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New developments in non-fullerene small molecule acceptors for
polymer solar cells
ab a a a
N. N. Liang, W. Jiang,* J. H. Hou, Z. H. Wang
During the past two years, non-fullerene electron acceptors for organic solar cells have attracted considerable attention.
Significant progress has been made that the power conversion efficiency of polymer solar cells based on non-fullerene
small molecule acceptors exceed 12%, exhibiting many advantages over their fullerene counterparts. One of the greatest
strengths for NFAs is their tunability via chemical modulation to fine-tune their absorption, energy level and electronic

mobility, which is difficult to achieve with fullerene derivatives. This review describes very recent developments of
polymer donor:small molecular non-fullerene acceptors in several systems since 2015, including rylene imide,
indacenodithiophene and diketopyrrolopyrrole based small molecular acceptors. Molecular design considerations and
structure-property relationships are also discussed.

do present some challenges in terms of chemical modification to

1. Introduction
It is well known that solar cell devices used to convert solar energy
into electricity are a major topic within the academic and business
communities. Recently, scientists from the Energy Department's
National Renewable Energy Laboratory (NREL) and the Swiss Center
for Electronics and Microtechnology (SCEM) have jointly set a new
world record using a dual-junction III-V/Si solar cell with the newly
certified record conversion efficiency of 29.8%, exceeding the
[1-2]
theoretical limit of 29.4% for crystalline silicon solar cells.
Great improvements have also been achieved with solution
processed bulk heterojunction (BHJ) organic solar cells (OSCs)
consisting of electron donors and electron acceptors. Over the past
few decades, these solar cells have also attracted attention from
the scientists worldwide due to the following important and distinct
advantages: 1) low-cost, mechanical flexibility, light weight, and the
ability to be produced by the roll-to-roll method, providing
possibility for large-area industrial production; 2) the donor and
acceptor materials can be easily tuned via organic synthesis to fine-
tune the energy level and the light capture capability.
The first bilayer OSC device was proposed by Tang in 1986 and
the first BHJ OSCs based on polymer:fullerene was demonstrated by
[3,4]
Heerger and coworkers in 1995. During the past decades,
fullerene derivatives as electron acceptors have played a dominant
role in the field of OSCs. The power conversion efficiency (PCE) of
single-junction polymer solar cells (PSCs) have exceeded 11.7%
largely due to excellent morphology and high mobilities as well as
the ultrafast photo-induced electron transfer between the fullerene
[5-8]
acceptors and polymer donors. However, fullerene derivatives
a.
Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular
Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190,
China; E-mail: jiangwei@iccas.ac.cn.
b.
University of Chinese Academy of Sciences, Beijing 100049, China.
tune the light absorption and the energy level. Thus, much
attention had been paid to the non-fullerene acceptors (NFAs), for
the judicious design and synthesis of novel chemical structures, the
optimization of the device structure, and BHJ morphology. Efforts
have been rewarded and some new NFAs have exhibited
outstanding performance: PSCs with the PCEs > 12% have recently
[9]
been reported. Therefore, summarizing the critical achievements
in NF-PSCs, and making a systematic and sensible analysis of these
materials, are considered to be essential to guide molecular design.
The development of NFAs in polymeric donor-based solar cells
(NF-PSCs) prior to 2015 having given a detailed introduction and
[10-13]
summary in several reviews. In this review article, therefore,
we only summarize recent progress, molecular design strategies
and structure–property relationships in NF-PSCs since 2015.
According to the structural features, we classified non-fullerene
electronic acceptors into three groups, including the rylene imide
dyes, indacenodithiophene (IDT)-based and diketopyrrolopyrrole
(DPP)-based small molecule acceptors (SMAs).
2. Rylene imide dyes
2.1 PDI based small molecule acceptors
Among the non-fullerene electron acceptors, perylene diimide (PDI)
derivatives have attracted considerable attention. They exhibit
great potential due to their excellent electron-accepting ability,
high electron mobility, and especially their highly tunable electronic
[14-16]
energy levels, achieved by chemical modification. Whereas,
PDI derivatives have a strong self-aggregation to form overly large
aggregations in BHJ active layers due to the large planar π-
conjugated system. This prevents the formation of sufficiently large
donor-acceptor interfacial area for the exciton diffusion/separation,
[17-18]
thereby limiting the PCEs of such device. Now, after several
years of development, researchers have achieved great success in

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Fig. 1 Chemical structures of the bay-position functionalized PDI molecules.

disrupting the aggregation tendency by means of chemical

functionalization. Nevertheless, the highly twisted structures lead
to low crystallinity and poor electron transport ability, which is a
bottleneck for improvements in the short-circuit current (JSC), fill
[19-25]
factor (FF), and PCE. It has therefore been challenging to
design NFAs possessing both suitable domain size in BHJs and high
electron mobility. As is well known, an effective way to improve the
carrier mobility is to expand ring functionalization. For PDI
derivatives, two kinds of functionalization positions are termed as
imide position and lateral positions including bay- and nonbay-
positions, respectively.
Bay–position functionalized PDI
Wang and coworkers reported a family of PDI dyes with different
bay-linkages between the PDI subunits. In particular, the PSCs
devices based on PBDTTT-C-T:SdiPDI (singly-linked PDI dimer)
exhibited the best PCE values of up to 3.63%.
[26]
The PTB7-
Th/SdiPDI-based PSCs exhibited a high PCE of up to 4.5%,
collectively due to the broad absorption, appropriate HOMO level
[27]
and moderate crystallinity of PTB7-Th. When the PTB7-Th/SdiPDI
solar cells were fabricated with the inverted configuration, the PSCs

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Table 1 Optoelectronic properties and PSC device parameters for PDI based small molecule acceptors. DOI: 10.1039/C6QM00247A

LUMO/HOMO VOC JSC FF PCE

Acceptor Donor Device Structure Ref.
(eV) (V) (mA cm-2) (%)
SdiPDI PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.92/-5.99 b 0.79 12.86 0.54 5.56 26

