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Recent advances, challenges and prospects in

Cite this: Nanoscale, 2021, 13, 2181
ternary organic solar cells
Congcong Zhao,a Jiuxing Wang, *a Xuanyi Zhao,a Zhonglin Du, *a
Renqiang Yang *b and Jianguo Tang *a

Received 31st October 2020,
Accepted 22nd December 2020
DOI: 10.1039/d0nr07788g
rsc.li/nanoscale
The past decade has seen a tremendous development of organic solar cells (OSCs). To date, high-per-
formance OSCs have boosted power conversion efficiencies (PCEs) over 17%, showing bright prospects
toward commercial applications. Compared with binary OSCs, ternary OSCs, by introducing a third com-
ponent as a second donor or acceptor into the active layer, have great potential in realizing outstanding
photovoltaic performance. Herein, a comprehensive review of the recent advances of ternary solar cells is
presented. According to the chemical components of active layer materials, we classify the ternary
systems into four categories, including polymer/small molecule/small molecule, polymer/polymer/small
molecule, all-polymer and all-small-molecule types. The relationships among the photovoltaic materials
structure and weight ratio, active layer morphology and photovoltaic performance are systematically ana-
lyzed and summarized. The features and design strategies of each category are also discussed and sum-
marized. Key issues and challenges faced in ternary OSCs are pointed out, and potential strategies and
solutions are proposed. This review may provide guidance for the field of ternary OSCs.

a
Institute of Hybrid Materials, National Center of International Joint Research for
Hybrid Materials Technology, National Base of International Sci. & Tech.
Cooperation on Hybrid Materials, College of Materials Science and Engineering,
Qingdao University, 308 Ningxia Road, Qingdao 266071, China.
E-mail: jiuxingwang@qdu.edu.cn
b an ideal alternative energy resource, due to its clean and rich
Key Laboratory of Optoelectronic Chemical Materials and Devices (Ministry of
Education), School of Chemical and Environmental Engineering, Jianghan University,
Wuhan 430056, China. E-mail: yangrq@qibebt.ac.cn
1. Introduction
Due to the increasing global consumption of fossil fuels and
serious problems of energy shortage, exploiting renewable and
environmentally friendly energy resources has become an
urgent issue around the world. Solar energy is considered as
reserve advantages. Silicon-based solar cells have already been
commercialized, but complex manufacture and high cost limit

Congcong Zhao received his B.S.
degree in Materials Science and
Engineering from Liaocheng
University in 2018. He is cur-
rently pursuing his M.S. degree
at the National Center of
International Joint Research for
Hybrid Materials Technology of
Qingdao University under the
supervision of Dr Jiuxing Wang.
His research interests are the
design and synthesis of efficient
Congcong Zhao organic and polymer materials
in solar cells.
Jiuxing Wang received his B.S.
degree in Polymer Materials and
Engineering from Sichuan
University in 2011 and Ph.D.
degree in Chemical Engineering
with Prof. Renqiang Yang from
the University of Chinese
Academy of Sciences in 2016. He
has been an assistant professor
at the National Center of
International Joint Research for
Hybrid Materials Technology of
Jiuxing Wang Qingdao University since 2016.
His research interests focus on
organic and polymer materials
for photovoltaic applications.

