Dyes and Pigments 186 (2021) 109049

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Dyes and Pigments

journal homepage: http://www.elsevier.com/locate/dyepig

Terpolymer acceptors based on bithiophene imide for all-polymer

solar cells
Weipeng Sun a, 1, Junwei Wang b, 1, Yongqiang Shi b, Ziang Wu c, Yumin Tang b, Kui Feng b,
Han Young Woo c, Xugang Guo b, Fei-Bao Zhang a, *
a
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, 310012, China
b
Department of Materials Science and Engineering, Southern University of Science and Technology (SUSTech), No. 1088, Xueyuan Road, Shenzhen, Guangdong,
518055, China
c
Department of Chemistry, College of Science, Korea University, Seoul, 136-713, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: In order to improve light absorption and promote n-type performance, random copolymerization strategy was
All-polymer solar cells employed to afford a series of random terpolymer acceptors with acceptor1-acceptor2-acceptor3 (A1-A2-A3) type
Polymer acceptors backbone. The polymers were synthesized from distannylated electron-deficient bithiophene imide monomer
Terpolymers
with various electron-deficient dibrominated co-monomers using the typical palladium-catalyzed Stille coupling
Bithiophene imide
Optical absorption
condensation polymerization. Compared with their parent polymers, these A1-A2-A3 type terpolymer acceptors,
particularly the dihexylthieno[3,4-b]pyrazine based terpolymer PBTP, can exhibit good miscibility, appropriate
polymer crystallinity, and improved absorption in the long-wavelength region due to the incorporation of a third
strong electron-withdrawing acceptor moiety thieno[3,4-b]pyrazine. Benefitting from the noncovalent S⋯N
interactions, PBTP possessed a planar skeleton and achieved the highest power conversion efficiency (PCE) of
7.35% in the polymer series when serving as the acceptor material in all-polymer solar cells. These results
indicate that the A1-A2-A3 type terpolymer acceptors should be promising candidates for developing high-
performance all-polymer solar cells.

1. Introduction
All-polymer solar cells (all-PSCs) comprised of polymers as both
donor and acceptor materials as the active layers are attracting sub­
stantial research interests in both academy and industry because of their
facile device fabrication using solution-based processing techniques,
their readily tunable optical absorption properties and energy levels,
good morphological stability, structural flexibility as well as mechanical
durability [1–4]. In all-PSCs system, polymer acceptors have been
employed to replace the n-type fullerene acceptors to overcome the
limitations of fullerenes acceptors, such as the weak light absorption in
the visible spectral region, difficulties in chemical modification of ful­
lerenes, and easily photoinduced dimerization [5–8]. To obtain efficient
n-type polymer acceptors for all-PSCs, polymer-based on perylene dii­
mide (PDI) [9,10], naphthalene diimide (NDI) [11] or bithiophene
imide (BTI) [12,13] acceptor units have been designed and explored in
all-PSCs during these years. Of these n-type polymers, considerable
attention has been given to the bithiophene fused dicarboximide named
BTI [14] which was initially employed to be a building block in OFETs
and a high μe of 0.19 cm2 V− 1 s− 1 was obtained [15,16]. Encouraged by
its promising electron mobility, BTI derivatives have been extensively
studied and employed as the typical electron-deficient units to build
n-type polymer materials served as polymeric acceptors in all-PSCs. In
2017, the polymer fBTI2-FT based on a fused BTI dimer exhibited a
power conversion efficiency (PCE) of 6.85% with Voc of 1.04 V and Jsc of
11.55 mA cm− 2 have been reported [17]. This high performance mainly
arose from the fused structure of the BTI dimers, which facilitated higher
polymer crystallinity and a more favorable blend film morphology.
Unfortunately, the polymer-based on nonfused BTI (s-BTI2-FT) showed
essentially no photovoltaic performance (PCEs < 0.1%) [17].
To adjust the polymer crystallinity and blend-film morphology, the
strategy of terpolymerization was introduced to synthesize imide-
functionalized heteroarene-based n-type terpolymers to balance crys­
tallinity and miscibility without sacrificing charge carrier mobilities and

* Corresponding author.
E-mail address: feibaozhang@hznu.edu.cn (F.-B. Zhang).
1
Weipeng Sun and Junwei Wang contributed equally.