Materials Chemistry Frontiers Accepted Manuscript

SdiPDI-S PDBT-T1 ITO/PEDOT:PSS/BHJ/Ca/Al -3.85/-6.05 b 0.90 11.65 0.66 7.16 29
SdiPDI-Se PDBT-T1 ITO/PEDOT:PSS/BHJ/Ca/Al -3.87/-6.09 b 0.95 12.48 0.70 8.42 30
PDI-T PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -4.02/-5.95 a 0.88 9.74 0.41 3.54 31
FPDI-F PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.80/-6.01 a 0.94 11.76 0.51 5.69 31
FPDI-T PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.77/-5.98 a 0.93 12.00 0.58 6.72 31
FPDI-Se PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.76/-5.96 a 0.92 11.19 0.55 5.77 31
Ph2 PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -4.07/-6.22 b 0.91 5.50 0.41 2.19 32
Ph2a PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -4.03/-6.36 b 0.93 7.68 0.54 3.89 32
Ph2b PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -4.04/-6.18 b 0.89 1.51 0.29 0.23 32
TT1 PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -4.14/-6.16 b 0.87 5.55 0.42 2.02 32
TT2 PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.99/-6.20 b 0.98 3.95 0.39 1.50 32
hPDI1 PTB7-Th ITO/ZnO/BHJ/MoO3/Al -3.77/-6.04 0.80 13.50 0.55 0.94 33
hPDI3 PTB7-Th ITO/ZnO/BHJ/MoO3/Al -3.86/-6.23 0.81 14.50 0.67 7.9 34
hPDI4 PTB7-Th ITO/ZnO/BHJ/MoO3/Al -3.92/-6.26 0.80 15.10 0.68 8.27 34
SF-DPI2 PffBT4T-2DT ITO/ZnO/ BHJ /V2O5/Al 3.71/5.71 a 0.98 10.74 0.57 6.30 36
SF-DPI2 P3TEA ITO/ZnO/ BHJ /V2O5/Al --- 1.11 13.27 0.64 9.50 37
B(PDI)3 PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.86/-6.00 a 0.83 13.12 0.52 5.65 39
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SF-PDI4 P4T2FBT ITO/ZnO/ BHJ /V2O5/Ag -3.78/-5.97 a 0.93 11.03 0.51 5.27 40
SF-PDI4 PV4T2FBT ITO/ZnO/ BHJ /V2O5/Ag --- 0.90 12.02 0.54 5.98 40
TPE-PDI4 PTB7-Th ---- -3.72/-5.77 b 0.91 11.70 0.52 5.53 41
TPC–PDI4 PffBT4T-2DT ITO/ZnO/ BHJ /V2O5/Al -3.75/-6.00 b 0.96 9.20 0.49 4.3 42
TPSi-PDI4 PffBT4T-2DT ITO/ZnO/ BHJ /V2O5/Al -3.75/-6.01 b 0.94 8.5 0.53 4.2 42
TPGe-PDI4 PffBT4T-2DT ITO/ZnO/ BHJ /V2O5/Al -3.68/-5.94 b 0.92 5.0 0.37 1.6 42
TPC-PDI4 PffBT-T3(1,2)-2 ITO/ZnO/ BHJ /MoO3/Al --- 1.04 8.70 0.51 4.60 43
TPE-PDI4 PffBT-T3(1,2)-2 ITO/ZnO/ BHJ /MoO3/Al --- 1.03 10.60 0.54 5.90 43
TPPz-PDI4 PffBT-T3(1,2)-2 ITO/ZnO/ BHJ /MoO3/Al -3.76/-5.86 b 0.99 12.50 0.56 7.10 43
αPPID PTB7-Th ITO/ZnO/ BHJ /MoO3/Al -4.19/-5.66 b 0.77 10.15 0.44 3.49 44
βPPID PTB7-Th ITO/ZnO/ BHJ /MoO3/Al -4.21/-5.59 b 0.78 9.14 0.45 3.20 44
αPBDT PTB7-Th ITO/ZnO/ BHJ /MoO3/Al -4.13/-4.80 b 0.81 12.74 0.46 4.76 44
βPBDT PTB7-Th ITO/ZnO/ BHJ /MoO3/Al -4.13/-5.05 b 0.81 9.80 0.44 3.49 44
TPB PTB7-Th ITO/ZnO/ BHJ /MoO3/Ag -3.81/-5.71 a 0.79 17.90 0.58 8.47 45
H-di-PDI PBDT-TS1 ITO/PEDOT:PSS/BHJ/PFN/Al -3.86/-5.90 b 0.82 12.85 0.53 5.58 47
H-di-PDI PTB7-Th ITO/ZnO/ BHJ /MoO3/Al --- 0.79 13.12 0.60 6.41 28
H-tri-PDI PBDT-TS1 ITO/ZnO/ BHJ /MoO3/Al -3.93/-6.01 a 0.73 16.52 0.60 7.25 48
2c-DACH-PPDIs PTB7-Th ITO/ZnO/ BHJ /MoO3/Al -3.88/-6.16 b 0.80 10.63 0.51 4.68 49
Me-PDI4 PBDTTT-C-T ITO/ZnO/BHJ/PEDOT:PSS/Ag -3.81/-5.96 b 0.77 7.83 0.45 2.73 50
a
calculated from the onset oxidation and reduction potential. b calculated from the absorption edge (λedge) with the equation of Eopt
g = 1240/λedge (eV); The value of λedge is obtained

from the absorption spectrum. c calculated from the method of photoelectron spectroscopy in air (PESA).
[28]
showed a high PCE of 5.9%. The fusion and extension of
heteroarenes has been recognized as a promising method to
construct effective electron acceptors. Various intermolecular
interactions can be induced by heteroatoms and the original
chemical structure can be modulated. Then, SdiPDI was modified by
insertion of thiophene and selenophene units in the bay positions
and two PDI dyes, SdiPDI-S and SdiPDI-Se were obtained. The
introduction of S bridges increased the electron density as well as
the steric hindrance of the PDI subunits and thus weakened the π-
conjugation between two PDI units, leading to a higher lying lowest
unoccupied molecular orbital (LUMO). The molecules had LUMO
energy of –3.85 eV for SdiPDI-S, compared to an energy of –3.91 eV
for SdiPDI. Accordingly, the PDBT-T1:SdiPDI-S solar cell showed a
high PCE of 7.16% with an FF of 0.66 and open circuit voltage (VOC)
[29]
of 0.90 V. Meanwhile, the selenium atom has a larger and looser
outermost electron cloud than that of sulfur, which improves
orbital overlap and increases the charge carrier mobility. Thus,
SdiPDI-Se was obtained with a high LUMO level of -3.87 eV and a
twisted molecular configuration as well as a higher electron
−3 2 −1 −1
mobility (μe) of 6.4  10 cm V s for a neat SdiPDI-Se film (3.2 
−3 2 −1 −1
10 cm V s for a neat SdiPDI-S film). PSCs based on PDBT-
T1:SdiPDI-Se showed a high efficiency of 8.4% with a VOC of 0.96 V
[30]
and a relatively satisfied FF of 0.70.
Jen et al. developed a new family of fused derivatives with
different chalcogen atoms from S to O to Se, namely FPDI-T, FPDI-F
and FPDI-Se. Compared with the non-fused PDI-T, fused FPDI-T
showed increased π-conjugation and delocalization of the LUMO
over the whole molecule. As the atomic size increases from O to S
to Se, the LUMO levels improved from -3.80, -3.77 to -3.76 eV. As a
result, PTB7-Th:FPDI-T based PSCs exhibited a superior photovoltaic
[31]
performance with a PCE of 6.72%. Thus, fused-ring
functionalization on PDIs could reduce reorganization energy and
extend effective π-conjugation, which is beneficial to facilitate
exciton diffusion and charge transport. This result was confirmed by
Marks and coworkers, who explored the effects of ring fusion in a
series of PDI dimers bridged by thiophene (T1 (PDI-T) and T2 (FPDI-
T)), phenylene (Ph1, Ph2a, and Ph2b), and thienothiophene (TT1,
and TT2) linkers. The PSCs utilizing twisted dimers, T2 and Ph2a,
blended with the donor PTB7-Th showed significantly increased in
performance compared to those fabricated with the non-fused
dimers, T1 and Ph1, respectively, which was attributed to the
decreased geminate recombination rates and increased electron