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Fig. 1 Schematic of OSC structures: (a) single-layer OSCs, (b) bilayer
OSCs, (c) binary BHJ OSCs, (d) tandem OSCs, and (e) ternary OSCs.
their further applications. In the past decades, organic solar
cells (OSCs) have become a hot-spot topic in photovoltaic
fields owing to their unique advantages such as light weight,
low cost, mechanical flexibility and solution processability.1–4
The rapid development of various donor and acceptor
materials greatly improves the PCEs of OSCs.5–11
OSC device configurations include single-layer, bilayer,
bulk-heterojunction (BHJ), tandem and ternary structures.
The first single-layer organic photovoltaic cell (Fig. 1a) was
reported by Kearns and Calvin in 1958.12 The maximum
power output was only 3 × 10−12 W, due to low-efficiency
charge separation. Thereafter, much research attention has
been paid to this emerging field.13–15 In 1986, Tang reported
the first bilayer solar cell (Fig. 1b).16 However, limited inter-
facial area and insufficient charge transport restricted the
PCE to 1%. In 1995, the concept of BHJ was introduced by
Heeger and coworkers to overcome the difficulties of short
exciton diffusion length and limited exciton lifetime.17 In a
BHJ structure (Fig. 1c), both donor and acceptor materials are
mixed together to form a bi-continuous interpenetrating
Zhonglin Du received his Ph.D.
degree from East China
University of Science and
Technology (ECUST) in 2017
under the supervision of
Professor Xinhua Zhong. He
worked as a postdoctoral fellow
with professor Dongling Ma at
the Institut National de la
Recherche Scientifique (INRS) of
Canada from 2019 to 2021.
Currently, he is an associate pro-
Zhonglin Du fessor at the National Center of
International Joint Research for
Hybrid Materials Technology of Qingdao University. His main
research interests include photoelectronic functional organic–in-
organic hybrid materials and their application in solar energy con-
version, especially photocatalysis and solar cells.
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network with large interfacial area for efficient exciton dis-
sociation. To date, the BHJ structure has become the most
widely used architecture in OSCs. With the rapid develop-
ment of materials design and device optimization, the PCEs
of single-junction OSCs have exceeded 17%, demonstrating
great potential for large-area manufacture and commerciali-
zation in the future.18
Generally, the active layer in the OSC is very thin (∼100 nm),
in order to achieve efficient charge collection. However, such a
thin blend film leads to insufficient photon harvesting, which
limits further enhancement in the performance of single-junc-
tion OSCs. To address this issue, several strategies focusing on
how to absorb a broad range of the solar spectrum in solar cell
devices have been developed. Constructing tandem (Fig. 1d)
and ternary device structures (Fig. 1e) is an efficient strategy to
extend light absorption and improve PCE. Tandem OSCs
consist of two or more single-junction solar cells, which are
linked either in series or in parallel.19 The individual sub-cells
work independently to absorb photons in different ranges of
the solar spectrum. To fully utilize sunlight, the wide- and low-
bandgap sub-cells are usually used as front and rear cells,
respectively. However, the complicated fabrication of tandem
OSCs may increase the cost.27
The active layer of binary OSCs is composed of one donor
(D) and one acceptor (A). The working mechanism of binary
OSCs can be summarized as follows. Firstly, the photo-
excitation of photovoltaic materials in the active layer gener-
ates electron–hole pairs, known as excitons. Secondly, the exci-
tons diffuse to the donor–acceptor interface. Thirdly, the exci-
tons dissociate at the donor–acceptor interface to form free
electrons and holes. Finally, free holes transport to the anode
through the donor material and free electron transport to the
cathode through the acceptor material. Ternary OSCs have a
composition of either one donor/two acceptors (D : A1 : A2) or
two donors/one acceptor (D1 : D2 : A) in the active layer. In
Renqiang Yang received his
Ph.D. degree from South China
University of Technology in 2004
and then conducted his postdoc-
toral work at the University of
California Santa Barbara with
Prof. Guillermo C. Bazan. In
2009–2019, he worked as a full
professor at Qingdao Institute of
Bioenergy and Bioprocess
Technology, Chinese Academy of
Sciences. Currently he is a full
Renqiang Yang professor at the School of
Chemical and Environmental
Engineering, Jianghan University. His research interests include
molecular design and synthesis of advanced organic opto-elec-
tronic materials and device applications thereof.
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Fig. 2 The comparison of PCEs of representative categories of binary
and ternary OSCs. (a) Blue bar: PBDB-TF : Y6,20 red bar:
PBDB-TF : Y6 : PC61BM20 ( polymer donor/non-fullerene acceptor/fuller-
ene acceptor). (b) Blue bar: PM6 : Y6,21 red bar: PM6 : Y6 : BTP-M21
( polymer donor/non-fullerene acceptor/non-fullerene acceptor). (c)
Blue bar: PTB7-Th : PC71BM,22 red bar: PTB7-Th : DR3TSBDT : PC71BM22
( polymer donor/small-molecule donor/fullerene acceptor). (d) Blue bar:
PTB7-Th : FOIC,23 red bar: PTB7-Th : TR : FOIC23 ( polymer donor/small-
molecule donor/non-fullerene acceptor). (e) Blue bar: PM6 : Br-ITIC,24
red bar: PM6 : J71 : Br-ITIC24 ( polymer/polymer/small molecule). (f ) Blue
bar: PTzBI : N2200,25 red bar: PTzBI : PBTA-BO : N220025 (all-polymer).
(g) Blue bar: DPP-2TTP : DR3TBDTTF,26 red
DPP-2TTP : DR3TBDTTF : PC71BM26 (all small molecule).
recent years, ternary OSCs have emerged as a competitive can-
didate to achieve high photovoltaic performances. As shown in
Fig. 2, the ternary OSCs usually outperform their binary
counterparts. Until now, various third components including
polymers, fullerene derivatives and small molecules have been
used in ternary OSCs. Compared with binary OSCs, ternary
OSCs have distinct advantages. (i) The third component can
Jianguo Tang received his Ph.D.
degree from Shanghai Jiaotong
University in 2000, after which
he worked at the University of
Bayreuth as a visiting professor
(2001). Then he joined Prof. L. A.
Belfiore’s group at Colorado
State University as a research
fellow (2002–2003). Currently he
is the director of the National
Center of International Joint
Research for Hybrid Materials at
Jianguo Tang Qingdao University. His research
interests include hybrid organic–
inorganic luminescent materials
and solar cells.
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enhance the absorption, which is favourable for increasing the
short circuit current density ( Jsc).28 However, some studies
indicated that it is not always the case unless the ternary blend
has quite narrow absorption.29 (ii) The third component can
also increase exciton dissociation and charge mobility by
building efficient charge transport pathways, resulting in high
fill factors (FF) in OSCs.30 (iii) The morphologies of active
layers in ternary OSCs could be optimized by the addition of
the third component.31 (iv) The Voc in ternary OSCs varies as a
function of the blend ratio, and it could be more easily and
finely tuned than that in binary devices.32,33 The strategies for
improving the photovoltaic performance of binary OSCs, such
as tuning energy levels, adjusting donor : acceptor blend ratios
and controlling phase separation, can also be applied in
ternary OSCs. However, the disadvantages of ternary OSCs
should also be noted. For some ternary systems, the introduc-
tion of the third component might lead to a more complex
morphology, which may give rise to difficulty in morphology
control. The Voc value of the ternary OSCs is in between those
of the two original binary OSCs, lower than the higher one of
the two binary OSCs. Despite these disadvantages, ternary
OSCs show great potential for high-performance solar cells.
The highest PCE of over 17% of ternary OSCs has been
reported recently, showing great potential for constructing
highly efficient OSCs.21
Typically, four working mechanisms could be involved in a
bar: ternary OSC: charge transfer, energy transfer, parallel-like
model and alloy model. In the charge transfer mechanism
(Fig. 3a), the highest occupied molecular orbital (HOMO) and
lowest unoccupied molecular orbital (LUMO) energy levels of
the third component are located between those of the host
donor and acceptor, forming a cascade energy level align-
ment.34 This cascade energy level can facilitate charge separ-
ation and charge transfer at the D : A interface because the
third component can function as a charge relay for electron
and hole transport.35 As for the energy transfer mechanism
(Fig. 3b), the third component does not directly generate free
charges but transfers the energy to either a donor or an accep-
tor through Dexter or Förster resonance energy transfer
Fig. 3 Schematic of the working mechanisms in ternary OSCs: (a)
charge transfer, (b) energy transfer, (c) parallel-like model and (d) alloy
model.
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Fig. 4 The classification of ternary OSCs.
(FRET). In some cases, the mechanisms of charge transfer and
energy transfer can simultaneously exist in a ternary blend. In
the parallel-like model (Fig. 3c), the third component forms its
independent hole-transport channels.36 In the alloy model
(Fig. 3d), the third component electronically couples with the
host donor to form a new charge transfer state.37
According to the possible combinations of three com-
ponents, all the ternary OSCs can be classified into four cat-
egories including polymer/small molecule/small molecule,
polymer/polymer/small molecule, all-polymer and all-small-
molecule types (Fig. 4). In this review, we have summarized the
recent progress of ternary OSCs and analyzed the relationships