https://doi.org/10.1016/j.dyepig.2020.109049
Received 20 September 2020; Received in revised form 22 November 2020; Accepted 29 November 2020
Available online 3 December 2020
0143-7208/© 2020 Elsevier Ltd. All rights reserved.
W. Sun et al.
all-PSCs based on BTI2-30TPD achieved an optimal PCE of 8.28% with a
small energy loss (0.53 eV) [1]. However, a small LUMO offset between
the selected polymer donor PTB7-Th and terpolymer acceptor [18–20]
was cuased due to the employment of distannylated fluorinated thio­
phene, which copolymerize with f-BTI2-Br and TPD-Br monomers via
Stille coupling reaction to form a random donor-acceptor-acceptor
(A-D-A)-type copolymer. Furthermore, incorporating an electron-rich
donor block in polymer backbone would suppress the n-type character
and improve the p-type character of the terpolymer acceptors, leading to
a broaden bandgap acceptors [21] with low harvest efficiency of the
solar photons [22]. Besides, combining two electron-deficient building
blocks on bithiophene imide (BTI) to construct A-A type polymer ac­
ceptors have shown remarkable success in obtaining high electron
mobility for organic thin-film transistors [6,22,23]. As for the above
issues in present BTI-based copolymers, it is of great significance to
explore new acceptor1-acceptor2-acceptor3 (A1-A2-A3)-type terpoly­
mers materials with narrow bandgap, moderate polymer crystallinity,
and uniform blend-film morphology for all-PSCs.
To further extend the applications of BTI derivatives, 2,3-dihex­
ylthieno[3,4-b]pyrazine (TP), benzothiadiazole (BT), and isoindigo (ID)
were employed to synthesize A1-A2-A3 type terpolymers with BTI and
BTI derivatives as polymer acceptors respectively. In this system, BTI
was successfully stannized in low temperature leading to a nice yield via
the Stille coupling reactions. Compared with BT and ID, incorporation
TP unit helps to narrow the bandgap, improve the initial absorption of
BTI-based copolymers, turn the polymer crystallinity, and blend film
morphology successfully. Moreover, PCE of 7.35% with Voc of 1.02 V
and Jsc of 13.28 mA cm− 2 have been obtained in the all-PSCs device.
2. Results and discussion
2.1. Synthesis and characterizations of terpolymers
BTI2-Br and TP-Br were prepared according to previous work [24,
25], and the BT-Br and ID-Br were obtained commercially and used
directly. The BTI1-Sn could not be synthesized via treating dibrominated
BTI (BTI-Br) with n-BuLi and then reacted with trimethyltin chloride to
get the product. However, lithium diisopropylamide (LDA) worked well
to deprotonate the α-protons of BTI and reacted with tributyltin chloride
to obtain the desired products successfully. After that, a random copo­
lymerization strategy was employed to afford the terpolymer acceptors
(BTI-BTI2-0.1 TP, BTI-BTI2-0.2 TP, and BTI-BTI2-0.4 TP) with different
feed molar ratios using a palladium-catalyzed cross-coupling conden­
sation polymerization. After a series of device optimization, it was noted
that the PCE of BTI-BTI2-0.2 TP was significantly higher than
BTI-BTI2-0.1 TP and BTI-BTI2-0.4 TP (Table S1-S3, Supporting Infor­
mation). For convenience, terpolymer BTI-BTI2-0.2 TP was denoted as
PBTP. Other terpolymers of PBBT and PBID were also synthesized
similarly with TP-Br replaced by BT-Br and ID-Br respectively. PBTP,
PBBT, and PBID appeared as dark purple solid, dark solid, and a light
purple solid with 92.0%, 92.4%, and 93.6% yields, respectively (Scheme
Scheme 1. Chemical structures and Synthetic routes of three terpolymers for PBTP, PBBT, and PBID.
2
Dyes and Pigments 186 (2021) 109049
1). The number-average molecular weights (Mn) of PBTP, PBBT, and
PBID were in the range of 36.9–57.3 kDa with the polydispersity (PDI)
2.0–2.1 (Table 1), which were determined by high-temperature gel
permeation chromatography (GPC) relative to polystyrene standards.
The three polymers showed good solubility in organic solvents
(dichloromethane, chloroform, chlorobenzene) and insoluble in hexane
and ethanol.
The thermal properties of PBTP, PBID, PBBT were investigated with
the thermogravimetric analysis (TGA) and the differential scanning
calorimetry (DSC). The three polymers showed good thermal stability
with 5% weight-loss temperatures of 367, 374, and 370 ◦ C for PBTP,
PBID, PBBT respectively (Fig. S1a). Besides, the glass transition tem­
peratures of these polymers were not observed in the differential scan­
ning calorimetry (DSC) in the temperature range of 25–300 ◦ C
(Fig. S1b).
The optical properties of three polymers were characterized by
UV–vis absorption spectroscopy in chloroform and film states. The
normalized absorption spectra and absorption coefficients in solution
are shown in Fig. 1 and Fig. S2 in the Supporting Information (SI), and
the relevant data are summarized in Table 1. PBBT and PBID exhibited
very similar absorption in the visible range (400–700 nm), which were
assigned to intramolecular charge transfer (ICT) [13]. More interest­
ingly, PBTP exhibited a pronounced absorption shoulder at 670–740 nm
in the low energy region. This might be attributed to the higher
electron-deficiency properties of TP relative to the properties of BT and
ID, together with the noncovalent S⋯N interactions between TP and BTI
or BTI2 increased planarity of the terpolymer. The optical band gaps
(Eopt
g ) of PBTP, PBID, and PBBT calculated from the film absorption
onsets were 1.61, 1.85, and 1.86 eV respectively. It is worth noting that
PBTP exhibited a low absorption coefficient (7.1 × 104 cm− 1) which was
almost same to that of PBBT (7.0 × 104 cm− 1) [26], while much lower
than that of PBID (9.2 × 104 cm− 1) and probably due to the weak molar
extinction coefficients of TP block [27,28] and the low molecular weight
which would affect the intermolecular packing and conjugation per­
formance [29,30]. This revealed that introducing the third comonomer
on the terpolymer system could affect the performance of absorbing the
solar radiation [15,18,31].
Cyclic voltammograms (CVs) were performed to investigate the
electronic states of three polymers under a nitrogen atmosphere with a
supporting electrolyte of 0.1 M (n-Bu)4N.PF6 in acetonitrile solution
[32], as shown in Fig. S3. The LUMO energy levels of PBTP, PBID, and
PBBT based on the onset of reduction potential were − 3.58, − 3.55, and
− 3.57 eV, at nearly the same potential as those of PBTI [33] and P
(BTI-BTI2) [34]. However, the corresponding HOMO energy levels
were − 5.19, − 5.40, and − 5.43 eV respectively, indicating that the in­
crease of the HOMO was responsible for the introduction of the third
acceptor in the polymer backbone.
To understand how the third component affects the geometry and
electronic states of the terpolymers, density functional theory (DFT)-
based calculations were performed with the N-alkyl substituents
replaced by short methyl groups. The results indicated that the
W. Sun et al. Dyes and Pigments 186 (2021) 109049