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Fig. 2 Chemical structures of the polymer donors mentioned in this review.
mobility. Other fused dimers TT2 and Ph2b with more planar
confirmation have decreased performances for PSCs due to the
[32]
increased charge recombination and excimer formation.
A family of helical PDI molecules (hPDI1, hPDI3, hPDI4) have been
reported by Nuckolls and coworkers. Those structures were
prepared by fusing adjacent PDI unites with a two-carbon bridge.
These small molecules have relatively high electron mobilities and
LUMO energy levels (∼ -4.0 eV), good absorption abilities from 350
5 -1 -1 5 -1 -1
to 600 nm (εmax of 1.1  10 M cm , 1.5  10 M cm and 1.8 
5 -1 -1
10 M cm for hPDI1, hPDI3 and hPDI4, respectively) and a slightly
reduced aggregation tendency due to the twisted molecular
conformation. Thus, the stronger light absorption and lack of
aggregation, together with the tendency of the isolated linear
structure to form networks all contributed to ensuring the PSCs
based on PTB7:hPDI3 and PTB7-Th:hPDI4 have superior
performances to those of PTB7-Th:hPDI1, with maximum PCEs of
[33, 34]
7.9% and 8.3%, respectively.
Yan et al. adopted a difluorobenzothiadiazole (ffBT)-based
polymer, named as PffBT4T-2DT, as electronic donor material.
When combined with two electronic acceptors diPDI and SF-PDI2,
[26,35]
as reported in previous study, reasonably high PCEs of 5.4%
[36]
and 6.3% were obtained, respectively. This group also reported
PSCs based on a novel polymer P3TEA and SF-PDI2, specifically
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Materials Chemistry Frontiers Accepted Manuscript
possessing a low voltage loss of 0.61 eV, a high VOC of 1.11 V and an
[37]
excellent PCE of 9.5%. Although the PSCs based on P3TEA:SF-
PDI2 have a negligible driving force (Egap - ECT), the solar cells exhibit
fast and efficient charge separation, creating a path towards highly
efficient PSCs with low voltage loss.
Recently, great achievements have been reported on the three-
dimensional (3D) PDI SMAs linked with different core blocks; they
have the advantages of high extinction coefficients and favorable
[38]
BHJ morphology featuring a small domain size. Chen
and coworkers reported a PDI derivative B(PDI)3, in which a central
benzene unit is adopted to connect three PDI arms, leading to a
twisted molecular geometry and suppressing the strong
crystallization tendency of PDI chromophores. Therefore, the PSCs
[39]
based on PTB7-Th:B(PDI)3 provided a good PCE of 5.65%. Cho
and et al. used a spiro-bifluorene (SF) core to connect four PDI
building blocks and obtained a SF-PDI4 acceptor, with a highly
twisted SF core that could suppress molecular aggregation and
facilitate excitation energy transfer among PDI subunits. The
devices combined SF-PDI4 with a difluorobenzo-thiadiazole (2FBT)-
-2
based donor polymer, PV4T2FBT, yielded a high Jsc of 12.02 mA cm
[40]
and a VOC of 0.90 V, leading to a high PCE of 5.98%. Yan and
coworkers reported a tetraphenylethylene (TPE) core-based 3D
SMA, TPE-PDI4, enabling the NF-PSCs based on PTB7-Th with a PCE
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[41]
of 5.53%. In 2015, this group reported a series of tetraphenyl PDI (PPDI) as the photoactive layer delivered a certificated PCE
View Article of
Online
[47] DOI: 10.1039/C6QM00247A
carbon-group core based 3D PDI acceptors (tetraphenyl-methane 5.40%.
(TPC-PDI4), tetraphenylsilane (TPSi-PDI4) and tetraphenylgermane Jen et al. then investigated the influence of molecular geometry
(TPGe-PDI4)), enabling the PffBT4T-2DT based PSCs with PCEs of up of the donor polymers and the PDI dimers on the bulk
to 4.3%, 4.2% for TPC and TPSi, respectively, which is higher than heterojunction (BHJ) morphology with an inverted structure device.

Materials Chemistry Frontiers Accepted Manuscript

[42]
that for TPGe. So it appears that whether the extent of the
intramolecular twisting of adjoined PDI units is optimal to give the
best performance. Rencently, Yan and coworkers carried out
systematic research into this issue. Three type of 3D PDI dyes were
prepared and compared. These dyes comprised four PDI units
linked by three different cores, TPC, TPE, and tetraphenylpyrazine
(TPPz), named as TPE-PDI4, TPC-PDI4 and TPPz-PDI4, respectively. In
3 [28]
these cores, TPC has a sp carbon atom in the middle A planar
structure TPE has a double bond at its core, leading to a TPE-shaped
core. The extent of intramolecular twisting of TPPz-PDI4 is further
reduced compared to TPE-PDI4 and TPC-PDI4. As the extent of
intramolecular twisting decreases from TPC-PDI4, TPE-PDI4 to TPPz-
PDI4, the aggregation tendency and electron mobility of the SMAs
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Results indicated that the pseudo 2D conjugated polymer PTB7-Th
had better miscibility with H-di-PDI (PPDI) compared to the 1D
polymer PTB7, facilitating more efficient exciton dissociation in the
BHJ films. In addition, the face-on oriented – stacking was only
slightly disrupted by H-di-PDI with a more rigid structure providing
suitable pathways for charge transport, compared with that of bay-
linked PDI dimer (SdiPDI). As a result, a very high PCE of 6.41% was
achieved in the PTB7-Th:H-di-PDI device. Furthermore, the
absorption intensity could be enhanced with the increasing number
of n in H-n-PDIs molecules. Thus, H-tri-PDI consisting of three PDI
5 -1 -1
blocks via imide position with εmax of 2.8 × 10 M cm and the
LUMO level of -3.93 eV was synthesized. Benefiting from the
appropriate energy level alignment and favorable morphology in

increase. As a result, the optimized PffBT-T3(1,2)-2:TPPz-PDI4 based PBDT-TS1:H-tri-PDI active layer, the JSC of PSCs was as high as 16.5
-2 [48]
device exhibits a highest PCE of 7.1%, which is significantly higher mA cm and the PCE reached 7.25%.
[43]
than that of TPE-PDI4 (6.0%) and TPC-PDI4 (4.7%) based devices.
Thus, it is also important to consider the intramolecular twisting of
3D molecular acceptors for improving the performance of non-
fullerene OSCs.

Nonbay-position-functionalized PDI
Yu et al. synthesized a family of PDI derivatives functionalized at the
nonbay-position (αPPID, αPBDT) and bay-position (βPPID, βPBDT).
The PSCs give the highest PCE values of 4.92% for αPBDT-based
devices and 3.61% for αPPID-based devices; these values were 39%
and 4% higher than the values of their bay-substituted counterparts
(βPBDT and βPPID), respectively. This is attributed to the αPPID and
αPBDT exhibiting a stronger tendency to form aggregates, which
endows the materials with higher electron mobility due to the good
[44]
planarity and strong π-stacking of nonbay-functionalized PDI.
Based on this theory, Yu et al. then synthesized a 3D PDI dyes
functionalized at nonbay-positions with BDT as the core, named as
TPB. The highest PCE of 8.47% was achieved with 8% diphenyl ether
−2
(DPE) as additive and the high JSC of about 18 mA cm was
comparable with that of solar cells based on PC71BM/PTB7-Th.
[45]
However, the bottleneck is the relatively low FF (<0.6) of devices.