among the molecular structure, active layer morphology and
photovoltaic performance. Especially, we have emphasized the
critical roles of the third component in ternary blends. Finally,
the potential challenges and promising outlook for ternary
OSCs are also discussed.
2. Recent advances in ternary
organic solar cells
2.1 Polymer/small molecule/small-molecule OSCs
In this type of ternary OSC, a small molecule as a third com-
ponent adding to the active layer can not only extend the
absorption which is beneficial for harvesting more photons, but
also improve the crystallinity of the polymer and tune active
layer morphology through the effect of small molecules.38–40
Two non-fullerene acceptors or mixed acceptors composed of a
fullerene acceptor and an non-fullerene acceptor could be used
in this type of ternary device, and thereby it can be classified
into four categories, which are polymer donor/non-fullerene
acceptor/fullerene acceptor, polymer donor/non-fullerene accep-
tor/non-fullerene acceptor, polymer donor/small-molecule
donor/fullerene acceptor, and polymer donor/small-molecule
donor/non-fullerene acceptor types.
(a) Polymer donor/non-fullerene acceptor/fullerene accep-
tor OSCs. Polymer donor/non-fullerene acceptor/fullerene
acceptor ternary OSCs combine the advantages of the high
electron mobility of the fullerene acceptor and broad absorp-
tion of the narrow bandgap non-fullerene acceptor. Over the
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past few years, many effective polymer donor/non-fullerene
acceptor/fullerene acceptor ternary OSCs with PCEs over 10%
have been developed.41–44 In these systems, fullerene deriva-
tives such as phenyl-C61-butyric acid methyl ester (PC61BM)
and phenyl-C71-butyric acid methyl ester (PC71BM) have been
commonly used as the third component to strengthen the
light-harvesting capability, facilitate charge dissociation and
tune the morphology of active layers, and thus lead to
enhanced Jsc and PCE.45–48 The structures of donors and
acceptors for polymer donor/non-fullerene acceptor/fullerene
acceptor ternary OSCs are shown in Fig. 5, and the photovol-
taic parameters are summarized in Table 1.
In 2019, Zou’s group first reported the non-fullerene accep-
tor Y, which promotes the progress of OSCs with a high PCE
over 15%, and Y6-based systems have been widely applied and
investigated to date.49 To further improve the PCEs of Y6-
based OSCs, Hou’s group incorporated PC61BM into a
PBDB-TF : Y6 blend to fabricate ternary OSCs.20 After the incor-
poration of 14% PC61BM, the hole mobilities (µh) and electron
mobilities (µe) of the PBDB-TF : Y6 : PC61BM (1 : 1.2 : 0.2) blend
were 2.5 and 2.1 × 10−4 cm2 V−1 s−1, respectively, leading to a
balanced charge transport process. Furthermore, PC61BM can
inhibit the high tendency to crystallize and aggregate in Y6,
which resulted in a high electroluminescence quantum
efficiency of 1.9 × 10−4 and a reduced non-radiative energy loss
(Eloss) of 0.22 eV. On introducing PC61BM to the PBDB-TF : Y6
blend, atomic force microscopy (AFM) measurements showed
that the optimal ternary blend exhibited a root-mean-square
(RMS) roughness of 2.64 nm, indicating that the large aggre-
gates in the PBDB-TF : Y6 blend were decreased. Benefiting
from these advantages, an open-circuit voltage (Voc) of 0.845 V,
a Jsc of 25.4 mA cm−2, an FF of 77.0% and a high PCE of 16.5%
were achieved. Ge et al. reported a flexible ITO-free ternary
OSC based on a PM6 : Y6 : PC71BM blend.50 As the 2D GIWAXS
patterns show in Fig. 6, the introduction of the PC71BM com-
ponent into PM6 : Y6 blends resulted in obvious (010) stacking
peaks in an out-of-plane (OOP) direction at 1.744 Å−1 (d =
3.60 Å), which demonstrated that the face-on orientation was
still maintained in the ternary blend film. The AFM image of
the PM6 : Y6 : PC71BM blend showed a well-mixed morphology
with an RMS roughness of 1.25 nm, which was slightly higher
than that of the PM6 : Y6 blend (0.964 nm). As shown in
Fig. 7d, the flexible devices exhibited excellent mechanical per-
formance. When the cylinder radius was 7.5 mm in the
bending test, the PCE of the flexible devices could still remain
at ∼98%. The optimal photovoltaic performances were: Voc =
0.828 V, Jsc = 23.57 mA cm−2, FF = 72.03%, and PCE = 14.06%.
Zhan et al. added PC71BM into the PM6 : Y6 system to increase
the Voc and phase purity of the devices.51 The lowest unoccu-
pied molecular orbital (LUMO) energy level of PC71BM was
higher than that of Y6, and lower than that of PM6. On blend-
ing PC71BM with a ratio of 1 : 1 : 0.2 for PM6 : Y6 : PC71BM, the
device Voc was increased from 0.848 to 0.861 V. Transmission
electron microscopy (TEM) and AFM measurements demon-
strated that the phase purity was also increased from 0.883 in
the binary blend to ∼1 in the ternary blend. Due to the stron-
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Fig. 5 The structures of donors and acceptors for polymer donor/non-fullerene acceptor/fullerene acceptor ternary OSCs.

