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MATERIALS CHEMISTRY FRONTIERS
REVIEW ARTICLE
Materials Chemistry Frontiers Accepted Manuscript

New developments in non-fullerene small molecule acceptors for
polymer solar cells
Received 00th January 20xx, ab a a a
Accepted 00th January 20xx N. N. Liang, W. Jiang,* J. H. Hou, Z. H. Wang
DOI: 10.1039/x0xx00000x 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
Rsc.li/frontiers-materials
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
Published on 06 February 2017. Downloaded on 08/02/2017 12:42:31.
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 tune the light absorption and the energy level. Thus, much
attention had been paid to the non-fullerene acceptors (NFAs), for
It is well known that solar cell devices used to convert solar energy
the judicious design and synthesis of novel chemical structures, the
into electricity are a major topic within the academic and business
optimization of the device structure, and BHJ morphology. Efforts
communities. Recently, scientists from the Energy Department's
have been rewarded and some new NFAs have exhibited
National Renewable Energy Laboratory (NREL) and the Swiss Center
outstanding performance: PSCs with the PCEs > 12% have recently
for Electronics and Microtechnology (SCEM) have jointly set a new [9]
been reported. Therefore, summarizing the critical achievements
world record using a dual-junction III-V/Si solar cell with the newly
in NF-PSCs, and making a systematic and sensible analysis of these
certified record conversion efficiency of 29.8%, exceeding the
[1-2] materials, are considered to be essential to guide molecular design.
theoretical limit of 29.4% for crystalline silicon solar cells.
The development of NFAs in polymeric donor-based solar cells
Great improvements have also been achieved with solution
(NF-PSCs) prior to 2015 having given a detailed introduction and
processed bulk heterojunction (BHJ) organic solar cells (OSCs) [10-13]
summary in several reviews. In this review article, therefore,
consisting of electron donors and electron acceptors. Over the past
we only summarize recent progress, molecular design strategies
few decades, these solar cells have also attracted attention from
and structure–property relationships in NF-PSCs since 2015.
the scientists worldwide due to the following important and distinct
According to the structural features, we classified non-fullerene
advantages: 1) low-cost, mechanical flexibility, light weight, and the
electronic acceptors into three groups, including the rylene imide
ability to be produced by the roll-to-roll method, providing
dyes, indacenodithiophene (IDT)-based and diketopyrrolopyrrole
possibility for large-area industrial production; 2) the donor and
(DPP)-based small molecule acceptors (SMAs).
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
2. Rylene imide dyes
the first BHJ OSCs based on polymer:fullerene was demonstrated by
[3,4] 2.1 PDI based small molecule acceptors
Heerger and coworkers in 1995. During the past decades,
fullerene derivatives as electron acceptors have played a dominant Among the non-fullerene electron acceptors, perylene diimide (PDI)
role in the field of OSCs. The power conversion efficiency (PCE) of derivatives have attracted considerable attention. They exhibit
single-junction polymer solar cells (PSCs) have exceeded 11.7% great potential due to their excellent electron-accepting ability,
largely due to excellent morphology and high mobilities as well as high electron mobility, and especially their highly tunable electronic
the ultrafast photo-induced electron transfer between the fullerene [14-16]
energy levels, achieved by chemical modification. Whereas,
[5-8]
acceptors and polymer donors. However, fullerene derivatives 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
a.
Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular donor-acceptor interfacial area for the exciton diffusion/separation,
Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, [17-18]
China; E-mail: jiangwei@iccas.ac.cn. thereby limiting the PCEs of such device. Now, after several
b.
University of Chinese Academy of Sciences, Beijing 100049, China. years of development, researchers have achieved great success in
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1

Materials Chemistry Frontiers Page 2 of 14
ARTICLE Journal Name
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DOI: 10.1039/C6QM00247A