Imide-position functionalized PDI

In 2012, Narayan and co-workers designed a nonplanar dimeric PDI
derivative, named as PPDI-1, in which the twisted N-N single bond
significantly reduced the planarity and thus the aggregation effect
of acceptors was weakened. And an encouraging PCE of ∼ 3% was
obtained when it was blended with the polymer donor PBDTTT-C-T Fig. 3 Chemical structures of nonbay- and imide-position functionalized PDI
with a 10-fold increase in JSC in comparison with the monomer small molecule acceptors.
[46]
PDI. To consider the effect of alkyl chain length on the device
Wang and coworkers then selected racemic 1,2-
performance, Wang and coworkers designed and synthesized a
diaminocyclohexane (rac-DACH) and enantiomerically pure 1R,2R-
finely optimized acceptor named H-di-PDI (PPDI) by replacing C7H15
DACH and 1S,2S-DACH as bridges to develop chiral bridged PPDI
with C5H11 in PPDI-1. H-di-PDI showed strong absorption in the
5 -1 -1 derivatives, namely DACH-PPDIs. The PSCs based on PTB7-Th:rac-
range 450-550 nm with a εmax of 2.2  10 M cm and the LUMO [49]
DACH-PPDI achieved a PCE of 4.68%. Chen and coworkers
level was –3.86 eV. The PSCs employing the blend of PBDT-TS1:H-di-
reported a novel 3D PDI acceptor employing tetraphenyl methane
with a tetrahedral architecture as the core connecting four PDI units

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via the imide position. The solution- processed BHJ OSCs based on
[50]
PBDTTT-C-T:Me-PDI4 exhibited a PCE as high as 2.73%.
In concerted efforts to judiciously design new PDI acceptors, PSCs
based on PDIs have attracted much attention and rapid
developments have been made. On the basis of achieving effective
disruption of excessive aggregation, attention was directed to the
balance between the charge mobility and the twisted molecular
configuration in PDI molecules. It is possible to find a PDI acceptor
with high mobility that works well with a polymeric donor with high
mobility. The non-fullerene solar cells based on PDI dyes will have a
further reduced recombination rates and higher FF values.
2.2 NI-based small molecule acceptors
Naphthalene diimide (NDI) molecules possess a planar aromatic
scaffold and two annulated electron-withdrawing imide groups,
hence the aromatic naphthalene core possesses strong polarization
of π-systems and low π-electron density.
[51-54]
This particular
structure endows NDIs as among the most investigated classes of
organic compounds, primarily due to the greatly modified optical
Published on 06 February 2017. Downloaded on 08/02/2017 12:42:31.
and electronic properties via easy and effective modulation by
appropriate simple functionalization. In addition, there are many
literatures reports on the NDIs possessing the excellent field
electronic transfer ability as air-stable n-type semiconductors due
to the electron-deficient character. What’s more, the broad
absorption bands over the whole visible spectral range through the
introduction of core substituents enabled NDIs with interesting
photosystems and photovoltaic applications.
Fig. 4 Chemical structures of the NI based small molecule acceptors.
6 | J. Name., 2012, 00, 1-3
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Journal Name
Core-functionalization of the NDIs has been considered ViewasArticle
a general
Online
method to extend the planar, rigid core andDOI: 10.1039/C6QM00247A
prepare novel materials
[55-59]
with new structures. For example, in 2015, Russell and
coworkers prepared a new small molecule, BiNDI by linking two NDI
monomers via a vinyl group, extending the -conjugation length,
Materials Chemistry Frontiers Accepted Manuscript
planarizing the molecular backbone and enhancing the
intermolecular – stacking. BiNDI exhibited an excellent electron
transport property: a highest electron mobility for a neat film 0.365
2 −1 −1
cm V s and the highest PCE for PSCs based on PTB7:BiNDI was
[60]
2.41%.
Furthermore, many research groups functionalized NDI by
inserting various electron-deficient chromophores, such as
tetraazabenzodifluoranthene diimide (BFI) and
diphenylanthrazoline (DPA), etc., between two naphthalimide (NI)
units, to form a π-conjugated framework. Park and coworkers
developed a class of novel NI-based NFAs (NIDCS, NIDCS-MO, and
NIDCS-HO) by incorporating a NI moiety into the terminal position
of the dicyanodistyrylbenzene. These molecules consist of different
substituents on the core phenyl unit, hydrogen, methoxy, and
hexyloxy, respectively. Introduction of THE cyano (CN) substituent
as the electron-withdrawing moiety is beneficial for increasing the
electron affinity; it promots the formation of crystalline structures,
and thus favors efficient charge transport. Thus, the PSCs based on
[61]
P3HT:NIDCS-HO exhibited a maximum PCE of 2.71%. The PSCs
based on PPDT2FBT:NIDCS-HO showed a maximum PCE of 7.6%
with a remarkably high VOC of 1.03 V and also a reduced energy loss
[62]
of 0.73 eV in the devices (Eoptg for PPDT2FBT is 1.76 eV).
Jenekhe and coworkers reported a novel class of NI-based
electron acceptors, 2,3,6,7-bis (naphthalene imide)-3,6-diphenyl-
trans-anthrazolines by modulating the DPA unit via two NI units
terminated. Photovoltaic devices composed of the BNIDPA-BO (2-
butyloctyl) acceptor with PSEHTT, PTB7-Th, and PTB7 had higher
PCEs of about 3.0% than those of BNIDPA-DT (2-decyltetradecyl)-
based PSCs, emphasizing the critical role of the size of alkyl chains
[63]
on NFAs.
Jenekhe et al. also synthesized two related molecules, BFI-P2 and
DBFI-T and performed comparative studies of their charge
photogeneration and photovoltaic properties by adopting a donor
polymer, PSEHTT. Although BFI-P2 had a maximum organic field-
2 -1 -1
effect transistor μe of 0.5 cm V s , much higher than that of DBFI-
2 -1 -1
T with 0.006 cm V s , PSEHTT:DBFI-T blends had sufficiently high
and balanced electron and space-charge limited current (SCLC) hole
−4 2 -1 -1 −4 2 -1 -1
mobilities (μe = 1.2  10 cm V s , μh = 2.8  10 cm V s ) than
−7 2 -1 -1
those of PSEHTT:BFI-P2 blends (μe = 3.5  10 cm V s , μh = 1.8 
−4 2 -1 -1
10 cm V s ). This may be caused by the high anisotropy in
charge transport of the highly crystalline molecule, BFI-P2. Thus, the
PSCs based on DBFI-T with nonplanar 3D architecture showed
[64]
better performance (5.04% PCE) than PSCs based on BFI-P2. This
research group then designed new acceptors (DBFI-T, DBFI-S, DBFI-
DMT, BFI-MTT) by varying the arylene (Ar) linker (Ar = thiophene,
selenophene, dimethylthiophene, dimethyl-thienothiophene)
between two BFI building block. As a result, the interplanar angle
between two BFI units in each molecule varied from 33° for DBFI-T,
40° for DBFI-S, 53° for DBFI-MTT to 62° for DBFI-DMT. This played
an important role in the absorption band, energy level, electron
transport property, and thus the device performance. The best
performing new electron acceptor material, DBFI-DMT, paired with
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DOI: 10.1039/C6QM00247A
Table 2 Optoelectronic properties and PSC device parameters for NI based small molecule acceptors.