ger absorption of PC71BM in the 300–700 nm wavelength Apart from Y6-based systems, fullerene derivatives were
region, a Jsc of 25.1 mA cm−2, an FF of 77.2%, and an impress- applied in conjunction with indacenodithiophene (IDT)-based
ive PCE of 16.7% were achieved. acceptors in ternary OSCs. In 2019, Sun’s group reported a

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Table 1 Photovoltaic parameters of ternary OSCs with polymer donor/non-fullerene acceptor/fullerene acceptor blends

Fullerene A2 Weight ratio FF PCE Working

Polymer (D) Non-fullerene A1 (third component) (D : A1 : A2) Voc (V) Jsc (mA cm−2) (%) (%) mechanism Ref.

PBDB-TF Y6 PC61BM 1 : 1.2 : 0.2 0.845 25.4 77 16.5 — 20

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PM6 Y6 PC71BM 1 : 1 : 0.2 0.828 23.57 72.03 14.06 Energy transfer 50

PM6 Y6 PC71BM 1 : 1 : 0.2 0.861 25.1 77.2 16.7 Energy transfer 51
PBT1-C IT-2F PC71BM 1 : 1 : 0.2 0.892 18.19 75.1 12.19 Energy transfer 52
PBT1-C ITIC-2Cl IC60BA 1 : 0.8 : 0.2 0.89 19.58 76.8 13.4 Energy transfer 53
PTB7-Th 3TT-FIC PC71BM 1 : 1.2 : 0.3 0.669 27.73 73 13.54 — 54
PBDTTPD-HT ITIC PC71BM 1 : 0.9 : 0.6 0.95 17.38 74 12.09 Parallel-like model 55
PTBTz-2 IT-M PC71BM 1 : 1 : 0.2 0.928 18.7 70.78 12.28 Energy transfer 56
P3TCO-1 ITIC PC71BM 1 : 1 : 0.2 0.941 18.16 66.78 11.41 Charge transfer 57
J52 IEICO-4F PC71BM 1 : 0.9 : 0.6 0.698 22.70 67.4 10.68 — 58
PTBTz-2 ITIC PC71BM 1 : 1 : 0.35 0.89 20.75 60.94 11.26 — 59
PBDB-T ITM Bis-PC71BM 1 : 1 : 0.2 0.952 17.39 73.7 12.20 Energy transfer 60
PTB7-Th COi8DFIC PC71BM 1 : 1.05 : 0.45 0.70 16.21 60.2 14.08 — 61
PPBDTBT ITIC PC71BM 1 : 1.2 : 0.8 0.898 16.82 68.26 10.41 Charge transfer 62