Table 1
Molecular weights, energy levels, absorptions onset of terpolymers PBTP, PBID, and PBBT.
a
Polymers Mn [kDa]a b
PDI c
λonset (nm) d
LUMO/eV d
HOMO e
HOMO f
Egcv/eV g
Egopt/eV
/eV /eV

PBTP 36.9 2.0 771 − 3.58 − 6.00 − 5.19 2.42 1.61

PBID 51.3 2.0 670 − 3.55 − 6.08 − 5.40 2.53 1.85
PBBT 57.3 2.1 665 − 3.57 − 6.04 − 5.43 2.47 1.86
a
Number-average molecular weights.
b
Polydispersity.
c
Absorption onset in solutions.
d
Estimated from EHOMO/LUMO = – [4.8 + Eox/red onset – E1/2
Fc ] eV.
e
LUMO-Egop.
f
|HOMO – LUMO|.
g
Optical bandgaps estimated from 1240/λonset.

5
Fig. 1. UV–vis absorption spectra of PBTP, PBID, PBBT in chloroform solution (10− mol L− 1) (a) thin films on glass substrates (b).

terpolymers possessed a planar skeleton basically and some of the
dihedral angles were shown in Fig. 2 and S4. It should be noted that
PBTP had smaller dihedral angles 0.22◦ and 0.61◦ in the three terpoly­
mers, which were similar to those of the parent polymer (BTI1-BTI2)
(0.14◦ and 0.47◦ ). This meant PBTP exhibited highly planar conforma­
tion due to the existence of intramolecular S⋯N noncovalent in­
teractions between the sulfur of the BTI core and the nitrogen of the TP
group, which would be in favor of acquiring efficient charge carrier
transport in all-PSCs devices. Similar to that of PBTP, PBBT also
exhibited a much more planar backbone due to the intramolecular
noncovalent S⋯N interaction enabled by BT incorporation. In marked
contrast, PBID exhibited a distorted geometry and maximal dihedral
angles of 20.97◦ and 0.68◦ . Also, the HOMO orbitals were delocalized
along the conjugated thienylene-thienylene backbone, while the LUMO
orbitals were generally less localized than the HOMO orbitals. Although
the TP units appeared to dominate the LUMO orbitals, strong delocal­
ization through the thienyl groups of the BTI units was also observed.
This delocalization might account for the ambipolar characteristics of TP

Fig. 2. HOMO and LUMO energy levels of dimers of (A) PBTP and (B) P(BTI-BTI2) at (B3LYP/6-31G (d, p)) level.

