Materials Today d Volume xxx, Number xx d xxxx 2017 RESEARCH

RESEARCH: Review
Naphthalenediimide (NDI) polymers for
all-polymer photovoltaics
Nanjia Zhou 1,*, Antonio Facchetti 2,3,*
1
National University of Singapore, EA-07-08, 9 Engineering Drive 1, 117575 Singapore, Singapore
2
Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States
3
Flexterra Corporation, 8025 Lamon Avenue, Skokie, IL 60077, United States

Naphthalenediimide (NDI) polymers are an important class of electron-accepting (acceptor or n-type)

semiconductors for organic photovoltaic (OPV) or organic solar cell (OSC) applications. Blending them
with compatible electron-donating (donor or p-type) polymers yields an OPV device known as bulk-
heterojunction (BHJ) all-polymer solar cells (all-PSCs). Compared to the more extensively studied OPVs
using fullerene derivatives as the acceptor material, all-PSCs provide important benefits such as
chemical tunability, mechanical flexibility and ambient/stress stability. Through an extensive research
on materials design and device optimization in the last five years, all-PSCs employing NDI-based
polymers have achieved remarkable improvement in device power conversion efficiency (PCE), now
surpassing 10% – a number that approaches the state-of-the-art organic photovoltaic (OPV) cells using
fullerenes. In this review, recent development of NDI-based conjugated polymers used in all-PSCs will
be highlighted.

Introduction cal flexibility [6–12]. Fueled by the increasing understanding of

The rising world energy consumption accompanied by the
increasing environmental awareness drives the pursuit of sus-
tainable energy sources [1,2]. Among several types of renewable
energy technologies, solar energy provides several unique advan-
tages such as being portable, environmentally friendly, and
readily-available [3]. The sharp cost decline of solar energy has
made it far more attractive in recent years, yet, further cost reduc-
tion is essential to reach competiveness with conventional fossil
fuels in a subsidy-free environment [4]. Since the discovery of
conductivity in polyacetylene [5], p-conjugated polymers have
attracted significant attention for electronics and energy applica-
tions. Compared to their inorganic counterparts, polymer solar
cells (PSCs) employing p-conjugated semiconductors offer poten-
tially significant cost advantage, and at the same time, add other
important benefits such as solution-processability and mechani-
⇑ Corresponding authors at: Northwestern University, 2145 Sheridan Road, Evanston, IL
60208, United States.
E-mail addresses: Zhou, N. (nus.nzhou@gmail.com), Facchetti, A. (a-facchetti@northwestern.
edu).
molecular structure–property relationships and device design,
PSC key figure of merits have improved tremendously over the
last few years to reach power conversion efficiencies (PCEs)
>10% (Table 1).
The most comprehensively studied PSCs are based on the bulk
heterojunction (BHJ) structure where the photoactive layer con-
sists of an interpenetrating network of an electron-donating
(donor or p-type) and an electron-accepting (acceptor or n-
type) semiconductors (Fig. 1a). To date, extensive efforts have
focused on developing PSCs based on new p-type electron-
donating materials, mixed with a fullerene derivative such as
PC61BM or PC71BM. Recently, efficiency close to 12% has been
demonstrated [13–15]. Despite this remarkable success, fullerene
derivatives have some drawbacks such as: (a) costly synthesis and
difficult purification; (b) negligible absorption in the visible, and
thus they do not contribute to the significant photocurrent gen-
eration; (c) limited chemical and energetic tunability, constrain-
ing the design of complementary donor materials for maximum
PSC metrics such as open circuit voltage (Voc) and short circuit
current density (Jsc); (d) poor ambient/operational stability. As a

1369-7021/Ó 2018 Elsevier Ltd. All rights reserved./https://doi.org/10.1016/j.mattod.2018.02.003

1
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 view
SEARCH: Re-
2

RESEARCH
TABLE 1
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Photoactive blend composition and all-PSC device performance.

Reference Donor NDI-based acceptor D:A blend ratio Voc (V) Jsc (mA/cm2) FF PCE (%) Device configurations
Moore et al. [64] P3HT (D1) P(NDI2OD-T2) (A1) 1:1 0.53 0.67 0.51 0.18 ITO/PEDOT:PSS/active layer/Al
Fabiano et al. [65] P3HT (D1) P(NDI2OD-T2) (A1) 1:2 0.50 0.48 0.67 0.16 ITO/PEDOT:PSS/active layer/LiF/Al
Fabiano et al. [47] P3HT (D1) P(NDI2OD-T2) (A1) 1:1 0.53 4.18 0.59 1.31 ITO/PEDOT:PSS/active layer/LiF/Al
Schubert et al. [66] P3HT (D1) P(NDI2OD-T2) (A1) 1:0.75 0.56 3.77 0.65 1.4 ITO/PEDOT:PSS/active layer/Sm/Al
Tang[67] PTB7 (D2) P(NDI2OD-T2) (A1) 1:1 0.62 3.4 0.39 1.1 ITO/PEDOT:PSS/active layer/Ca/Al
Zhou et al. [68] PTB7 (D2) P(NDI2OD-T2) (A1) 1:1.5 0.799 6.28 0.53 2.66 ITO/ZnO/active layer/MoO3/Ag
Mori et al. [69] PTQ1 (D3) P(NDI2OD-T2) (A1) 0.7:0.3 0.84 8.85 0.55 4.1 ITO/PEDOT:PSS/active layer/Ca/Al
Mori et al. [70] PTB7-Th (D4) P(NDI2OD-T2) (A1) 1:1 0.795 13.0 0.556 5.73 ITO/PEDOT:PSS/active layer/Ca/Al
Mu et al. [71] NT (D5) P(NDI2OD-T2) (A1) 1:1 0.77 11.5 0.56 5.0 ITO/ZnO/active layer/V2O5/Al
Kang et al. [72] PPDT2FBT (D6) P(NDI2OD-T2) (A1) 1:0.7 0.85 11.9 0.51 5.0 ITO/PEDOT:PSS/active layer/LiF/Al
Zhou et al. [73] PTPD3T (D7) P(NDI2OD-T2) (A1) 1:1 0.87 6.75 0.548 3.22 ITO/ZnO/active layer/MoO3/Ag
Lei et al. [74] P2F-DE (D8) P(NDI2OD-T2) (A1) 2:1 0.76 11.72 0.541 4.81 ITO/PEDOT:PSS/active layer/Al
Chen et al. [41] TQ-F (D9) P(NDI2OD-T2) (A1) 0.7:0.3 0.84 13.61 0.639 7.31 ITO/PEDOT:PSS/active layer/PDINO/Al
Lee et al. [75] PTB7-Th (D4) P(NDI2HD-T2) (A2) 1.3:1 0.82 13.97 0.53 6.11 ITO/ZnO/active layer/MoO3/Ag
Kranthiraja et al. [116] PBT-2F-ANTh-BDT (D10) P(NDI2HD-T2) (A2) 2.5:1 0.79 15.23 0.53 6.42 ITO/ZnO/active layer/MoO3/Al
Kim et al. [76] P[BDTT(m)-TT-F(n)] (D11) P(NDI2HD-T2) (A2) 1.5:1 0.89 14.40 0.52 6.81 ITO/ZnO/Active layer/MoO3/Ag
Gao et al. [77] J51 (D12) P(NDI2OD-T2) (A1) 2:1 0.83 14.18 0.702 8.27 ITO/PEDOT:PSS/active layer/PDINO/Al
Fan et al. [42] PTzBI (D13) P(NDI2OD-T2) (A1) 1:0.5 0.844 15.48 0.7010 9.16 ITO/PEDOT:PSS/active layer/PFNDI-Br/Al
Fan et al. [37] PTzBI-Si (D14) P(NDI2OD-T2) (A1) 1:0.5 0.87 15.57 0.7339 10.1 ITO/PEDOT:PSS/active layer/PFNDI-Br/Al
Lee et al. [78] PTB7-Th (D4) P(NDI1T-HD) (A3) 1.3:1 0.79 13.46 0.56 5.96 ITO/ZnO/active layer/MoO3/Ag
Shen et al. [40] PTB7-Th (D4) P(NDI1T-HD) (A3) 1.5:1 0.774 12.26 0.521 4.94 ITO/PEDOT:PSS/active layer/PDIN/Al
Kim et al. [24] PBDTTTPD (D15) P(NDI1T-HD) (A3) 1.3:1 1.06 11.22 0.56 6.64 ITO/PEDOT:PSS/active layer/LiF/Al
Choi et al. [79] PTB7-Th (D4) P(NDI2OD-TVT) (A4) 1.3:1 0.84 11.40 0.43 4.25 ITO/PEDOT:PSS/active layer/LiF/Al
Li et al. [53] PBDTTS-FTAZ (D16) P(NDI-T10) (A5) 2:1 0.88 12.2 0.61 6.6 ITO/PEDOT:PSS/active layer/LiF/Al
Li et al. [80] PTB7-Th (D4) P(NDI-T10) (A5) 1:1 0.83 12.9 0.71 7.6 ITO/PEDOT:PSS/active layer/LiF/Al
Li et al. [81] PTB7-Th (D4)+PBDTTS- P(NDI-T10) (A5) D4:D16:A5 = 1:0.15:1 0.84 14.6 0.73 9.0 ITO/ZnO/active layer/MoO3/Al
FTAZ(D16)
Li et al. [82] PTB7-Th (D4) P[NDI-TT(m)-TVT(n)], 3:1 0.790 12.66 0.431 4.86 ITO/PEDOT:PSS/active layer/PDIN/Al
m:n = 1:1 (A6)
Li et al. [83] PTB7-Th (D4) P[NDI-TT(m)-TVT(n)], 2:1 0.794 13.75 0.483 5.27 ITO/PEDOT:PSS/active layer/PDIN/Al
m:n = 1:3 (A6)

