:6919–21.
[535] Osella S, Narita A, Schwab MG, Hernandez Y, Feng XL, Müllen K,
Beljonne D. Graphene nanoribbons as low band gap donor materi-
als for organic photovoltaics: quantum chemical aided design. ACS
Nano 2012;6:5539–48.
[536] Zhang ZG, Liu YL, Yang Y, Hou KY, Peng B, Zhao GJ, Zhang MJ,
Guo X, Kang ET, Li YF. Alternating copolymers of carbazole and
triphenylamine with conjugated side chain attaching acceptor
groups synthesis and photovoltaic application. Macromolecules
2010;43:9376–83.
[537] Duan CH, Cai WZ, Huang F, Zhang J, Wang M, Yang TB, Zhong CM,
Gong X, Cao Y. Novel silafluorene-based conjugated polymers with
pendant acceptor groups for high performance solar cells. Macro-
molecules 2010;43:5262–8.
[538] Hsu SL, Chen CM, Wei KH. Carbazole-based conjugated polymers
incorporating push/pull organic dyes: synthesis, characterization,
and photovoltaic applications. J Polym Sci Part A Polym Chem
2010;48:5126–34.
[539] Duan CH, Chen KS, Huang F, Yip HL, Liu SJ, Zhang J,
Jen AKY, Cao Y. Synthesis, characterization, and photovoltaic
properties of carbazole-based two-dimensional conjugated poly-
mers with donor-pi-bridge-acceptor side chains. Chem Mater
2010;22:6444–52.
[540] Cheng YJ, Hung LC, Cao FY, Kao WS, Chang CY, Hsu CS. Alternat-
ing copolymers incorporating cyclopenta[2,1-b:3,4-b ]dithiophene
unit and organic dyes for photovoltaic applications. J Polym Sci Part
A Polym Chem 2011;49:1791–801.
[541] Sahu D, Padhy H, Patra D, Huang JH, Chu CW, Lin HC. Synthesis
and characterization of novel low-bandgap triphenylamine-based
conjugated polymers with main-chain donors and pendent accep-
tors for organic photovoltaics. J Polym Sci Part A Polym Chem
2010;48:5812–23.
[542] Fan HJ, Zhang ZG, Li YF, Zhan XW. Copolymers of fluorene and
thiophene with conjugated side chain for polymer solar cells:
effect of pendant acceptors. J Polym Sci Part A Polym Chem
2011;49:1462–70.
[543] Huo LJ, Hou JH, Zhang SQ, Chen HY, Yang Y. A Polybenzo[1,2-
b:4,5-b ]dithiophene derivative with deep HOMO level and its
application in high-performance polymer solar cells. Angew Chem
Int Ed 2010;49:1500–3.
[544] Huo LJ, Guo X, Zhang SQ, Li YF, Hou JH. PBDTTTZ: a broad band
gap conjugated polymer with high photovoltaic performance in
polymer solar cells. Macromolecules 2011;44:4035–7.
[545] Liu Y, Wang HF, Dong HL, Tan JH, Hu WP, Zhan XW. Synthesis
of a conjugated polymer with broad absorption and its appli-
cation in high-performance phototransistors. Macromolecules
2012;45:1296–302.
[546] Kularatne RS, Sista P, Nguyen HQ, Bhatt MP, Biewer MC, Ste-
fan MC. Donor–acceptor semiconducting polymers containing
benzodithiophene with bithienyl substituents. Macromolecules
2012;45:7855–62.
[547] Sista P, Hao J, Elkassih S, Sheina EE, Biewer MC, Janesko BG, Ste-
fan MC. Synthesis, characterization, and computational modeling
of benzodithiophene donor–acceptor semiconducting polymers. J
Polym Sci Part A Polym Chem 2011;49:4172–9.
[548] Zhou E, Cong J, Hashimoto K, Tajima K. Introduction of a
conjugated side chain as an effective approach to improving
donor–acceptor photovoltaic polymers. Energy Environ Sci 2012;5:
9756–9.