high efficiency ternary OSC with improved ambient stability by

Fig. 6 GIWAXS images of PM6 : Y6 : PC71BM blend films with different
ratios: (a) 1 : 1.2 : 0; (b) 1 : 1 : 0.2; and (c) 1 : 0 : 1.2; (d) GIWAXS intensity
profiles along the in-plane (dotted line) and out-of-plane (solid line)
directions; and AFM images (2 μm × 2 μm) of films with blend ratios of
(e) 1 : 1.2 : 0 and (f ) 1 : 1 : 0.2. Reproduced with permission.50 Copyright
2019, Wiley.
adding PC71BM into a PBT1-C : IT-2F blend.52 The three
materials showed complementary absorptions across the
whole visible region. AFM images indicated that the crystalline
aggregates of IT-2F were suppressed after adding PC71BM with
decreased RMS roughness from 1.69 to 1.11 nm, leading to a
reduced trap-assisted recombination. The Voc of the ternary
device was improved because of the higher lying LUMO energy
level of PC71BM than that of IT-2F. At a ratio of 1 : 1 : 0.2 of
PBT1-C : IT-2F : PC71BM, a maximum PCE of 12.19% was
achieved, together with a Voc of 0.892 V, a Jsc of 18.19 mA
cm−2, and an FF of 75.1%. To study the morphology of ternary
OSCs, the same group used an indene-C60 bisadduct (IC60BA)
as the second acceptor in the PBT1-C : ITIC-2Cl blend.53 The
addition of 20% IC60BA disturbed the intermolecular π–π
stacking of crystalline ITIC-2Cl and then improved the film
morphology. As a consequence, the RMS roughness of the film
decreased from 1.70 to 1.28 nm (Fig. 8), leading to balanced
charge mobility. The optimal device exhibited an impressive
PCE of 13.4%, with a Jsc of 19.58 mA cm−2, a Voc of 0.89 V, and
a high FF of 76.8%. Chen et al. reported that the introduction
of PC71BM could increase the PCE of the PTB7-Th : 3TT-FIC
binary OSC from 12.21% to 13.54%.54 The enhancement of
PCE was mainly ascribed to the improved external quantum
efficiency (EQE) response in the visible range of 300–700 nm
with the addition of PC71BM. Meanwhile, the µe and µh of the

Fig. 7 (a) The schematic structure of the flexible device; (b) J–V curves;
(c) EQE spectrum; and (d) bending performance with different bending
diameters (10, 5, and 2 mm) based on the ternary devices with the
PM6 : Y6 : PC71BM photoactive layer in an optimized ratio of 1 : 1 : 0.2.
Reproduced with permission.50 Copyright 2019, Wiley.
Fig. 8 (a)–(e) TEM and (f)–( j) AFM height images of ternary blends with
different ICBA contents. Reproduced with permission.53 Copyright 2018,
Wiley.