Materials Today
Yuan et al. [84] P3HT (D1) P(NDI-xfTh) (A7)* 1:1 0.47 0.57 0.55 0.13 ITO/PEDOT:PSS/active layer/Al
Xue et al. [85] J51 (D12) P(NDI-TDT) (A8) 2:1 0.69 11.91 0.621 5.10 ITO/PEDOT:PSS/active layer/PDINO/Al
Huang et al. [86] PTB7 (D2) P(NDI-TVTOEt) (A9) 1:1 0.86 4.11 0.46 1.70 ITO/ZnO/active layer/MoO3/Ag
Cho et al. [87] PBDTTTPD (D15) P(NDICVT-HD) (A10) 1.3:1 0.94 12.15 0.65 7.4 ITO/ZnO/active layer/MoO3/Ag
Jung et al. [89] PTB7-Th (D4) P(NDI2DT-FT2) (A11) 1:1 0.81 13.53 0.62 6.71 ITO/ZnO/active layer/MoO3/Ag

d
Deng et al. [90] PTB7-Th (D4) P(NDIT-FB-T) (A12) 1.5:1 0.80 14.3 0.44 5.20 ITO/PEDOT:PSS/active layer/LiF/Al

Volume xxx, Number xx

Xue et al. [91] J51 (D12) P(FVF-NDI) (A13) 2:1 0.83 13.09 0.477 5.21 ITO/PEDOT:PSS/active layer/PDINO/Al
Hwang et al. [92] P3HT (D1) P(NDIBS) (A14) 1:3 0.53 3.79 0.44 0.84 ITO/PEDOT:PSS/active layer/LiF/Al
Earmme et al. [93] PSEHTT (D17) P(NDIS-HD) (A15) 1:1 0.76 7.78 0.55 3.16 ITO/ZnO/active layer/MoO3/Ag
Hwang et al. [48] PTB7-Th (D4) P(NDIS-HD) (A15) 1:1 0.81 18.80 0.51 7.73 ITO/ZnO/PEI/active layer/MoO3/Ag
Oh et al. [94] BDT-F (D18) P(NDIS-HD) (A15) 1:1 0.94 12.22 0.62 7.13 ITO/ZnO/active layer/MoO3/Ag
Hwang et al. [95] PSEHTT (D17) P(NDIS-30BO) (A16) 1:1.5 0.77 10.37 0.56 4.44 ITO/ZnO/active layer/MoO3/Ag
Hwang et al. [96] PBDTTT-CT (D19) 30PDI (A17) 1:1 0.79 18.55 0.45 6.29 ITO/ZnO/PEI/active layer/MoO3/Ag
Sharma et al. [97] PTB7-Th (D4) NDI-Th-PDI30 (A18) 1.3:1 0.792 11.39 0.552 4.98 ITO/ZnO/PFN/active layer/MoO3/Ag
Schubert et al. [66] P3HT (D1) P(NDI-TCPDTT) (A19) 1:1.5 0.63 2.43 0.70 1.1 ITO/PEDOT:PSS/active layer/Samarium/Al

d
xxxx 2018
Zhou et al. [98] P3HT (D1) PF-NDI (A20) 2:1 0.68 3.63 0.66 1.63 ITO/PEDOT:PSS/active layer/Ca/Al
Geng et al. [99] TTV2 (D20) P(DTS-NDI) (A21) 1:1 0.44 5.22 0.52 1.19 ITO/PEDOT:PSS/active layer/Ca/Al
Materials Today d Volume xxx, Number xxx d xxxx 2018 RESEARCH

result, whether fullerene derivatives are ultimately the best can-

didates as PSC acceptors remains in question.
layer/PDINO/Al

layer/PDINO/Al An alternative strategy has emerged in the last decade employ-

layer/Mg/Al

ing p-conjugated polymer donor + polymer acceptor semicon-

layer/Ca/Al
layer/Ca/Al

layer/Ca/Al
layer/Ca/Al
layer/Ca/Al
layer/Ca/Al
layer/Ca/Al
layer/Ca/Al
ductors as the components for the photoactive layer, resulting
in solar cells called all-PSCs [16–19] (Fig. 1a). The simultaneous
optimization of both structural and electronic properties of both
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active

ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active
ITO/PEDOT:PSS/active donor and acceptor polymers offers significant advantages for
the optimization of PSC performance metrics. From the band
engineering perspective, all-PSCs provide the freedom to opti-

RESEARCH: Review
mize the absorption properties of both donor and acceptor mate-
rials to cover a broad range of photon harvesting. From the
charge transport point of view, n-type polymers can potentially
offer a continuous network for charge transport and afford
higher charge carrier mobilities than fullerene derivatives
4.35
2.88
5.33
1.20
3.14