3
W. Sun et al.
unit, which could exhibit both donor and acceptor properties combining
with a strong acceptor unit, resulted in a predominant contribution to
both the HOMO and LUMO [25,27,30]. As expected, the HOMO/LUMO
levels of the PBTP, PBID, and PBBT were calculated to be − 5.25/-3.37,
− 5.47/-3.35, and − 5.47/-3.46 eV respectively, which were in good
accordance with the optical and electrochemical tendencies.
2.2. Photovoltaic performance and device characterizations
To investigate the different blocks of the terpolymers on the device
performance, a series of organic photovoltaic devices were fabricated
with a conventional structure of the following layers: glass/ITO/PEDOT:
PSS/active layer/Zracac/Al. The device structures were displayed in
supporting information (Fig. S5) and the parameters were summarized
in Table S4-S7. A well-known donor polymer PTB7-Th blended with the
terpolymers were served as active layers, which were spin-cast from a
solution of chlorobenzene (CB). After systematically optimized with
different donor and acceptor ration, polymer solution concentration,
rotation speed, and so on, it was found that PTB7-Th: PBTP (1:1.2) was
the best ratio, 2000 rpm was the best rotation speed, chlorobenzene as
the processing solvent and under annealing at 80 ◦ C for 10 min to obtain
the high performance. (Table S4).
The current density (J)-voltage (V) curves and the external quantum
efficiency (EQE) spectra of all-PSCs were displayed in Fig. 3a–b and the
detailed parameters were listed in Table 2. The external quantum effi­
ciency (EQE) curves of the polymer blend films showed broad and high
photoresponses covering the range from 300 to 800 nm (Fig. 3b) which
accorded with their absorption spectra. Interestingly, the EQE curve of
PBTP blend film exhibited a different photoresponse curve with a
maximum EQE approaching 60% in the spectral range of 560–720 nm
due to the pronounced absorption shoulder in the low energy region,
while PBBT and PBID blend films obtained maximum EQE approaching
61% and 60% in the spectral range of 500–600 nm, respectively. Also,
the integrated JSC values from the EQE curves were consistent with those
derived from J-V curves (Table 2).
A low short-circuit current density (Jsc) of 11.10 mA cm− 2 and a fill
factor (FF) of 41.81% were observed for the PTB7-Th: PBBT all-PSCs,
resulting in an inferior PCE of 4.60%. A higher JSC of 12.19 mA cm− 2
and FF of 47.58% were obtained for the PTB7-Th: PBID devices,
contributing to a better PCE of 5.86%. The highest PCE of 7.35% with a
Jsc of 13.28 mA cm− 2, a large open-circuit voltage (Voc) of 1.02 V, and a
FF of 54.14% was obtained for the all-PSCs containing PBTP as the
polymer acceptor. Although PBBT also possessed intramolecular non­
covalent S⋯N interactions in the polymer backbone, the PTB7-Th:PBBT
blend film displayed a coarser morphology with a root-mean-square
(RMS) of 0.85 nm (Fig. 4) larger than that of PTB7-Th:PBTP (RMS
roughness: 0.81 nm) (vide infra), which might be due to the poor sol­
ubility of BT unit. Also, the broadest absorption spectra of PBTP would
Fig. 3. The current density-voltage (J–V) characteristics of all-PSCs (a) and EQE data of solar cells based on PTB7-Th: Terpolymers weight ratio of 1:1.2 (b).
4
Dyes and Pigments 186 (2021) 109049
result in better absorption of the solar radiation and higher JSC values,
yielding better performance. Unfortunately, the PCE of terpolymer PBTP
was still lower than our early report based on P(BTI-BTI2) [34], which