LUMO/HOMO VOC JSC PCE

Acceptor Donor Device Structure FF Ref.
(eV) (V) (mA cm-2) (%)

Materials Chemistry Frontiers Accepted Manuscript

BiNDI PTB7 ITO/PEDOT:PSS/BHJ/Ca/Al -4.35/-6.74 0.75 5.47 0.59 2.41 60
NIDCS PTB7 ITO/PEDOT:PSS/BHJ/Ca/Al -3.42/-5.90 a 0.73 8.04 0.46 2.71 61
NIDCS-MO PTB7 ITO/PEDOT:PSS/BHJ/Ca/Al -3.66/-5.75 0.54 6.23 0.43 1.45 61
NIDCS-HO PTB7 ITO/PEDOT:PSS/BHJ/Ca/Al -3.41/-5.79 0.67 8.15 0.47 2.55 61
NIDCS-HO PPDT2FBT ITO/PEDOT:PSS/BHJ/Ca/Al --- 1.03 11.88 0.63 7.64 62
BNIDPA-BO PSEHTT ITO/ZnO/BHJ/MoO3/Ag -3.60/-5.80 0.94 6.64 0.48 3.02 63
BNIDPA-BO PTB7-Th ITO/ZnO/BHJ/MoO3/Ag --- 0.96 9.02 0.35 3.00 63
BNIDPA-BO PTB7 ITO/ZnO/BHJ/MoO3/Ag --- 0.98 8.13 0.39 3.08 63
BNIDPA-DT PSEHTT ITO/ZnO/BHJ/MoO3/Ag -3.60/-5.80 0.95 2.67 0.50 1.26 63
BNIDPA-DT PTB7-Th ITO/ZnO/BHJ/MoO3/Ag --- 0.90 5.20 0.36 1.71 63
BNIDPA-DT PTB7 ITO/ZnO/BHJ/MoO3/Ag --- 0.95 4.12 0.36 1.42 63
BFI-P2 PSEHTT ITO/ZnO/BHJ/MoO3/Al -3.60/-5.80 0.94 3.16 0.49 1.44 64
DFI-T PSEHTT ITO/ZnO/BHJ/MoO3/Al -3.60/-5.80 0.86 10.14 0.58 5.04 64
DBFI-S PSEHTT ITO/PEI/BHJ/MoO3/Ag -3.70/-5.74 0.82 5.61 0.57 2.61 65
DBFI-DMT PSEHTT ITO/PEI/BHJ/MoO3/Ag -3.66/-5.82 a 0.92 12.56 0.55 6.37 65
DBFI-MTT PSEHTT ITO/PEI/BHJ/MoO3/Ag -3.67/-5.76 a 0.94 8.33 0.51 3.94 65
DBFI-EDOT PSEHTT ITO/PEI/BHJ/MoO3/Ag -3.65/-5.76 a 0.93 13.82 0.63 8.10 66
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SM1 PCDTBT-C12 ITO/PEDOT:PSS/BHJ/LiF/Al -3.50/-5.93 a 1.04 4.79 0.56 2.78 67

SM2 PCDTBT-C12 ITO/PEDOT:PSS/BHJ/LiF/Al -3.62/-5.98 a 1.11 2.21 0.30 0.74 67
SM3 PCDTBT-C12 ITO/PEDOT:PSS/BHJ/LiF/Al -3.68/-5.95 a 1.09 1.71 0.30 0.56 67
SM4 PCDTBT-C12 ITO/PEDOT:PSS/BHJ/LiF/Al -3.65/-5.80 a 1.24 0.37 0.28 0.13 67
NI-AA-NI P1 ITO/PEDOT:PSS/BHJ/LiF/Al -3.57 b/-6.00 a 1.06 4.10 0.43 1.87 68
NI-AA-NI P2 ITO/PEDOT:PSS/BHJ/LiF/Al --- 1.07 6.27 0.55 3.71 68
NTz-Np P3HT ITO/PEDOT:PSS/BHJ/Ca/Al -3.60 a/-6.01 c 0.90 5.18 0.60 2.81 69
BTz-Np P3HT ITO/PEDOT:PSS/BHJ/Ca/Al -3.44 a/-5.95 c 0.94 3.52 0.46 1.53 69
a
calculated from the onset oxidation and reduction potential. b calculated from the absorption edge (λedge) with the equation of Eopt
g = 1240/λedge (eV); The value of λedge is obtained

from the absorption spectrum. c calculated from the method of photoelectron spectroscopy in air (PESA).

PSEHTT, had a PCE of 6.4%, a VOC of 0.92 V and a maximum external
[65]
quantum efficiency value of 80%. They also designed a very
highly twisted 3D electron acceptor dimer, DBFI-EDOT, with a
twisted angle of 76° between the two planar monomeric BFI units.
A maximum PCE of 8.10% was achieved for the optimized DBFI-
EDOT:PSEHTT devices and a PCE of 8.52% for DBFI-
[66]
EDOT:PSEHTT:PBDTT-FTTE ternary blend solar cells. Thus
increasing the twisted angle between the large rigid π-conjugated
building blocks in dimeric molecules can result in a large variation in
the PCE in BHJ solar cells. This suggests that the twisted angle is a
potential means to further improve the performance of NFAs in
PSCs, since it improves molecular isotropy and symmetry, efficient
molecular packing, isotropic carrier transport, and compatibility
with a donor polymer in BHJ blends.
Bo and coworkers reported a series of NI based planar small
molecules (SM1-4) comprising a central benzene core, two
thiophene bridges and two NI terminal groups, attached with
different substituents on the central benzene ring. With a decrease
in planarity of small molecules, by attachment of different
substituents on the central benzene ring, the twisted angles
between the two NI end groups of SM1-4 gradually increased, and
the PCEs based on these electron acceptors, when adopting
PCDTBT-C12 as electron donor, decreased from 2.78% to 0.13% due
[67]
to the decreased electron mobility. Bo and coworkers also
reported a new planar acceptor NI-AA-NI, with a diacetylene group
as the bridge. This acceptor had a high crystallinity and a higher
lying LUMO level of -3.57 eV. As a result, the P2:NI-AA-NI based
[68]
OPVs exhibited a PCE of 3.71% with a VOC of 1.07 V.
Aso and coworkers developed new NI based electron-accepting
compounds containing NTz and BTz as an electron-deficient unit,
respectively. Conventional OPV devices fabricated from NTz-Np as
an acceptor with P3HT as a donor showed superior performance
with PCE as high as 2.81% compared to the corresponding BTz-Np
[69]
based devices.
As a weaker electron withdrawing group, NI based small
molecule acceptors have a high-lying LUMO level, which will reduce
the energy loss and produce a high VOC. Whereas, NI-based small
molecule acceptors generally exhibit a low electron mobility,
usually leading to unbalanced electron and hole mobility when
blending with polymer donors. Therefore, strategies for designing
NI based small molecule acceptors with planar configuration are
urgently to facilitate the electron transport in the active layer.
3. IDT-based small molecule acceptors
During the past two years, chemists have adopted the rigid
indacenodithiophene (IDT) or indacenodithieno[3,2-b]-thiophene
(IDTT) as core, substituted with strong electron-withdrawing groups,
to provide electron acceptor materials, while also providing out-of-
plane side chains for tuning processability and morphology/phase
separation. Moreover, the rigid coplanar structure of the molecules
can prevent rotational disorder and reduce reorganization energy,
which may enhance charge carrier mobility. The IDT/IDTT based
PSCs have exhibited great potential in achieving outstanding
photovoltaic performance.
In 2012, Zhan and coworkers first reported a novel acceptor DC-
IDT2T applying IDT unit as a central building block, 1,1-