1.54
2.59

5.57
1.2
2.0
3.2

[20,21]. Furthermore, all-PSCs possess other important benefits

such as superior thermal, mechanical, and photostability com-
pared to the devices employing fullerenes [22–24].
0.420

0.603
0.456

0.596

0.624
0.46

0.49
0.46
0.50
0.51
0.59

To date, several families of polymeric acceptors have been

developed for all polymer solar cells (all-PSCs), most notable
are those based on perylene diimide (PDI) [25], naphthalenedi-
imide (NDI) and azaacenes containing boron-nitrogen coordina-
13.26

13.68

tion bond (B N) [26,27]. Among them, naphthalenediimide

3.77
7.65

5.62
9.55
3.62
8.05
4.8
6.4
9.6

(NDI)-based polymers have received particular attention and

are the most studied polymer acceptors [28,29]. As the smallest
0.682

homologue of the rylenediimide family, NDI can be synthesized

0.76
0.90
0.71
0.86
0.93

0.66
0.56
0.62
0.66
0.69

from commercially available 1,4,5,8-naphthalenetetracarboxylic

acid dianhydride (NDA), which is widely used industrially as a
precursor for perinone pigments [30]. NDI groups possess high
thermal and oxidative stability. The strongly electron-deficient
(acceptor unit) aromatic core with two electron-withdrawing
imide groups yields low-lying LUMO energy levels, thus making
1.5:1

1.5:1

1.5:1

NDI-based systems excellent electron-transporting semiconduc-

1:1

1:1

2:1
3:1
1:1
1:1
1:1
1:1

tors [28,29,31–34]. NDI is an extremely versatile building block

for developing optoelectronic materials. The functionalization
P(PDI25-co-NDI75) (A27)

of the NDI can be carried out both at the imide nitrogen atoms
P(NDTI-BT-DT) (A28)
P(NDIBTOC8) (A23)

and at the carbon 2 and 6 positions (Fig. 2), the latter via highly
P(BDTNDI-T) (A25)

P(NDTI-DTT) (A31)
P(NDTI-DTT) (A31)
P(NDTI-TT) (A30)
P(NDIBTH) (A22)

P(IDT-NDI) (A26)

P(NDTI-T) (A29)

regioselective bromination [35]. At the imide nitrogen position,

P(NTZ) (A24)

the installation of alkyl chains renders the polymers soluble in

common organic solvents for solution processing. The proper
selection of side chains also plays an important role in NDI poly-
mer intermolecular packing, which is critical for charge carrier
All-PSC characteristics based on PNDI-4Th:P3HT is included here.

transport. Side chain engineering is also important for the opti-

mization of all-PSC blend morphology to achieve nanoscale
bicontinuous donor/acceptor polymer domains required for
PBDTBDD-T (D21)

PBDTBDD-T (D21)
PBDTTT-CT (D19)
PBDTTT-CT (D19)

high-efficiency all-PSCs. Functionalization with (hetero)aromatic

PTB7-Th (D4)

moieties at the NDI 2,6-positions extends the p-conjugation,

P3HT (D1)
PTB7 (D2)
PTB7 (D2)
PTB7 (D2)
PTB7 (D2)
J51 (D12)

leading to tunable optical bandgaps, electronic structures, and

chain-chain stacking properties. Many types of electron-rich
(donor) monomers have been copolymerized with NDI for all-
PSC acceptor applications. (Fig. 2) The most extensively studied
groups include oligothiophenes and thiophene derivatives. In
Nakano et al. [106]
Nakano et al. [106]
Nakano et al. [106]
Weng et al. [101]

addition, modification of the NDI core can also be achieved

Zhou et al. [105]

Yang et al. [107]

Xue et al. [103]
Dai et al. [104]
Liu et al. [100]
Liu et al. [100]

Ye et al. [102]

through core-extension to yield (hetero)aromatic-fused NDI

units which could lead to larger planar core systems with tuned
charge transport [36].
Thanks to various optimization strategies at both the molecu-
*

lar/structural and the device levels, as well as the increasing

3
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 RESEARCH Materials Today d Volume xxx, Number xx d xxxx 2018
RESEARCH: Review

FIGURE 1
Basic operation an all-polymer solar cell (all-PSC). (a) Structure of a bulk heterojunction (BHJ) all-PSCs. (b) Energy diagram of an all-PSC heterojunction and (c)
All-PSC figure-of-merits including short circuit current density, Jsc; open circuit voltage, Voc, fill factor, FF, and the power conversion efficiency, PCE.
Reproduced from Refs. [43,115].

FIGURE 2
NDI polymers for all-PSCs obtained from different design strategies.

fundamental understandings of the photophysical processes, describe the major NDI-based polymer structures and device
despite having a relatively short history, all-PSCs employing optimization that have led to this progress and attempt to
NDI polymers have demonstrated remarkable progress from rationalize, by reporting several examples, why NDI polymers
below 3% in 2014 to above 10% [37] now. In this review we have been so successful.