mainly due to the low Jsc caused by low absorption coefficients. The
corresponding energy losses (Eloss) values calculated from the equation,
Eloss = Eopt
g − eVoc [1], were in the range of 0.56–0.59eV (Table 2), where
Egopt was the smaller optical bandgap between the donor and the
acceptor. The Eloss of three terpolymers based devices were 0.56 eV,
0.57 eV, 0.59 eV for PBTP, PBID, PBBT, respectively.
To elucidate the charge carrier mobilities in the all-PSCs devices, the
electron mobility (μe) and hole mobility (μh) of the blend films of PTB7-
Th:PBTP, PTB7-Th:PBID, and PTB7-Th:PBBT were measured using the
space charge-limited current (SCLC) method(Fig. S6, Table 2).
Compared to the charge carrier properties of parent blend films PTB7-
Th:PBTI (electron mobility, μe = 2.40 × 10− 6 cm2/V; hole mobility,
μh = 5.14 × 10− 6 cm2/V) and PTB7-Th:P(BTI-BTI2) (μe = 1.50 × 10− 5
cm2/V; μh = 3.10 × 10− 5 cm2/V),23 the blend films of PTB7-Th:PBTP,
PTB7-Th:PBID, and PTB7-Th:PBBT displayed much higher charge car­
rier mobilities (μe = 1.33 × 10− 4 cm2/V; μh = 3.02 × 10− 4 cm2/V; μe =
3.47 × 10− 4 cm2/V; μh = 2.44 × 10− 4 cm2/V; μe = 2.25 × 10− 4 cm2/V;
μh = 1.39 × 10− 4 cm2/V), respectively(Table 2).
To further understand the relationship of high current, fill factor, and
PCE in PTB7-Th: PBTP system, atomic force microscopy (AFM) and
transmission electron microscopy (TEM) were employed to probe the
surface topography and phase morphologies of the blend films (Fig. 4).
All the blend films showed rather flat morphologies with the small root-
mean-square (RMS) roughness in the range of 0.81–0.85 nm which were
much smaller than our previous reports.13 It revealed that the domain
sizes in all the films were small, suggesting that the incorporation of
terpolymers were beneficial to the phase-separated morphology of host
blend films. However, some dark spots and color variations appeared in
the TEM images of the PBID and PBBT polymer blend films. The large
agglomerates of the blend films were probably composed mainly of
aggregated polymers [35–37]. In contrast, the PTB7-Th: PBTP system
appears homogeneous and no such defects were observed not only in
AFM images but also in TEM images. The pronounced characteristic
might be caused by the increased polymer backbone planarity and the
solubility of PBTP with the long alkyl chain.
Next, we investigated the morphology and microstructure of the neat
films and blend films by two-dimensional grazing incidence wide-angle
X-ray scattering (2D GIWAXS) measurement. The GIWAXS 2D scattering
patterns of the films were displayed in Fig. 5 and Fig. S7-S8, and the
packing parameters were summarized in Table S8, S10. For neat films,
the GIWAXS data showed poorly developed crystalline order of ter­
polymers PBTP, PBID, and PBBT, with similar sharp peaks (100) in in-
plane (IP) or out-of-plane (OOP) directions. The terpolymers all
showed face-on dominant orientations, with a sharp peak (010) in the
out-of-plane (OOP) direction corresponding to π-π stacking occurs
W. Sun et al. Dyes and Pigments 186 (2021) 109049

Table 2
Optimized device performance parameters of the all-PSCs using terpolymers as the electron acceptor and PTB7-Th as the electron donor.
Active layer Voc (V) Jsc (mA/cm2) FF (%) PCE (%) μh (cm2/Vs) μe (cm2/Vs) μh/μe Eloss
− 4 − 4
PTB7-Th:PBTP 1.02 13.28(12.64) 54.14 7.35 1.33 × 10 3.02 × 10 0.44 0.56
4 4
PTB7-Th:PBID 1.01 12.19(12.03) 47.58 5.86 3.47 × 10− 2.44 × 10− 1.42 0.57
4 4
PTB7-Th:PBBT 0.99 11.10(11.97) 41.81 4.60 2.25 × 10− 1.39 × 10− 1.62 0.59