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Table 3 Optoelectronic properties and PSC device parameters for IDT based small molecule acceptors. DOI: 10.1039/C6QM00247A

LUMO/HOMO VOC JSC PCE

Acceptor Donor Device Structure FF Ref.
(eV) (V) (mA cm-2) (%)
DC-IDT2T PBDTTT-C-T ITO/PEDOT:PSS/BHJ/Ca/Al -3.85/-5.43a 0.90 8.33 0.52 3.93 70

Materials Chemistry Frontiers Accepted Manuscript

IDT–2BM PTB7 ITO/PEDOT:PSS/BHJ/Ca/Al -3.80/-5.66 a 0.77 10.10 0.55 4.26 71
IDTT–2BM PTB7 ITO/PEDOT:PSS/BHJ/Ca/Al -3.80/-5.50 a 0.85 9.87 0.57 4.81 71
IDT-IC PTB7-Th ITO/PEDOT:PSS/BHJ/Ca/Al -3.88/-5.61 a 0.83 9.53 0.40 3.16 72
IDTIDT-IC PTB7-Th ITO/PEDOT:PSS/BHJ/Ca/Al -3.82/-5.42 a 0.94 14.5 0.48 6.48 72
IEIC PTB7-Th ITO/PEDOT:PSS/BHJ/PDNI/Al -3.82/-5.42 a 0.97 13.6 0.48 6.31 73
IEIC PffT2-FTAZ-2DT ITO/ZnO/ BHJ /V2O5/Al --- 1.00 12.2 0.59 7.30 74
IEICO PTB7-Th ITO/PEDOT:PSS/BHJ/PFN-Br/Al -3.95/-5.32 a 0.82 17.7 0.58 8.40 75
IDSe-T-IC J51 ITO/PEDOT:PSS/BHJ/PDNIO/Al -3.79/-5.45 a 0.91 15.20 0.62 8.58 76
ITIC PTB7-Th ITO/ZnO/BHJ/MoO3/Ag -3.83/-5.48 a 0.90 5.20 0.36 1.71 77
ITIC PBDBT ITO/ZnO/BHJ/MoO3/Al --- 0.90 16.8 0.74 11.2 78
ITIC J51 ITO/PEDOT:PSS/BHJ/PDNIO/Al --- 0.82 16.5 0.69 9.26 79
IT-M PBDBT ITO/ZnO/BHJ/MoO3/Al -3.98/-5.58 a 0.94 17.4 0.74 12.05 79
IT-DM PBDBT ITO/ZnO/BHJ/MoO3/Al -3.93/-5.56 a 0.97 16.5 0.71 11.29 79
ITIC-Th PDBT-T1 ITO/PEDOT:PSS/BHJ/Ca/Al -3.93/-5.66 a 0.88 16.2 0.67 9.60 9
IC-C6IDT-IC PDBT-T1 ITO/PEDOT:PSS/BHJ/Ca/Al -3.91/-5.69 a 0.89 15.1 0.65 8.71 80
g = 1240/λedge (eV); The value of λedge is obtained
a
calculated from the onset oxidation and reduction potential. b calculated from the absorption edge (λedge) with the equation of Eopt
from the absorption spectrum. c calculated from the method of photoelectron spectroscopy in air (PESA).
Published on 06 February 2017. Downloaded on 08/02/2017 12:42:31.

dicyanomethylene-3-indanone (DC) as electron-withdrawing end

Fig. 5 Chemical structures of the IDT based small molecule acceptors.
groups, and thiophene as π-bridges. Without any post treatment,
BHJ PSCs based on PBDTTT-C-T:DC-IDT2T blends yielded a PCE as
[70]
high as 3.93%. In 2015, Zhan and coworkers explored two novel
A-D-A type molecules, IDT-2BM and IDTT-2BM with extended fused-
ring IDT or IDTT units as cores and strong electron-withdrawing unit
2-(benzo[c][1,2,5]thiadiazol-4-ylmethylene)-malononitrile (BM) as
the end-capping group as electron acceptors in solution-processed
PSCs. The PSCs based on PBDTTT-C-T:IDT-2BM and PBDTTT-C-
T:IDTT-2BM blends exhibited promising PCEs of 4.26% and 4.81%,
respectively, the BM unit held great potential for constructing
[71]
efficient non-fullerene acceptors.
Liao and coworkers presented a non-fullerene electron acceptor
bearing a fused 10-heterocyclic ring (indacenodithiopheno-
indacenodithiophene), IDTIDT-IC. It had a broadened absorption
(λedge = 810 nm) and a deep LUMO level due to the enhancement of
effective conjugation length. In comparison with the device based
on PTB7-Th:IDT-IC with a highest PCE value of 3.16% and a VOC of
0.83 V, the device based on IDTIDT-IC reached a maximum PCE
value of 6.48% with VOC of 0.94 V. More interestingly, when this
molecule was paired with PTB7-Th, an Eloss as low as 0.59 eV was
[72]
obtained.
They then employed IDT as the core, end-capped with electron
withdrawing 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile
(INCN) groups, namely IEIC. The acceptor exhibited a strong and
broad absorption spectrum in the 500-750 nm region, with an
absorption edge of 790 nm. The optical bandgap was estimated to
be 1.57 eV. The PSCs based on the blend of a narrow bandgap
[73]
polymer donor PTB7-Th and IEIC exhibited PCEs of up to 6.31%.
Nonetheless, it is observed that the IEIC’s absorption range largely
overlaps with the absorption spectrum of PTB7-Th. Yan and
coworkers then presented a wide-bandgap (WBG) polymer named
as PffT2-FTAZ-2DT with a complementary absorption to IEIC
molecules from 450 to 800 nm, leading to a high PCE of 7.3% for the
[74]
PffT2-FTAZ-2DT:IEIC-based PSCs. Therefore, developing and
seeking a highly efficient donor material that matches well with
NFAs is an important engineering. Based on IEIC, Hou replaced the
alky groups in IDT block with alkoxy ones, namely IEICO, possessing