4
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Materials Today d Volume xxx, Number xxx d xxxx 2018
The operation of all-polymer solar cells
Fig. 1a. shows the typical structure of a solar cell, here based on all-
polymer semiconductors. Briefly, at the heart of this device is a
blend of donor- and acceptor-types of conjugated semiconduct-
ing polymers, forming a photoactive layer, which is sandwiched
between two charge-selective interfacial layers [38]. For hole trans-
port purpose, PEDOT:PSS, MoO3, and V2O5 are most often used,
and for electron transport, ZnO as well as organic interfacial mate-
rials such as perylene diimides functionalized with amino PDIN
[39,40] or amino N-oxide PDINO [39,41], and PFNDI-Br [37,42]
are commonly utilized. The two adopted PSC device structures
are known as conventional and inverted architectures. In a con-
ventional device, a transparent, conducting indium tin oxide
(ITO) film is used as the hole-extracting anode contact and a
low work function metal (e.g., Ca, Al) is used as electron-
extracting cathode contact. In an inverted device, using proper
charge selecting interlayers, the ITO is used as cathode and a high
work function metal (e.g., Ag) is used as anode. Fig. 1b reports the
schematic illustration of the working mechanisms of an all-PSC
[43]. The generation of electron from photon source occurs in four
sequential steps: (1) absorption of photons by both the donor and
the acceptor polymers leads to the formation of bound electron-
hole pairs, known as excitons. (2) The excitons diffuse to the
donor/acceptor interfaces. (3) The energy differences of the donor
and acceptor polymers in their electron affinities (EAs) and ioniza-
tion potentials (IPs) lead to dissociation of excitons into free
charge carriers. (4) Free carriers transport to the anode and cath-
ode through the donor and acceptor polymer domains.
Upon exposing the all-PSCs to light, the current–voltage (I–V)
(or current density–voltage, J–V) characteristics can be recorded,
from which the major PSC parameters are extracted. Upon illu-
mination, a voltage called open circuit voltage (Voc) originates
from the splitting of electron and hole quasi-Fermi energy levels:
1 yield systems with peak EQE as high as 85% [48] and FF up to
V oc ¼ ðEFn  EFp Þ
e 0.73 [37,42]. Predictive models based on Flory–Huggins interac-
where EFn and EFp are the electron and hole quasi-Fermi levels,
respectively.
The power conversion efficiency (PCE) is represented as the
ratio between solar cell maximum power output, Pm, and the
input power from incident light, Pin:
Pm
PCE ¼  100%
Pin
Pm is a product of voltage and current density at the maximum
power point, Pm = VmpJmp. The Fill factor (FF) is defined as the
ratio between Pm and the product of Voc and the short current
density (Jsc):
V mp J mp
FF ¼
V oc J sc
Rearranging Eqs. (2) and (3) yields:
V oc  J sc  FF
PCE ¼
P in
These parameters are usually measured using a simulated solar
light, AM1.5G, which enables to compare materials from different
laboratories.
Please cite this article in press as: N. Zhou, A. Facchetti, (2018), https://doi.org/10.1016/j.mattod.2018.02.003
RESEARCH
The photoactive layer blend film morphology is critical for all-
PSC operation. Briefly, due to the limited exciton diffusion
lengths [44,45], a nanoscale domain size of donor and acceptor
polymers is the prerequisite for efficient exciton dissociation
[11,19,46]. Following exciton dissociation into free carriers,
domain connectivity to the respective electrodes is important
for the prevention of free carrier recombination. The optimiza-
tion of all-PSC morphology is an interesting and challenging
topic. Compared to the conventionally studied polymer:fullerene
solar cells, the use of two polymeric materials often results in rel-
RESEARCH: Review
atively large phase-separated morphology due to the immiscibil-
ity of the two polymers [17]. However, in a comprehensive
study done by Lee et al. [46], the authors optimized the all-PSC
blend morphology using different solvents, and discovered a sub-
stantial Jsc enhancement when reducing the donor/acceptor
domain sizes. Interestingly, the highest device performance was
found when the donor/acceptor domain sizes were optimized at
30 nm, notably similar to that of the best polymer/fullerene
cells. Furthermore, the degree of phase separation in all-PSC
blend films greatly influenced the in-plane and out-of-plane
charge transport mobilities, which are often characterized using
field effect transistor (FET) and/or space-charge limited current
(SCLC) in a single-carrier diode device configurations. In short,
the general guideline of morphology optimization for all-PSC
demands an out-of-plane preferential charge transport, or high
SCLC mobilities, which is often obtained with a laterally phase-
separated morphology with relatively small domain sizes [47].
In earlier studies of all-PSCs covered in this review, strong poly-
mer aggregation often results in large domain sizes unfavorable
for exciton dissociation and charge transport, thus constraining
the device EQE or Jsc, and FFs. However, extensive efforts in the
recent studies focus on the suppression of polymer aggregation
through a combination of optimization strategies regarding mate-
rials design and photoactive layer processing conditions, which
ð1Þ
tion parameters and solubility parameters are useful tools for
understanding and further improving all-PSC morphology and
thus device performance [17].
In addition to the extent of the domain sizes, other important
morphology characteristics of the polymer blend play a critical
role in all-PSC performance [49]. Thus, the efficient split of the
ð2Þ geminate electron-hole pair is largely influenced by the polymer
donor–polymer acceptor chain orientation at the polymer/poly-
mer interfaces with the preferred orientation being face-on to
face-on crystallite orientation [50–52]. Through controlling the
aggregation kinetics during thin film formation, enhanced
domain purity can enhance charge transport and ultimately
the device performance [49].
ð3Þ
General design considerations for NDI-based all-PSCs
regarding Jsc and Voc
ð4Þ While each conjugated donor and acceptor polymers alone often
have limited absorption and relatively narrow absorption bands,
the freedom to fine-tune the frontier molecular orbitals (FMOs)
of both donor and acceptor polymer presents a powerful and
viable strategy for full-spectrum photon harvesting. The
5
 RESEARCH
absorption spectrum of an all-PSC BHJ active layer can be divided
into absorption contributed separately by donor and acceptor
polymers, AD(k), and AA(k) which are described as [53]:
f D kD ðkÞ
AD ðkÞ ¼ AðkÞ
f D kD ðkÞ þ f A kA ðkÞ
ð5Þ
f D kD ðkÞ
AA ðkÞ ¼ AðkÞ
f D kD ðkÞ þ f A kA ðkÞ
where fD and fA are the volume fractions, while kD and kA are the
extinction coefficients, of the donor and acceptor, respectively.
RESEARCH: Review
The photon absorption contributed separately by donor and
acceptor polymers weighted over the AM1.5G spectrum is repre-
sented as:
Z tions of polymer donors (Fig. 3) – polymer acceptors (Figs. 4–6)
N D ¼ AD ðkÞAM1:5GðkÞdk
Z ð6Þ
N A ¼ AA ðkÞAM1:5GðkÞdk
Evidently, this simple calculation considering AM1.5G spectrum,
D:A polymer absorption spectra and their absorption coefficients,
and D:A ratio would provide valuable information on all-PSC
optimization as well as understanding the theoretical maximal
Jsc output from a particular polymer:polymer blend.
The ability to engineer band structures of the acceptor poly-
mers provides the unique benefits over fullerene-based OPVs
on Voc optimization. Considering charge recombination, the
Voc for all-PSCs can be further expressed as [54]:
!
1  Acceptor polymer Donor polymer
 kT ne nh
V oc ¼ ELUMO  EHOMO D  ln ð7Þ
e e N 2c
where D is the energy attributed to disorder within the all-
polymer domains, and ne and nh are the electron and hole density
in the acceptor and donor polymer domains, respectively, under
open circuit conditions. Nc is the density of states (DOS) at the
conduction band edge of the donor and acceptor polymers.
Undoubtedly, the design of high Voc all-PSCs requires maximizing
Acceptor polymer Donor polymer
the difference of ELUMO and EHOMO . Note that at finite
temperature (T – 0 K), the acceptor and donor polymer quasi-
Fermi energy levels can shift into the polymer optical bandgaps
which can result in loss in device Vocs [55].
As shown in the band diagram of a typical all-PSC in Fig. 1b,
the difference in the LUMO energies or EAs, and the difference in
the HOMO energies or IPs of the donor and acceptor polymers
create the driving force for the electron transfer from the donor
to the acceptor, and hole transfer from the acceptor to the donor.
To afford efficient charge separation and prevent recombination,
the LUMO–LUMO and HOMO–HOMO offset energies (DLUMO
and DHOMO) between donor and acceptor materials play a critical
role in all-PSC operation. Conventionally, it is argued that both
DLUMO and DHOMO >0.3 eV (estimated from exciton binding
energy) are required [53,56]. However, recent experimental
results suggest that this is not a fundamental requirement [57].
In all-PSCs, DLUMO as small as 0.1 eV was found to be sufficient
for exciton dissociation [58,59]. Regarding DHOMO, despite that
most experimental results focus on systems with relatively large
offset values of >0.3 eV, it should be noted that recent reports
[60–62] using polymer donors and small molecule non-
fullerene acceptors suggest DHOMO even smaller than 0.1 eV is
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Materials Today d Volume xxx, Number xx d xxxx 2018
already sufficient for hole transfer. For all-PSCs, more rigorous
photophysical measurements and theoretical studies are
necessary to help understand the exciton dissociation processes
associated with molecular structures, which will further guide
the experimental band structure design for both polymer semi-
conductors for all-PSCs. The possible further shrinkage of DLUMO
and DHOMO energies may potentially point to a feasible strategy
for further all-PSC efficiency improvement.
Recent development of NDI-based polymers as
acceptors for all-PSCs
In the following section, we will summarize selected combina-
blends for all-PSCs and the readers should refer to these figures
to access the polymers’ structures. For the sake of convenience
of discussion, the blend systems are arranged based on the struc-
tural features of different NDI acceptor polymers.
NDI acceptor polymers copolymerized with oligothiophenes
and thiophene derivatives
Conjugated NDI acceptor polymers copolymerized with different
oligothiophenes and thiophene derivatives are represented
in Fig. 4. One of the first reported and among the most
investigated polymer acceptors is poly[[N,N0 -bis(2-octyldode-
cyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,50-(2,
20-bithiophene)] [P(NDI2OD-T2) or Polyera Active
InkTM N2200] [20,63]. Thanks to its high n-type mobility
(me,FET = 0.85–6.4 cm2V1 s1) and excellent ambient stability,
P(NDI2OD-T2) has quickly become a benchmark acceptor for
all-PSC studies. In 2011, Sirringhaus et al. [64] and Loi et al.
[65] independently pioneered the investigation of all-PSCs based
on P(NDI2OD-T2) (A1) and P3HT (D1). These initial studies
demonstrated only modest PCEs of 0.16–0.18% which was attrib-
uted to the non-ideal blend morphology and low SCLC (diode)
carrier mobilities of this polymer blend. The PCEs of the same
D/A blend system was greatly improved by Fabiano et al. [47]
and Schubert et al. [66], who found that P(NDI2OD-T2) strongly
aggregates when processed using several common organic
solvents such as toluene and p-xylene, which results in poor
morphology for active layer blends and ultimately constrains
the all-PSC performance. The addition of chloronaphthalene
(CN), on the other hand, can successfully suppress the aggrega-
tion of the P(NDI2OD-T2) acceptor chains and prevent the for-
mation of strongly phase-separated domains of donor and
acceptor components in the active layer blends. In the important
work by Fabiano et al. [47], the authors comprehensively
compared the blend film carrier mobilities in both FET and
SCLC configurations, and discovered the self-stratified and
strongly phase-separated films obtained using 1,2-
dichlorobenzene (o-DCB) and p-xylene adversely affect the
out-of-plane charge transport and PCE, despite having high
FET mobilities. On the other hand, the high degree of laterally
separated domains obtained with the help of CN promotes the
preferential out-of-plane charge transport and high PCEs, despite
having low in-plane FET mobilities. Using a binary solvent mix-
ture of 1:1 p-xylene:CN, PCEs of 1.31% and 1.4% were reported
by Fabiano et al. [47] and Schubert et al. [66], respectively,
Materials Today d Volume xxx, Number xxx d xxxx 2018 RESEARCH