Fig. 4. AFM height images (a–c) and phase images (d–f) of terpolymers blend film; TEM images of terpolymers blend film (g–k).

around 1.70 Å− 1 (dπ-π: 0.37–0.38 nm). PBTP showed better crystallinity.
This might be due to the intramolecular noncovalent S⋯N interactions
triggered by incorporating the TP unit, which could enhance the
planarity and rigidity of the polymer backbones leading to higher
crystallinity. When blended with donor polymer PTB7-Th, almost all the
mixture films still showed a face-on dominant orientation along with a
stronger scattering peak (010) in the out-of-plane (OOP) direction. The
PTB7-Th: PBTP, PTB7-Th: PBID, and PTB7-Th: PBBT blend films showed
a sharper (010) peak at around 1.63 Å (dπ-π: 0.39 nm). Besides, it should
be noted that all the blend films showed a smaller coherence length of
1.2 nm than that of neat films (Table S9 and S11). The improved mo­
lecular packing and small coherence length were helpful to the charge
transport for the terpolymers-based all-PSCs, which had been proved by
the SCLC results (Table 2).
3. Conclusion
In conclusion, we have synthesized three A1-A2-A3 n-type terpoly­
mers based on bithiophene imide core with different electron-deficient
components (TP, ID and BT) and explored the effects of incorporation