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 Bay–position functionalized PDI
to low crystallinity and poor electron transport ability, which is a Wang and coworkers reported a family of PDI dyes with different
bottleneck for improvements in the short-circuit current (JSC), fill bay-linkages between the PDI subunits. In particular, the PSCs
[19-25]
factor (FF), and PCE. It has therefore been challenging to devices based on PBDTTT-C-T:SdiPDI (singly-linked PDI dimer)
design NFAs possessing both suitable domain size in BHJs and high exhibited the best PCE values of up to 3.63%.
[26]
The PTB7-
electron mobility. As is well known, an effective way to improve the Th/SdiPDI-based PSCs exhibited a high PCE of up to 4.5%,
carrier mobility is to expand ring functionalization. For PDI collectively due to the broad absorption, appropriate HOMO level
derivatives, two kinds of functionalization positions are termed as [27]
and moderate crystallinity of PTB7-Th. When the PTB7-Th/SdiPDI
imide position and lateral positions including bay- and nonbay- solar cells were fabricated with the inverted configuration, the PSCs
positions, respectively.
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Page 3 of 14
Journal Name ARTICLE
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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

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

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DOI: 10.1039/C6QM00247A

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

Page 5 of 14

[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.

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

via the imide position. The solution- processed BHJ OSCs based on Core-functionalization of the NDIs has been considered ViewasArticle
a general
Online
[50]
PBDTTT-C-T:Me-PDI4 exhibited a PCE as high as 2.73%. method to extend the planar, rigid core andDOI: 10.1039/C6QM00247A
prepare novel materials
[55-59]
In concerted efforts to judiciously design new PDI acceptors, PSCs with new structures. For example, in 2015, Russell and
based on PDIs have attracted much attention and rapid coworkers prepared a new small molecule, BiNDI by linking two NDI
developments have been made. On the basis of achieving effective monomers via a vinyl group, extending the -conjugation length,

disruption of excessive aggregation, attention was directed to the planarizing the molecular backbone and enhancing the
balance between the charge mobility and the twisted molecular intermolecular – stacking. BiNDI exhibited an excellent electron
configuration in PDI molecules. It is possible to find a PDI acceptor transport property: a highest electron mobility for a neat film 0.365
2 −1 −1
with high mobility that works well with a polymeric donor with high cm V s and the highest PCE for PSCs based on PTB7:BiNDI was
[60]
mobility. The non-fullerene solar cells based on PDI dyes will have a 2.41%.
further reduced recombination rates and higher FF values. Furthermore, many research groups functionalized NDI by
2.2 NI-based small molecule acceptors inserting various electron-deficient chromophores, such as
Naphthalene diimide (NDI) molecules possess a planar aromatic tetraazabenzodifluoranthene diimide (BFI) and
scaffold and two annulated electron-withdrawing imide groups, diphenylanthrazoline (DPA), etc., between two naphthalimide (NI)
hence the aromatic naphthalene core possesses strong polarization units, to form a π-conjugated framework. Park and coworkers
of π-systems and low π-electron density.
[51-54]
This particular developed a class of novel NI-based NFAs (NIDCS, NIDCS-MO, and
structure endows NDIs as among the most investigated classes of NIDCS-HO) by incorporating a NI moiety into the terminal position
organic compounds, primarily due to the greatly modified optical of the dicyanodistyrylbenzene. These molecules consist of different
and electronic properties via easy and effective modulation by substituents on the core phenyl unit, hydrogen, methoxy, and
appropriate simple functionalization. In addition, there are many hexyloxy, respectively. Introduction of THE cyano (CN) substituent
literatures reports on the NDIs possessing the excellent field as the electron-withdrawing moiety is beneficial for increasing the
electronic transfer ability as air-stable n-type semiconductors due electron affinity; it promots the formation of crystalline structures,
to the electron-deficient character. What’s more, the broad and thus favors efficient charge transport. Thus, the PSCs based on
[61]
absorption bands over the whole visible spectral range through the P3HT:NIDCS-HO exhibited a maximum PCE of 2.71%. The PSCs
introduction of core substituents enabled NDIs with interesting based on PPDT2FBT:NIDCS-HO showed a maximum PCE of 7.6%
photosystems and photovoltaic applications. 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
Fig. 4 Chemical structures of the NI based small molecule acceptors.
transport property, and thus the device performance. The best
performing new electron acceptor material, DBFI-DMT, paired with

Page 7 of 14
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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) (%)