RESEARCH: Review

FIGURE 3
Chemical structures of selected donor polymers used in all-PSCs.

primarily because of the enhanced Jsc and FF. (Jsc = 3.77 mA/cm2 In 2012, McNeil et al. [67] reported that by changing from
and FF = 65% in the latter). P3HT (D1) to a smaller bandgap PTB7 (D2) donor polymer, an

7
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 RESEARCH Materials Today d Volume xxx, Number xx d xxxx 2018
RESEARCH: Review

FIGURE 4
Chemical structures of NDI acceptor polymers copolymerized with thiophenes and thiophene derivatives.

efficiency of 1.1% can be achieved. This result was later improved
by Marks et al. [68], who used the same active layer blend system
and found that the morphology of the active layer blends and
the performance of the resulting all-PSCs are strongly influenced
by the processing solvents. A highest PCE of 2.66% was found in
a cell using p-xylene. In 2014, Ito et al. [69] investigated an all-
PSC based on a BHJ blend of a medium bandgap (1.8 eV)
PTQ1 polymer (D3) and P(NDI2OD-T2) (A1). Photolumines-
cence (PL) quenching experiments is a powerful method to
investigate charge dissociation efficiency for both donors and
acceptors polymers in all-PSCs. In this D/A blend system, the
authors found that the PL of PTQ1 is highly quenched indepen-
dently of its composition. By contrast, the PL quenching effi-
ciency of P(NDI2OD-T2) is optimal with a D:A weigh ratio of
70:30. This result indicates the relatively small domain size of
PTQ1 compared to that of P(NDI2OD-T2), which again suggests
the importance of suppressing P(NDI2OD-T2) aggregation dur-
ing all-PSC thin film processing. By optimizing the D:A ratio, a

8
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Materials Today d Volume xxx, Number xxx d xxxx 2018 RESEARCH

RESEARCH: Review
FIGURE 5
NDI acceptor polymers copolymerized with other (hetero)aromatic donor monomers.

FIGURE 6
Chemical structures of acceptor polymers based on core-extended naphthodithiophene diimide (NDTI).

4.1% efficiency with a high Jsc of 8.85 mA/cm2 was achieved.
Later in the same year, the same group reported all-PSCs based
on blends of PBDTTT-EF-T or PTB7-Th (D4) with P(NDI2OD-
T2) (A1) exhibiting a PCE up to 5.7% [70]. In this active layer
blend system, the authors found the efficiencies of both the
charge carrier generation and collection processes are >80%. To
address the relatively poor charge transport issues in the above-
mentioned devices employing poorly textured polymer donors
such as PTB7, Mu et al. [71] used an active layer based on a pair
of crystalline low-bandgap polymers, NT (D5) and P(NDI2OD-
T2) (A1). In this system, it was found that the crystallinity of
the NT donor polymer is well preserved when blended with P
(NDI2OD-T2), resulting in balanced hole and electron transport
and a PCE of up to 5% using an inverted cell configuration.