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Materials Chemistry Frontiers
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Fig. 6 Chemical structures of the DPP based small molecule acceptors.
a narrow optical bandgap of 1.34 eV with a LUMO level of −3.95
eV. As a result, the PSC device based on PTB7-Th:IEICO showed a
PCE of 8.4%. A PCE of 10.7% was recorded in a tandem PSC
[75]
adopting PTB7-Th:IEICO as rear cell. Liao coworkers presented an
IDSe-T-IC acceptor bearing a fused five-membered heterocyclic ring
containing selenium atoms, withEg of 1.52 eV, strong absorption in
the 600-850 nm region, and a high LUMO level of -3.79 eV. The
solar cell based on J51:IDSe-T-IC gave a PCE of 8.6%, much higher
than that of J51:PC71BM-based PSCs under similar device
[76]
fabrication conditions (PCE = 6.0%).
Based on the acceptor IEIC, Zhan and coworkers designed ITIC by
introducing rigid out-of-plane side chains onto the fused rings to
facilitate the effective interchain π−π overlaps and enhance
intermolecular charge transport, and the PCE of PTB7-Th:ITIC was
[77]
6.80%. Hou and coworkers adopted a new conjugated polymer,
PBDB-T with a strong aggregation effect in solution and small
ΔHOMO (HOMOd - HOMOa) to fabricate the solar cell devices.
Outstanding performance with a PCE of 11.21% and excellent
[78]
thermal stability were obtained. Li and coworkers used ITIC as
acceptor in the J51-based nonfullerene PSCs; encouragingly, the
non-fullerene PSCs based on J51:ITIC exhibited a high PCE of
[79]
9.26%. This group also designed and synthesized a new medium
bandgap 2D-conjugated copolymers (J61) adopting linear alkylthio
substituents on the thiophene conjugated side chain of the
benzodithiophene (BDT) units. The devices based on J61:ITIC
[80]
showed a PCE of up to 9.53%. Hou and coworkers rationally
designed two new molecular acceptors by incorporating methyl-
modified end groups on ITIC, namely IT-M, IT-DM, increasing the
energy levels slightly, without causing too much steric hindrance for
intermolecular packing. Finally, a high PCE of 12.05% was obtained
[9]
for PBDB-T:IT-M.
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Materials Chemistry Frontiers Accepted Manuscript
Zhan and coworkers successfully developed ITIC-Th based on ITIC
after altering the phenyl side chains to thienyl side-chains to
downshift molecular energy levels and facilitate the compatibility
with high-performance electron donors, especially moderate- or
WBG donors. The PSCs based on ITIC-Th and low-bandgap (LBG)
PTB7-Th and WBG polymer donor PDBT-T1 exhibited PCEs up to
[81]
8.7% and 9.6%, respectively. Furthermore, based on the IDT unit,
Zhan and coworkers also reported the IC-C6IDT-IC acceptor with
four n-hexyl side chains and a highly planar backbone, prepared in
high yield using a one-step facile reaction. The PSCs based on PDBT-
T1:IC-C6IDT-IC without additional treatments yield PCEs of up to
8.71%, demonstrating that the planar acceptor also exhibits good
[82]
performance in PSCs.
These electron-donating extended fused rings, IDT and IDTT,
bearing extended π-frameworks and rigid coplanar structures are
beneficial to the enhanced charge carrier mobility. In addition, this
type of non-fullerene SMAs possessing a narrow bandgap and
appropriate energy level fits in well with the WBG polymers that
usually exhibit a high molar absorption coefficient in the range 350
to 700 nm and high hole mobility. These properties endow the
devices based on IDT:WBG polymers with high EQEs, which is
favorable for the JSC and FF.
4. DPP based small molecule acceptors
Due to the strong electron withdrawing ability and high polarity of
the DPP moiety, DPP-conjugated materials often exhibit a broad
and tunable optical absorption, high mobilities for holes and
electrons, and an enhanced crystalline tendency, which are
beneficial for high photocurrents and good fill factors in solar
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Table 4 Optoelectronic properties and PSC device parameters for DPP based small molecule acceptors DOI: 10.1039/C6QM00247A

LUMO/HOMO VOC JSC PCE

Acceptor Donor Device Structure FF Ref.
(eV) (V) (mA cm-2) (%)
DPP5 P ITO/PEDOT:PSS/BHJ/Al -4.22/-5.54 a 0.92 8.23 0.52 3.90 88

Materials Chemistry Frontiers Accepted Manuscript

DPP6 P ITO/PEDOT:PSS/BHJ/Al -4.36/-5.64 a 0.86 10.28 0.56 4.95 88
DPP-Ph2 P3HT ITO/ZnO/BHJ/MoO3/Ag -4.13/-5.88 a 0.89 5.91 0.50 3.28 89
LBL P3HT ITO/ZnO/BHJ/MoO3/Ag --- 0.89 5.80 0.50 3.23 90
BBB P3HT ITO/ZnO/BHJ/MoO3/Ag --- 0.15 2.72 0.25 0.12 90
BLB P3HT ITO/ZnO/BHJ/MoO3/Ag --- 0.50 4.40 0.40 1.10 90
LLL P3HT ITO/ZnO/BHJ/MoO3/Ag --- 0.14 0.51 0.25 0.02 90
DTBT(TDPP)2 PTB7 ITO/ZnO/BHJ/MoO3/Ag -4.18/-5.70 0.83 7.77 0.47 3.03 91
DTDfBT(TDPP)2 PTB7 ITO/ZnO/BHJ/MoO3/Ag -4.33/-5.85 0.81 12.1 0.51 5.00 91
F(DPP)2B2 P3HT ITO/PEDOT:PSS/BHJ/PFN/Al -3.39/-5.21 a 1.18 5.35 0.50 3.17 92
4D(TPE-DPP4) P3HT ITO/PEDOT:PSS/BHJ/Ca/A -3.81 a /-5.53 c 1.18 5.17 0.64 3.86 94
SF(DPPB)4 P3HT ITO/PEDOT:PSS/BHJ/PFN/Al -3.51/-5.26 a 1.14 8.29 0.55 5.16 95
a b
calculated from the onset oxidation and reduction potential. calculated from the absorption edge (λedge) with the equation of Eopt
g = 1240/λedge (eV); The value of λedge is