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ternary device were 2.28 × 10−4 and 2.16 × 10−4 cm2 V−1 s−1,
respectively, which were slightly larger and more balanced
than those of the binary device (1.67 × 10−4 and 2.09 × 10−4
cm2 V−1 s−1). Jang et al. achieved high-performance ternary
devices based on PBDTTPD-HT : ITIC : PC71BM blends.55 The
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maximum charge generation rate (Gmax) value of 1.09 × 1028
for the ternary device was higher than that of the
PBDTTPD-HT : ITIC binary device (9.06 × 1027 m−3 s−1) and the
PBDTTPD-HT : PC71BM binary device (7.25 × 1027 m−3 s−1). In
addition, the incorporated PC71BM enhanced the ordering of
ITIC and was uniformly dispersed with sufficient continuity.
This favorable morphology resulted in significantly higher
charge generation and extraction of the ternary device. As a
result, a Voc of 0.95 V, a Jsc of 17.38 mA cm−2, an FF of 74%
and a PCE of 12.09% were achieved. Recently, Xia et al. studied
the synergistic effect of PC71BM and IT-M in a PTBTz-
2 : IT-M : PC71BM ternary OSC.56 2D GIWAXS patterns showed
that the diffraction signal at 3.50 nm−1 was enhanced by
doping 20% PC71BM in the blend film, indicating an increased
crystallinity of IT-M. Meanwhile, TEM measurements
suggested that a favorable phase separation was achieved,
which was beneficial for charge generation and collection in
OSCs. Therefore, the ternary OSCs exhibited a desirable PCE of
up to 12.28%, a Voc of 0.928 V, a Jsc of 18.70 mA cm−2 and an
FF of 70.78%. An et al. synthesized a new polymer, P3TCO-1,
with a twisted conjugated backbone to enhance the solubility
in organic solvents at room temperature.57 P3TCO-1 has a wide
optical bandgap of 1.90 eV and a deep HOMO energy level of
−5.39 eV. When the two acceptors of ITIC and PC71BM were
combined, the P3TCO-1-based ternary OSC exhibited a high
PCE of 11.41% with a simultaneously improved Jsc of 18.16 mA
cm−2 and an FF of 66.78%. Cao et al. fabricated ternary OSCs
based on a J52 : IEICO-4F : PC71BM ternary blend.58 The
addition of PC71BM into the J52 : IEICO-4F binary blend con-
tributed to the suppressed trap-assisted recombination and
enhanced charge extraction. Therefore, the PCE of the ternary
OSCs reached up to 10.68%, accompanied by a Jsc of 22.70 mA
cm−2 and an FF of 67.4%. Yang et al. used PTBTz-2 as a
polymer donor, and ITIC and PC71BM as two acceptors to fab-
ricate ternary OSCs.59 The performance of ternary devices was
enhanced when 35% PC71BM was added into the PTBTz-
2 : ITIC blend, resulting in an optimized PCE of 11.26% with a
high Jsc of 20.75 mA cm−2. The study showed that the addition
of PC71BM can not only affect the structural character of the
donor but also enhance the crystallization of ITIC in the in-
plane direction. Hou and coworkers introduced bis-PC71BM as
the third component into a PBDB-T : IT-M blend and fabri-
cated ternary OSCs.60 At a ratio of 1 : 1 : 0.2 for
PBDB-T : IT-M : bis-PC71BM, the ternary device exhibited an
outstanding PCE of 12.2%. The enhanced PCE was due to the
complementary light absorption of bis-PC71BM in the short
wavelength range from 380 to 550 nm and effective exciton
diffusion at the PBDB-T : bis-PC71BM and PBDB-T : IT-M blend
interface. Ding et al. reported a highly efficient ternary OSC
based on PTB7-Th, COi8DFIC and PC71BM.61 The PC71BM
enlarged light absorption at short wavelengths, facilitated elec-
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tron transfer from PTB7-Th to COi8DFIC and optimized the
morphology of the active layer, leading to a high Jsc of
16.21 mA cm−2 and an FF of 60.2%. When the ratio of PTB7-
Th : COi8DFIC : PC71BM was 1 : 1.05 : 0.45, the ternary solar
cells gave a PCE of 14.08%. Bo and coworkers employed
PC71BM and ITIC as small-molecule acceptors to fabricate
PPBDTBT-based ternary devices.62 PC71BM can disrupt the
molecule stacking of ITIC to reduce its aggregation, leading to
increased D/A interface area in the blend films. Meanwhile,
the cascade-like energy levels of the three components can
facilitate charge transfer at the D/A interfaces. Consequently,
at the PPBDTBT : ITIC : PC71BM ratio of 1 : 1.2 : 0.8, the ternary
solar cell gave a PCE of 10.41%, a Voc of 0.898 V, a Jsc of
16.82 mA cm−2 and an FF of 68.26%.
As analyzed above, the use of fullerene derivatives as the
third component in the non-fullerene blends can often
improve the device performance, which can be ascribed to: (a)
enhanced absorption in the short-wavelength region by the
fullerene derivatives; (b) the intrinsic advantages of high elec-
tron affinity, high electron mobility and isotropic charge trans-
port, enabling fullerene derivatives to promote efficient charge
separation in blend films; and (c) the addition of fullerene
derivatives often inhibiting the aggregation of acceptors,
showing a decreased phase separation size.
(b) Polymer donor/non-fullerene acceptor/non-fullerene
acceptor OSCs. Most recently, great efforts have been devoted
to the non-fullerene ternary OSCs due to the advantages of
non-fullerene acceptors, such as easily tunable energy levels,
strong light absorption, and high stability.22,63–67 Thus many
highly efficient non-fullerene acceptors have been developed,
such as indacenodithiophene (IDT)-based, arylene imide-
based and diketopyrrolopyrrole-based small molecules.68,69
The new emerging highly efficient acceptors show various
absorption spectra and energy levels, suggesting great poten-
tial in constructing high-performance ternary OSCs. In a non-
fullerene ternary OSC, the two acceptors with similar struc-
tures are usually selected to form an alloy-like composite due
to their good compatibility.70–74 The energy levels and crystalli-
nity of the composite can be further adjusted by changing the
ratios of blends. The structures of donors and acceptors for
polymer donor/non-fullerene acceptor/non-fullerene acceptor
ternary OSCs are shown in Fig. 9, and the photovoltaic para-
meters are summarized in Table 2.
In several studies, benzothiadiazole (BT)-based non-fuller-
ene acceptors were rationally employed as the third com-
ponents in ternary OSCs. In 2020, Chen’s group reported a
new non-fullerene acceptor named BTP-M as the third com-
ponent for the PM6 : Y6 binary system.21 As an analogue of Y6,
electron-donating methyl groups were introduced at the term-
inals of BTP-M to elevate the LUMO energy level of the accep-
tor alloy (Y6 : BTP-M). With the addition of 20% BTP-M, the Voc
was increased from 0.844 to 0.875 V, and Eloss was reduced
from 0.49 to 0.45, due to the higher lying LUMO level of the
acceptor alloy (Fig. 10). Meanwhile, the Jsc values were
increased from 24.67 to over 26.5 mA cm−2, which could be
ascribed to the optimized morphology. As for the FF, ternary
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Fig. 9 The structures of donors and acceptors for polymer donor/non-fullerene acceptor/non-fullerene acceptor ternary OSCs.