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 RESEARCH
Polymer molecular weight plays a critical role in the polymer
optoelectronic properties. Moreover, in all-PSCs, the molecular
weight of both donor and acceptor polymers strongly influences
the thin film processing and blend film morphology evolution.
Kang et al. [72] investigated an all polymer blend based on
PPDT2FBT (D6):P(NDI2OD-T2) (A1). They discovered that the
device PCE increases as a function of the donor polymer molec-
ular weight, which is primarily due to the enhanced hole and
electron mobilities using higher molecular weight polymer
donors. In a separate study, Zhou et al. [73] selected a blend
RESEARCH: Review
system of PTPD3T (D7):P(NDI2OD-T2) (A1) and studied a two-
dimensional molecular weight optimization strategy which
locates the best PCE of 3.22% at a “sweet spot” of intermediate
molecular weights for both donor and acceptor polymers
(D7: Mn = 45 kDa; A1: Mn = 41 kDa). Similarly, Lei et al. [74] also
studied the molecular weight effect of the polymer acceptor in
P2F-DE (D8):P(NDI2OD-T2) (A1)-based all-PSC systems and
found that increasing the molecular weight of P(NDI2OD-T2)
enhances blend light absorption and electron mobility, but this
comes at the cost of strong aggregation and poor blend film
morphology. Therefore, the highest all-PSC performance was
achieved when using a medium molecular weight acceptor
polymer (Mn = 56 kDa). Chen et al. [41] recently studied an all-
PSC blend based on P(NDI2OD-T2) (A1) and a fluorinated donor
polymer TQ-F (D9). Interestingly, by increasing the molecular
weight of P(NDI2OD-T2) up to Mn = 63.3 kDa enables the highest
PCE in the studied series, which was attributed to the enhanced
charge transport and exciton dissociation properties. Undoubt-
edly, these studies indicate that special care must be taken when
selecting the molecular weight of the polymers for all-PSCs.
In addition to molecular weight, the polymer backbone side
chain functionalization, which enables solubility, is also an
important parameter to consider when optimizing all-PSCs.
Lee et al. [75] fabricated all-PSCs based on PTB7-Th
(D4):P(NDIR-T2) (A2), where the alkyl chain (R) was selected
from 2-hexyldecyl (2-HD), 2-octyldodecyl (2-OD), and 2-
decyltetradecyl (2-DT). The authors discovered that the polymer
with the shortest side chain, P(NDI2HD-T2), exhibits the greatest
crystallinity and carrier mobility, which afforded the highest PCE
of 6.11% among the three acceptor polymers. Using the same
polymer acceptor, P(NDI2HD-T2) (A2), the same group later
improved the device PCE to 6.42% by employing a different
donor polymer, PBT-2F-ANTh-BDT (D10).
More recent studies in 2016 and 2017 have shown intensified
interests and exciting progresses for P(NDI2OD-T2)-based all
PSCs. Thus, when employing different donor polymers, several
groups have achieved power conversion efficiencies of 8–10%,
which made P(NDI2OD-T2) the most efficient n-type polymer
for all-PSCs to date. An important strategy behind these
successful demonstrations is the pairing of donor polymers hav-
ing complementary absorption spectra to that of P(NDI2OD-T2).
For example, Kim et al. [76] studied all-PSCs based on
P(NDI2HD-T2) (A2) with different donor polymers,
P[BDTT(m)-TT-F(n)] (D11). By optimizing the ratio of m:n ratio
and hence the absorption spectra of the donor polymers, a pair
of donor:acceptor polymers with complementary absorption
spectra is found when m:n = 5:1, yielding a highest PCE of
6.81% in the studied series. Gao et al. [77] selected a medium
10
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Materials Today d Volume xxx, Number xx d xxxx 2018
bandgap polymer, J51 (D12), which has an absorption band cen-
tered at 550 nm, and demonstrated a PCE of 8.27%. Recently,
Fan et al. [42] used a relatively wide bandgap imide functional-
ized benzotriazole, PTzBI (D13) as the donor polymer in combi-
nation with P(NDI2OD-T2) (A1), and achieved an impressive
9.16% efficiency. In that study, the authors also used an environ-
mentally friendly 2-methyltetrahydrafuran (MeTHF) as the pro-
cessing solvent, which significantly improves the active layer
morphology. In a more recent work [37], the same group modi-
fied PTzBI polymer with a novel siloxane-terminated side chain,
and synthesized a new polymer, PTzBI-Si (D14). This novel side
chain functionalization approach helps increase polymer solubil-
ity in MeTHF and further promotes blend film morphology. They
demonstrated an all-PSC with a PCE of 10.1% – the highest so far
observed for all-PSCs.
In addition to P(NDI2OD-T2) (A1) and P(NDI2HD-T2) (A2),
many other thiophene-based co-monomers have been
incorporated with NDI to develop alternative acceptor polymers
for all-PSCs. Lee et al. [78] synthesized a series of NDI-based D-A
acceptor copolymer P(NDIT-R). They performed systematic stud-
ies on all-PSCs using PTB7-Th (D4) as the donor polymer
blended with P(NDIT-R) installed with different side chains.
The authors discovered that the NDI polymer with the shortest
side chain, P(NDI1T-HD) (A3), provides the highest electron
mobility and promotes face-on orientation of the polymer chains
with respect to the substrate, and therefore affords the highest
all-PSC PCE of 5.96%. Shen et al. [40] also used the same active
layer blend system and obtained a PCE of 4.94% using a non-
halogenated solvent, 1,2-dimethylbenzene (1,2-DMB). Kim
et al. [24] also used the same acceptor polymer, P(NDI1T-HD)
(A3), with a donor polymer, PBDTTTPD (D15), and obtained
an even higher PCE of 6.64% compared to that of
PBDTTTPD:PC61BM-based cells using the same device configura-
tion. Furthermore, the all-PSC demonstrates far superior mechan-
ical flexibility than cells using fullerene derivatives as the
acceptor component. Specifically, the all-PSC exhibits 60- and
470-fold improvements in elongation at break and toughness,
respectively, compared to the devices based on PCBM. This result
is attributed to both the greater intrinsic mechanical flexibility of
polymer acceptors vs. fullerenes, as well as the strengthened
donor/acceptor interface in all-PSCs due to polymer chain entan-
glement. The same group [23] further performed photo-induced
degradation studies on all-PSCs based on the same PBDTTTPD
(D14):P(NDI1T-HD) (A3) blend and discovered that the all-PSCs
exhibit far superior photo-stability than that of PCBM-PSCs with
85% vs. 50% retention of the initial PCE, respectively, after
100 h illumination. These two studies suggest a bright future
for all-PSCs in commercial applications such as wearable devices
where device endurance to mechanical deformation, along
with photostability, is critical. Choi et al. [79] compared the
performance of additive-free devices using P(NDI2OD-TVT), P
(NDI2OD-T2) and P(NDI2OD-T) as the acceptors. Thanks to
its high coplanarity and high crystallinity, P(NDI2OD-TVT)
(A4) shows the highest transistor electron mobility of
2.31 cm2 V1 s1 among the three polymers. The SCLC hole
and electron mobilities of the PTB7-Th (D4):PNDI2OD-TVT
(A4) are well balanced, mh = 1.6  104 and me = 7.0  105,
respectively, which resulted in the highest PCE of 4.25%.
Materials Today d Volume xxx, Number xxx d xxxx 2018
By replacing a certain number of bithiophene (2T) units in the
P(NDI2OD-T2) backbone by a single thiophene (T) units, Li et al.
[53,80] developed the randomized copolymers PNDI-Tx (A5),
where x is the percentage of single T vs. 2T. With enhanced back-
bone flexibility, these acceptor polymers show lower crystallinity
than P(NDI2OD-T2). By tuning the fraction of T, the authors