5
W. Sun et al.
Fig. 5. 2D GIWAXS images of PTB7-Th: Terpolymers blend films and the line-cut profiles in the IP (a) and OOP (b) directions.
of the third component on the parent polymers on the charge transport,
film morphology, and photovoltaic properties. The calculation and
experimental results revealed that incorporating an electron-deficient
component into parent BTI derivatives could affect HOMO energy
levels significantly, resulting in a narrow bandgap acceptor. The PTB7-
Th: PBTP blended films showed flat morphology with smaller domain
sizes to afford more Donor/Acceptor interfaces for exciton dissociation,
leading to high charge transport performance. Also, intramolecular
noncovalent S⋯N interactions triggered by incorporating the TP unit
might enhance the planarity and rigidity of the polymer backbones,
which would be helpful to balance the crystallinity and miscibility of the
blended films. Further studies to prepare high-performance A1-A2-A3 n-
type terpolymers with other electron-deficient components are
underway.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research was supported by Zhejiang Provincial Natural Science
Foundation of China under Grant No. LY18B040003, Zhejiang Provin­
cial Medical Health Project (2019KY546), the China Postdoctoral Sci­
ence Foundation (No. 2019M662696). X.G. is grateful to the Shenzhen
Science and Technology Innovation Commission (No.
JCYJ20190809162003662).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.dyepig.2020.109049.
References
[1] Sun HL, Liu B, Koh CW, Zhang YJ, Chen JH, Wang Y, et al. Imide-functionalized
heteroarene-based n-type terpolymers incorporating intramolecular noncovalent
sulfur center dot center dot center dot oxygen interactions for additive-free all-
polymer solar cells. Adv Funct Mater 2019;29(42):1903970.
[2] Sun HL, Guo XG, Facchetti A. High-performance n-type polymer semiconductors:
applications, recent development, and challenges. Chem-Us 2020;6(6):1310–26.
[3] Genene Z, Mammo W, Wang EG, Andersson MR. Recent advances in n-type
polymers for all-polymer solar cells. Adv Mater 2019;31(22):e1807275.
[4] Lee C, Lee S, Kim GU, Lee W, Kim BJ. Recent advances, design guidelines, and
prospects of all-polymer solar cells. Chem Rev 2019;119(13):8028–86.
6
Dyes and Pigments 186 (2021) 109049
[5] Chen NY, Yue QH, Liu WR, Zhang HL, Zhu XZ. A benzo[1,2-d:4,5-d]bisthiazole-
based wide-bandgap copolymer semiconductor for efficient fullerene-free organic
solar cells with a small energy loss of 0.50 eV. J Mater Chem 2019;7(10):5234–8.
[6] Wadsworth A, Hamid Z, Kosco J, Gasparini N, McCulloch I. The bulk
heterojunction in organic photovoltaic, photodetector, and photocatalytic
applications. Adv Mater 2020;32(38):2001763.
[7] Nakashima M, Murata N, Suenaga Y, Naito H, Sasaki T, Kunugi Y, et al.
Disilanobithiophene-dithienylbenzothiadiazole alternating polymer as donor
material of bulk heterojunction polymer solar cells. Synthetic Met 2016;215:
116–20.
[8] Zhang FB, Ohshita J, Miyazaki M, Tanaka D, Morihara Y. Effects of substituents and
molecular weight on the optical, thermal and photovoltaic properties of alternating
dithienogermole-dithienylbenzothiadiazole polymers. Polym J 2014;46(9):628–31.
[9] Shi QQ, Wu JF, Wu XX, Peng AD, Huang H. Perylene diimide-based conjugated
polymers for all-polymer solar cells. Chem Eur J 2020;26(55):1–14.
[10] Wu ZH, Huang ZT, Guo RX, Sun CL, Chen LC, Sun B, et al. 4,5,9,10-Pyrene
diimides: a family of aromatic diimides exhibiting high electron mobility and two-
photon excited emission. Angew Chem Int Ed 2017;56(42):13031–5.
[11] Zhao CC, Wang JX, Jiao JQ, Huang LJ, Tang JG. Recent advances of polymer
acceptors for high-performance organic solar cells. J Mater Chem C 2020;8(1):
28–43.
[12] Shi YQ, Wang YF, Guo XG. Recent progress of imide-functionalized N-type polymer
semiconductors. Acta Polym Sin 2019;50(9):873–89.
[13] Shi YQ, Guo H, Qin MC, Zhao JY, Wang YX, Wang H, et al. Thiazole imide-based
all-acceptor homopolymer: achieving high-performance unipolar electron
transport in organic thin-film transistors. Adv Mater 2018;30(10):1705745.
[14] Letizia JA, Salata MR, Tribout CM, Facchetti A, Ratner MA, Marks TJ. n-channel
polymers by design: optimizing the interplay of solubilizing substituents, crystal
packing, and field-effect transistor characteristics in polymeric bithiophene-imide
semiconductors. J Am Chem Soc 2008;130(30):9679–94.
[15] Guo XG, Ortiz RP, Zheng Y, Hu Y, Noh YY, Baeg KJ, et al. Bithiophene-imide-based
polymeric semiconductors for field-effect transistors: synthesis, structure-property
correlations, charge carrier polarity, and device stability. J Am Chem Soc 2011;133