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
SM1 PCDTBT-C12 ITO/PEDOT:PSS/BHJ/LiF/Al -3.50/-5.93 a 1.04 4.79 0.56 2.78 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
PSEHTT, had a PCE of 6.4%, a VOC of 0.92 V and a maximum external Aso and coworkers developed new NI based electron-accepting
[65]
quantum efficiency value of 80%. They also designed a very compounds containing NTz and BTz as an electron-deficient unit,
highly twisted 3D electron acceptor dimer, DBFI-EDOT, with a respectively. Conventional OPV devices fabricated from NTz-Np as
twisted angle of 76° between the two planar monomeric BFI units. an acceptor with P3HT as a donor showed superior performance
A maximum PCE of 8.10% was achieved for the optimized DBFI- with PCE as high as 2.81% compared to the corresponding BTz-Np
[69]
EDOT:PSEHTT devices and a PCE of 8.52% for DBFI- based devices.
[66]
EDOT:PSEHTT:PBDTT-FTTE ternary blend solar cells. Thus As a weaker electron withdrawing group, NI based small
increasing the twisted angle between the large rigid π-conjugated molecule acceptors have a high-lying LUMO level, which will reduce
building blocks in dimeric molecules can result in a large variation in the energy loss and produce a high VOC. Whereas, NI-based small
the PCE in BHJ solar cells. This suggests that the twisted angle is a molecule acceptors generally exhibit a low electron mobility,
potential means to further improve the performance of NFAs in usually leading to unbalanced electron and hole mobility when
PSCs, since it improves molecular isotropy and symmetry, efficient blending with polymer donors. Therefore, strategies for designing
molecular packing, isotropic carrier transport, and compatibility NI based small molecule acceptors with planar configuration are
with a donor polymer in BHJ blends. urgently to facilitate the electron transport in the active layer.
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 3. IDT-based small molecule acceptors
different substituents on the central benzene ring. With a decrease During the past two years, chemists have adopted the rigid
in planarity of small molecules, by attachment of different indacenodithiophene (IDT) or indacenodithieno[3,2-b]-thiophene
substituents on the central benzene ring, the twisted angles (IDTT) as core, substituted with strong electron-withdrawing groups,
between the two NI end groups of SM1-4 gradually increased, and to provide electron acceptor materials, while also providing out-of-
the PCEs based on these electron acceptors, when adopting plane side chains for tuning processability and morphology/phase
PCDTBT-C12 as electron donor, decreased from 2.78% to 0.13% due separation. Moreover, the rigid coplanar structure of the molecules
[67]
to the decreased electron mobility. Bo and coworkers also can prevent rotational disorder and reduce reorganization energy,
reported a new planar acceptor NI-AA-NI, with a diacetylene group which may enhance charge carrier mobility. The IDT/IDTT based
as the bridge. This acceptor had a high crystallinity and a higher PSCs have exhibited great potential in achieving outstanding
lying LUMO level of -3.57 eV. As a result, the P2:NI-AA-NI based photovoltaic performance.
[68]
OPVs exhibited a PCE of 3.71% with a VOC of 1.07 V. In 2012, Zhan and coworkers first reported a novel acceptor DC-
IDT2T applying IDT unit as a central building block, 1,1-

View Article Online

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

(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

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

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
Fig. 5 Chemical structures of the IDT based small molecule acceptors. NFAs is an important engineering. Based on IEIC, Hou replaced the
alky groups in IDT block with alkoxy ones, namely IEICO, possessing

Page 9 of 14
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DOI: 10.1039/C6QM00247A

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

View Article Online

Table 4 Optoelectronic properties and PSC device parameters for DPP based small molecule acceptors DOI: 10.1039/C6QM00247A

(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

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

Page 11 of 14
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This review describes developments of non-fullerene small molecular acceptors in solar cells since 2015, including rylene imide, indacenodithiophene
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diketopyrrolopyrrole. DOI: 10.1039/C6QM00247A


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do present some challenges in terms of chemical modification to

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

disrupting the aggregation tendency by means of chemical

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Fig. 2 Chemical structures of the polymer donors mentioned in this review.

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Imide-position functionalized PDI

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Jenekhe and coworkers reported a novel class of NI-based

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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

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

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Fig. 6 Chemical structures of the DPP based small molecule acceptors.

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