demonstrated that the best performing polymer, P(NDI-T10),
has medium domain sizes and balanced hole/electron mobilities,
which leads to a PCE of 6.6% using PBDTTS-FTAZ (D16) as the
donor polymer. The all-PSC performance is further improved
when blended with PTB7-Th (D4) as the donor polymer:
PCE = 9.0% with an excellent FF of 0.71. Recently, the same
group [81] developed a ternary all-PSC based on a blend of
P(NDI-T10) (A5) and two polymer donors, PTB7-Th (D4) and
PBDTTS-FTAZ (D16) (D4:D16:A5 = 1:0.15:1). Compared to con-
ventionally used binary blend systems, the addition of a second
donor broadens the photoactive layer absorption spectrum and
reduces carrier recombination loss, which leads to an impressive
PCE of 9.0% and a high FF of 0.73.
Another interesting series of random D-A-type NDI-based
copolymers was demonstrated by Li et al. [82,83], namely,
P[NDI-TT(m)-TVT(n)] (A6), which is based on NDI as the
electron-deficient unit, and randomly distributed thieno[3,2-b]
thiophene (TT) and TVT as the electron-rich moieties. Using
A6 with m:n = 1:1 and PTB7-Th (D4) as the donor polymer,
the all-PSC exhibits a PCE of 4.86% – a value higher than the
control devices using either P(NDI-TT) (PCE = 0.79%) or
P(NDI-TVT) (PCE = 2.94%) alone. This result is attributed to the
improved blend morphology using P(NDI-TT-TVT) as well as
more balanced SCLC electron and hole mobilities. In the same
group later study [83], by carefully tuning the TT-to-TVT ratios
from 1:3 to 3:1, the optical, charge transport properties, thin film
morphology, and photovoltaic performance using the random
copolymers of P(NDI-TT-TVT) can be precisely controlled. Using
a copolymer with m:n = 1:3, the authors demonstrated the high-
est efficiency of this series at 5.27% again using PTB7-Th (P4) as
the donor polymer.
Several other NDI-thiophene-based acceptors have been
investigated. Yuan et al. [84] synthesized a series of fused-
thiophene containing NDI copolymers, P(NDI-xfTh) (x = 2–4)
(A7). Despite a modest PCE of 0.13% when employing P3HT
(D1):P(NDI-4fTh) (A7) as the active layer, this work demon-
strated the ability to engineer different polymer band structures
and charge carrier mobilities by varying the number of fused
thiophenes. Xue et al. [85] also compared different fused-
thiophene containing NDI copolymers with different side chains
and demonstrated a far greater PCE of 5.10% using P(NDI-TDT)
(A8) and J51 (D12) as the donor polymer. Huang et al. [86]
developed a novel series of electron-neutral alkoxy-
functionalized thienyl-vinylene (TVTOEt) building blocks with
NDI as the acceptor moiety. The OS interactions between the
alkoxy group and the S atom of thiophenes promote macro-
molecular planarity. Using TVTOEt-NDIR (A9) with PTB7 (D2),
a PCE of 1.70% was achieved. Recently, the Kim group [87]
reported a novel series of NDI acceptors incorporating the
electron-withdrawing cyanovinylene group into the backbone
P(NDICVT-R) (A10). This moiety promotes a large dipole
moment difference between the ground and excited states,
Please cite this article in press as: N. Zhou, A. Facchetti, (2018), https://doi.org/10.1016/j.mattod.2018.02.003
RESEARCH
Dlge, resulting in a high PCE of 7.4% when PBDTTTPD (D15) is
used vas the donor polymer.
In donor polymer:fullerene PSCs, fluorination of the donor
polymer is an established strategy for improving polymer crys-
tallinity and the device performance [88]. For all-PSCs, Jen’s group
[89] demonstrated that the fluorination of a NDI-containing
acceptor polymer can afford better molecular organization and
film crystallinity as well as enhance charge-carrier mobility. Using
this strategy, the authors have demonstrated a PCE of 6.71% using
a PTB7-Th (D4):P(NDI2DT-FT2) (A11), primarily because of the
higher electron mobility and higher crystallinity of A11 than that
of P(NDI2OD-T2) (A1). Other fluorination strategies have also
been explored. For example, recently Deng et al. [90] synthesized
a regioregular difluorobenzene-containing NDI polymer acceptor,
P(NDIT-FB-T) (A12), and achieved a PSC with PCE of 5.20%.
Replacing thiophenes with their derivatives presents an inter-
esting strategy to further fine-tune the optoelectronic and mor-
phology characteristics of NDI-based acceptors. For example,
replacing TVT moieties with furanylene–vinylene–furanylene
(FVF) as the donor co-unit introduces another interesting accep-
tor copolymer, P(FVF-NDI) (A13) [91] which demonstrates a PCE
of 5.21% using J51 (D12) as the donor polymer. Replacing thio-
phenes with selenophenes has been demonstrated to enhance
polymer crystallinity and all-PSC efficiencies. Jenekhe’s group
[92,93] first reported polymer acceptors of NDI copolymerized
with oligoselenophene monomers: P(NDIBS) (A14) and
P(NDIS-HD) (A15). Using PSEHTT (D17) and P(NDIBS) (A14)
as the active layer blend, they obtained a PCE of 3.16%. The
all-PSCs using P(NDIS-HD) (A15) shows a significant improve-
ment over all-PSCs using its NDI-thiophene counterpart, PNDIT.
The superior all-PSC efficiency using P(NDIS-HD) (A15) is
mainly due to its significantly enhanced Jsc. Thanks to the larger
atomic radius of selenium compared to sulfur, the replacement of
thiophenes with selenophenes results in shorter d100 spacing,
thus greater p-overlap, of NDI-selenophene compared to NDI-
thiophene, which enhances active layer morphology and charge
transport properties. Using the same acceptor polymer
P(NDIS-HD) (A15) and a small bandgap donor polymer,
PTB7-Th (D4), the same group [48] have demonstrated a PCE
of 7.7% with a Jsc of 18.8 mA cm2 and 85% peak EQE thanks
to the balanced electron and hole transport in the active layers.
Kim and Jin groups [94] also used P(NDIS-HD) (A15) with a
fluorinated donor polymer, BDT-F (D18), and demonstrated a
PCE of 7.13%. To study the effect of side chains on NDI-
selenophene polymers, in 2014, Jenekhe group [95] also synthe-
sized a series of acceptor copolymers, P(NDIS-xBO) (x = 10, 30,
50) (A16), containing an identical NDI-selenophene backbone
structure but different compositions of the alkyl chains, namely
DT and BO. Their systematic studies on side chain engineering
resulted in an effective strategy for fine-tuning polymer–polymer
blend morphology, leading to a PCE of 4.44%.
Another interesting approach is the copolymerization of both
NDI and perylene diimide (PDI) moieties into polymer
backbones. Jenekhe group [96] developed a series of NDI-
selenophene/PDI-selenophene random copolymers (A17) which
are blended with a crystalline donor polymer, PBDTTT-CT (D19).
By varying the PDI to NDI ratio, the authors discovered that the
crystallinity of the acceptor polymer can be precisely controlled.
11
RESEARCH
Specifically, the increase in PDI content results in a decrease of
polymer crystallinity and increase of the p-p stacking distance.
When x = 30% (30PDI, A17), the all-PSCs show optimized
morphology and significantly enhanced PCE of 6.29%
when compared to the control device using PBDTTT-CT
(D19):P(NDIS-HD) (A15) (PCE = 1.36%). A similar copolymeriza-
tion method has been demonstrated by Sharma et al. [97] The
inclusion of PDI as a co-acceptor unit with NDI successfully
reduces the large size domains formed using P(NDI2OD-T2).
Interestingly, 30 mol% of PDI is also found as the best perform-
ing polymer in the investigated series of NDI-Th-PDIx (x = 0.15,
0.3, 0.5) (A18) (PCE = 4.98% using PTB7-Th, D4, as the donor
polymer), which is attributed to the relatively low polymer crys-
tallinity and high exciton dissociation energy using random
copolymers.
NDI acceptor polymers copolymerized with other donor co-
moieties