(5):1405–18.
[16] Wang YF, Guo H, Ling SH, Arrechea-Marcos I, Wang YX, Navarrete JTL, et al.
Ladder-type heteroarenes: up to 15 rings with five imide groups. Angew Chem Int
Ed 2017;56(33):9924–9.
[17] Wang YF, Yan ZL, Guo H, Uddin MA, Ling SH, Zhou X, et al. Effects of bithiophene
imide fusion on the device performance of organic thin-film transistors and all-
polymer solar cells. Angew Chem Int Ed 2017;56(48):15304–8.
[18] Vandewal K, Tvingstedt K, Gadisa A, Inganas O, Manca JV. On the origin of the
open-circuit voltage of polymer-fullerene solar cells. Nat Mater 2009;8(11):904–9.
[19] Vandewal K, Albrecht S, Hoke ET, Graham KR, Widmer J, Douglas JD, et al.
Efficient charge generation by relaxed charge-transfer states at organic interfaces.
Nat Mater 2014;13(1):63–8.
[20] Zhang CF, Tong SW, Jiang CY, Kang ET, Chan DSH, Zhu CX. Origin of different
dependences of open-circuit voltage on the electrodes in layered and bulk
heterojunction organic photovoltaic cells. IEEE Trans Electron Dev 2010;57(2):
397–405.
[21] Cheng P, Wang JY, Zhan XW, Yang Y. Constructing high-performance organic
photovoltaics via emerging non-fullerene acceptors and tandem-junction structure.
Adv Energy Mater 2020;10(21):2000746.
[22] Cheng P, Yang Y. Narrowing the band gap: the key to high-performance organic
photovoltaics. Accounts Chem Res 2020;53(6):1218–28.
[23] Sun HL, Yu H, Shi YQ, Yu JW, Peng ZX, Zhang XH, et al. A narrow-bandgap n-type
polymer with an acceptor-acceptor backbone enabling efficient all-polymer solar
cells. Adv Mater 2020;32(43):1905161.
[24] Saito M, Osaka I, Suda Y, Yoshida H, Takimiya K.
Dithienylthienothiophenebisimide, a versatile electron-deficient unit for
semiconducting polymers. Adv Mater 2016;28(32):6921–5.
W. Sun et al.
[25] Culver EW, Anderson TE, Navarrete JTL, Delgado MCR, Rasmussen SC. Poly(thieno
[3,4-b]pyrazine-alt-2,1,3-benzothiadiazole)s: a new design paradigm in low band
gap polymers. ACS Macro Lett 2018;7(10):1215–9.
[26] Ren JZ, Bao XC, Han LL, Wang JX, Qiu M, Zhu QQ, et al. 4,7-Di-2-thienyl-2,1,3-
benzothiadiazole with hexylthiophene side chains and a benzodithiophene based
copolymer for efficient organic solar cells. Polym Chem-Uk 2015;6(24):4415–23.
[27] Becerril HA, Miyaki N, Tang ML, Mondal R, Sun YS, Mayer AC, et al. Transistor and
solar cell performance of donor-acceptor low bandgap copolymers bearing an
acenaphtho[1,2-b]thieno[3,4-e]pyrazine (ACTP) motif. J Mater Chem 2009;19(5):
591–3.
[28] Mondal R, Miyaki N, Becerril HA, Norton JE, Parmer J, Mayer AC, et al. Synthesis
of acenaphthyl and phenanthrene based fused-aromatic thienopyrazine Co-
polymers for photovoltaic and thin film transistor applications. Chem Mater 2009;
21(15):3618–28.
[29] SambathKumar B, Kumar PSV, Deepakrao FS, Iyer SSK, Subramanian V, Datt R,
et al. Two donor-one acceptor random terpolymer comprised of
diketopyrrolopyrrole quaterthiophene with various donor pi-linkers for organic
photovoltaic application. J Phys Chem C 2016;120(47):26609–19.
[30] Li JF, Yang J, Hu JY, Chen Y, Xiao B, Zhou EJ. The first thieno[3,4-b]pyrazine
based small molecular acceptor with a linear A(2)-A(1)-D-A(1)-A(2) skeleton for
fullerene-free organic solar cells with a high V-oc of 1.05 V. Chem Commun 2018;
54(76):10770–3.
Dyes and Pigments 186 (2021) 109049
[31] Wang CH, Gao ZC, Sun WP, Guo XG, Zhang FB. P⋯O noncovalent conformational
locks for constructing highly planar Bis(diphenylphosphanyl) Bi(benzofurano).
Dyes Pigments 2020;184:108820.
[32] Cardona CM, Li W, Kaifer AE, Stockdale D, Bazan GC. Electrochemical
considerations for determining absolute frontier orbital energy levels of conjugated
polymers for solar cell applications. Adv Mater 2011;23(20):2367–71.
[33] Wang YF, Guo H, Harbuzaru A, Uddin MA, Arrechea-Marcos I, Ling SH, et al.
(Semi)ladder-Type bithiophene imide-based all-acceptor semiconductors:
synthesis, structure-property correlations, and unipolar n-type transistor
performance. J Am Chem Soc 2018;140(19):6095–108.
[34] Shi YQ, Guo H, Huang JC, Zhang XH, Wu Z, Yang K, et al. Distannylated
bithiophene imide: enabling high-performance n-type polymer semiconductors
with an acceptor-acceptor backbone. Angew Chem Int Ed 2020;59(34):14449–57.
[35] Shin I, Ahn H, Yun JH, Jo JW, Park S, Joe SY, et al. High-performance and uniform
1 cm(2) polymer solar cells with D-1-A-D-2-A-type random terpolymers. Adv
Energy Mater 2018;8(7):1701405.
[36] Jinnai H, Spontak RJ, Nishi T. Transmission electron microtomography and
polymer nanostructures. Macromolecules 2010;43(4):1675–88.
[37] Jinnai H, Spontal RJ. Transmission electron microtomography in polymer research.
Polymer 2009;50(5):1067–87.