obtained from the absorption spectrum. c calculated from the method of photoelectron spectroscopy in air (PESA).
[83-87]
cells. Based on the above considerations, DPP has now electron mobility of the fluorinated electron acceptor and thereby
[91]
become one of the most favored electron-deficient units in the suppressed bimolecular recombination.
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constructing electron acceptors.
Sharma and coworkers reported two small molecules,
unsymmetrical DPP5 and symmetrical DPP6 substituted by
triphenylamine based TCBD. The DPP5 and DPP6 exhibited LBG with
excellent absorption ability in the regions 500-800 and 500-900
nm, respectively. The devices based on optimized active layers of
DPP5 and DPP6 and conjugated copolymer P showed PCEs of 3.90%
[88]
and 4.95%, respectively.
Cabanetos and coworkers reported two electron acceptors built,
by attaching phthalimide groups on DPP through the use of
acetylenic linkages. This permitted the extension of the effective
conjugation, lowering the energy level of the frontier orbitals and
reducing the steric interactions between thiophene units and
phenyl rings. Once blended with P3HT, promising PCEs of 3.28% for
[89]
DPP-Pht2 based devices were achieved. On the basis of this work,
Cabanetos and coworkers also invested the effect of side chains on
the electronic and photovoltaic properties of DPP-Pht2 with
different alkyl groups (linear and branched solubilizing groups on
the phthalimide end or the DPP core, namely LBL, LLL, BLB and
BBB). It turns out that BBB and LBL acceptors with branched side
chains exhibited enhanced molecular light absorption and
electronic mobility by favoring the formation of J-aggregates and
more favorable phase separation with P3HT. Thus, the
corresponding solar cells based on BBB and LBL had better PCEs (of
3.2%, 1.1%) than solar cells based on LLL and BLB (PCEs of 0.1%,
[90]
0.02%).
Jo and coworkers synthesized two small-molecule electron
acceptors using 4, 7-dithien-2-yl-2,1,3-benzothiadiazole (DTBT) or
fluoro-substituted DTBT (DTDfBT) as a core and DPP as a flanking
unit to investigate the effect of fluorine substitution on the
photovoltaic performance of NF-PSCs. Both electron acceptors
exhibited a low bandgap of 1.5 eV with broad absorptivity in the
range 500-800 nm, high electron affinity, favorable energy levels,
and high crystallinity due to the coplanar backbone structures and
extended conjugation. As a result, the PSCs based on
PTB7:DTDfBT(TDPP)2 exhibited a higher PCE of 5.00% that the
DTBT(TDPP)2 based solar cells. The PTB7:DTDfBT(TDPP)2 based PSCs
benefit from enhanced crystallinity and the resulting higher
Chen and coworkers designed and synthesized a bipolar DPP
derivative F(DPP)2B2, in which a fluorene ring functioned as the
core, two DPP units as the arms, and two benzene rings as the end-
groups. This molecule had an intense absorption in the range 550-
700 nm. The solar cells based on P3HT:F(DPP)2B2 exhibited a PCE of
3.17% with a VOC of 1.18 V and those based on F(DPP)2B2:PC71BM
[92]
showed a PCE of 3.26%. They then also developed a ternary PSC
system P3HT:F(DPP)2B2:PC61BM using the bipolar
F(DPP)2B2 molecule as energy cascade material and obtained a best
PCE of 3.92%, which corresponded to  23% improvement. This was
attributed to the enhanced light absorption in the 550-700 nm,
exciton dissociation and charge carrier transport by the
[93]
introduction of the third bipolar component.
Through the conjunction of TPE and DPP functionalities, a novel
four-directional NFA (denoted as 4D) was designed, synthesized,
and characterized. A PCE of 3.86% was obtained in solution-
processable BHJ devices based on P3HT:4D with a very high VOC of
[94]
1.18 V.
Chen and coworkers synthesized SF(DPPB)4 with SF as core and
four benzene end-capped DPP as arms. This molecule with cross-
shaped molecular geometry was beneficial for suppressing strong
intermolecular aggregation in a P3HT:SF(DPPB)4 blend. It exhibited
energy levels matches well with those of P3HT, and thus the devices
gave a PCE of 5.16% with an extremely high VOC of 1.14 V.
Furthermore, the devices exhibited excellent thermal stability at
[95]
150°C for 3 h. On the basis of the SF(DPPB)4 molecule, Chen and
coworkers also investigated the effects of substituted alkyl side
chains on molecular packing, crystallinity, and BHJ film morphology.
They found the following: 1) The unique star-shaped molecular
structure resulting from the spiro linkage imparted those molecules
with high solubility and suppressed aggregation. 2) Small
perturbations of the chemical structure, for example, the choice of
different side chains and C–C single bond or C–C triple bond
connection, led to quite different physical properties, since the lack
of structure order in SF-A-DPP thin films substantially reduces their
electron transport characteristics. 3) In BHJ blends, SF-DPPEH
crystallizes well after thermal annealing, while SF-DPPC8 and SF-
DPPC12 showed low crystallinity. 4) The branched 2-ethylhexyl (EH)

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Journal Name
group provided SF-DPPEH interacted less with P3HT, leading to an
increased in the VOC. Thus, together with moderate crystallization of
the acceptors, the nanoscale phase separation (20-30 nm), and thus
the less-pronounced geminate recombination led to an increase in
[96]
the device performance of P3HT:SF-DPPEH blends up to 3.63%.
In conclusion, the DPP unit has a strong electron affinity and a
planar, well-conjugated lactam skeleton, giving rise to strong π−π
interactions. Molecules based on DPP building block usually display
a strong aggregation tendency in film. Hence, many strategies for
constructing the twisted molecule have been proposed. The devices
based on these electron acceptors have a high VOC and low voltage
loss.
5. Conclusion and Outlook
After decades of development, non-fullerene electron acceptors for
PSCs have attracted considerable attention. Significant progress has
been made, and the PCE of non-fullerene based polymer solar cells
Published on 06 February 2017. Downloaded on 08/02/2017 12:42:31.
now exceeds 12%. Those developments demonstrated that some
new non-fullerene acceptors have outperformed fullerenes in
devices and will promote the further development of the PSCs field.
However, NFAs still present challenges. First, the relatively low
electron mobility and strong recombination losses seriously limit
the development of NF-OSCs. Therefore, it is meaningful to design
the acceptors with an appropriate aggregation nature to form pure
domains with a preferable charge transport pathway and decrease
the bimolecular recombination possibility. Second, several
examples demonstrate that some existing electron donors that are
not suitable for the fullerene derivatives are fit in well with the NFA
materials. Hence, much effort should be devoted to the exploration
of new donors that could form more appropriate alignment with
the NFAs and endow the solar cells with low voltage losses as well
as fast and efficient charge separation. Third, it must be noted that
the lack of systematic perception about the exciton
diffusion/separation process about the NFA based solar cells limits
the further improvement of solar cells. Thus, much effort is urgently
needed to explore further possible new donors and understand the
charge separation process.
Benefiting from the diversification and implementability of
chemical modification on non-fullerene acceptor materials along
with the ongoing efforts to control the BHJ morphology, device
engineering, and the availability of new donor materials, NFAs will
become competitive with their fullerene counterparts and the
dominant acceptors.
Acknowledgements
For financial support of this research, we thank 973 Program (Grant
2014CB643500 and 2013CB933503), the National Natural Science
Foundation of China (51673202, 21428304, and 21225209), NSFC-
DFG Joint Project TRR61, and the Chinese Academy of Sciences
(XDB12010400).
Notes and references
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This review describes developments of non-fullerene small molecular acceptors in solar cells since 2015, including rylene imide, indacenodithiophene
View Articleand
Online
diketopyrrolopyrrole. DOI: 10.1039/C6QM00247A

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