The ability to combine NDI with various donor co-moieties
opens the possibility to realize several other D–A type acceptor
polymers. Thus, in addition to oligothiophenes and thiophene
derivatives as co-monomers discussed above, other (hetero)aro-
matic co-units have also been successfully polymerized with
the NDI core, and they are included in Fig. 5. Schubert et al.
[66] developed a P(NDI-TCPDTT) (A19) copolymer by inserting
a cyclopentadithieno (CPDT) group into the P(NDI2OD-T2)
backbone. The use of tetralin as solvent suppresses the aggrega-
tion of P(NDI-TCPDTT), which leads to an improved PCE up to
1.1% using P3HT (D1) as the donor polymer. Zhou et al. [98]
synthesized a new polymer based on NDI and fluorene
(F), PF-NDI (A20). The resulting all-PSCs based on P3HT
(D1):PF-NDI (A20) presents a PCE of 1.63%. Geng et al. [99]
developed a new P(DTS-NDI) (A21) copolymer by combining
NDI with a dithienosilole (DTS) group, and demonstrated a
PCE of 1.19% with TTV2 (D20) as the donor polymer.
Liu et al. [100] synthesized two acceptor polymers incorporat-
ing a benzothiadiazole (BT) moiety, P(NDIBTH) (A22) and P
(NDIBTOC8) (A23). The installation of alkoxy side chains onto
BT in P(NDIBTOC8) helps elevate the LUMO energy level, which
leads to a higher Voc of 0.90 V and a higher PCE of 3.14% com-
pared to P(NDIBTH) (Voc = 0.76 V and PCE = 1.20%) when using
the same donor polymer, PBDTTT-CT (D19). Recently, Weng
et al. [101] synthesized a n-type copolymer containing NDI
and 1,3,4-thiadiazole (TZ), P(NTZ) (A24), which reduces the con-
formational disorder of P(NDI2OD-T2), and a PCE of 4.35%
using PTB7-Th (D4) as the donor polymer was demonstrated.
Adopting a benzo[1,2-b:4,5-b0 ]dithiophene (BDT) building block
which is widely used for p-type donor polymers, Ye et al. [102]
developed a new acceptor polymer, P(BDTNDI-T) (A25), by com-
bining NDI with a alkylthiothiophene-substituted BDT. A 2.88%
PCE is demonstrated using PBDTBDD-T (D21) as the donor
polymer. Xue et al. [103] combined indacenodithienothiophene
(IDT) and NDI, and developed a new n-type polymer P(IDT-NDI)
(A26) for all-PSCs. A PCE of 5.33% is obtained using J51 (D12) as
the donor polymer. Finally, Dai et al. [104] combined PDI, NDI,
and IDT, and synthesized a three-component acceptor polymer,
P[PDIx%-co-NDI(1x)%] (A27), and the highest all-PSC perfor-
mance is found when x = 25. The authors also compared the
12
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Materials Today d Volume xxx, Number xx d xxxx 2018
device performance using a binary blend of P3HT (D1):PPDI25-
co-NDI75 (A27) with a ternary blend of P3HT:PPDI100:PNDI100
employing the same PDI, NDI, and IDT component molar ratio.
Interestingly, the binary blend shows significant enhancement
in PCE (1.45%) vs. the ternary blend (0.80%). The performance
improvement is attributed to less phase separation using the
three-component copolymer which leads to higher SCLC mobil-
ities and Jscs in the active layers.
Acceptor polymers based on core-extended
naphthodithiophene diimide (NDTI)
A relatively new building block based on NDI is the core-
extended naphtho[2,3-b:6,7-b0 ]dithiophene-4,5,9,10-diimide
(NDTI) (Fig. 6). This unit was first introduced by Zhou et al.
[105] in 2014 as a building block of n-type polymer acceptors
for all-PSCs. The acceptor copolymer containing NDTI and
bithiophene, P(NDTI-BT-DT) (A28), shows an extended absorp-
tion spectrum up to 900 nm. When blended with PTB7 (D2), a
PCE of 2.59% was demonstrated for all-PSC. This research was
followed by another comprehensive study on polymer acceptors
of NDTI copolymerized with thiophene [P(NDITI-T), A29],
thienothiophene [P(NDIT-TT), A30], and dithienothiophene
[P(NDIT-DTT), A31] [106]. Interestingly, the variation in donor
co-moieties leads to different polymer orientation in the film:
P(NDIT-TT) shows an edge-on orientation whereas P(NDITI-T)
and P(NDIT-DTT) show a face-on orientation of the polymer
chains. The different chain orientations of p-conjugated poly-
mers lead to enhanced electron transport favorable either for
field effect transistors (FETs, edge-on) or for all-PSCs (face-on).
All-PSCs with PCEs of 2.0% and 3.2% are demonstrated using
the two face-on orientation polymers, P(NDITI-TT) (A30) and
P(NDITI-DTT) (A31), respectively. Recently, Yang et al. [107]
used a blend of PBDTBDD-T (D21):P(NDITI-DTT) (A31), and
improved PCE to 5.57%. The high PCE was attributed to the
broad, complementary absorption by the donor and acceptor
polymers, as well as the well-balanced hole and electron trans-
port in the blend films.
Outlook and perspectives
The discovery of several NDI-based polymer semiconductors is
playing an increasingly important role in the development of
all-PSCs. Their complementarity, and for some aspects unique
advantages, compared to fullerene derivatives include chemical
tunability, enhanced mechanical flexibility, and ambient/opera-
tion stability, combined with processing versatility. In summary,
to further improve all-PSC performance to ultimately achieve
PCEs >15%, a synergistic optimization strategy should focus on
both molecular design and device processing. The general design
guidelines for all-PSCs employing NDI-based acceptor polymers
should follow: (a) Careful selection of the donor and acceptor
polymers to achieve proper energy cascades and complementary
optical absorption. (b) Rational design of D-A type p-conjugated
structures which can self-assemble with moderate crystallinity
and form domains with face-on oriented polymer chains favor-
ing electron transport perpendicular to the substrate. (c) Design
of polymers with proper molecular weight and backbone side
chains to afford good solution processability and depress aggre-
gation, however, without disrupting substantial intermolecular
Materials Today d Volume xxx, Number xxx d xxxx 2018
interactions. At the device level, one should consider: (a) Selec-
tion of proper processing solvents and use of processing additives
to achieve optimal BHJ morphology and a good interpenetrating
network of the donor and acceptor polymer domains. (b) Balance
donor/acceptor weight content in BHJ blend to obtain optimal
absorptivity throughout the spectrum and proper domain size
and phase separation. (c) Optimization of blend morphology
by post-film deposition thermal and solvent annealing. (d) Opti-
mization of charge extraction by using proper interfacial layers
and electrodes.
Beyond the studies summarized above in this review, several
recent reports point to other exciting applications using NDI
polymers. e.g., as electron transport layers for polymer:fullerene
cells [108]; as n-type interfacial layers for silicon-organic hetero-
junction solar cells [109]; as electron transport layers for per-
ovskite solar cells [110]. Lastly, regarding polymer synthesis,
unlike the traditional Stille polycondensation methods which
involve environmentally harmful organotin compounds, recent
reports also show interests in developing NDI conjugated poly-
mers via carbon–hydrogen (C–H) direct arylation polycondensa-
tion reactions, which represent an important step toward
environmentally benign synthetic methodologies for high-per-
formance n-type semiconductors [111–114]. Thanks to a collec-
tive effort on design, structure, and understanding of polymer
chemistry and physics, the NDI unit and the corresponding poly-
mers hold a great promise for next-generation photovoltaics,
which could become a ubiquitous, portable, flexible, and sustain-
able power source soon.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.mattod.2018.02.
003.
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