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Table 2 Photovoltaic parameters of ternary OSCs with polymer donor/non-fullerene acceptor/non-fullerene acceptor blends

Non-fullerene A2 Weight ratio Working

Polymer (D) Non-fullerene A1 (third component) (D : A1 : A2) Voc (V) Jsc (mA cm−2) FF (%) PCE (%) mechanism Ref.

PM6 Y6 BTP-M 1 : 1 : 0.2 0.875 26.56 73.46 17.03 Energy transfer 21

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PM6 Y6 BTF 1 : 1.2 : 0.1 0.853 26.11 74.22 16.53 Energy transfer 75
J71 ITIC BTF 1 : 1 : 0.1 0.952 18.48 70.03 12.35 Energy transfer 75
PM6 Y6 3TP3T-4F 1 : 1.02 : 0.18 0.85 26.10 75.4 16.7 Energy transfer 76
PM6 Y6 3TP3T-IC 1 : 1.02 : 0.18 0.86 25.2 71.6 15.6 Energy transfer 76
PBDB-T-SF Y6 ITCT 1 : 1.1 : 0.1 0.885 24.75 73.67 16.14 — 77
PBDB-T-2Cl IXIC-4Cl IT-4F 1 : 0.3 : 0.7 0.847 23.65 74.7 14.96 Energy transfer 79
J71 T6Me IT-4F 1 : 1 : 0.5 0.82 22.65 70.82 13.16 Energy transfer 80
PBDB-T-2F IT-2F FTTCN 1 : 1 : 0.2 0.94 18.18 76.03 12.99 Alloy model 78
PBDB-T IEICF-DMOT IEICO-4F 1 : 1 : 0.1 0.86 23.31 69.75 14.00 — 81
PBDB-T IE4F-S IBC-F 1 : 1 : 0.2 0.887 22.83 74.4 15.06 Energy transfer 6
PBDB-T IT-M DTF-IC 1 : 1 : 0.1 0.94 17.95 72 12.14 Energy transfer 82
PBDB-TF IT4F O6T-4F 1 : 0.85 : 0.15 0.83 21.60 74.6 13.37 Energy transfer 65
PBDBT-SF IDIC IT4F 1 : 0.6 : 0.4 0.917 16.89 74.35 11.52 — 84
PBDB-T Y16 MeIC1 1 : 1 : 0.15 0.909 22.76 68.22 14.11 Energy transfer 85
PBDB-T ITIC ITIF 1 : 0.95 : 0.05 0.865 17.31 70.3 10.53 Energy transfer 83
PBDB-T IEICO-4F 4TIC 1 : 0.6 : 0.4 0.82 21.52 65.9 11.63 Energy transfer 86
PBTA-PS IDIC-C4Ph 6TIC 1 : 0.7 : 0.3 0.84 22.33 75.94 14.24 Energy transfer 87
PBTA-PS ITIC IT4F 1 : 1 : 0.2 0.91 19.60 74.45 13.27 Energy transfer 88
PM6 C8-SF Y-MODF 1 : 0.9 : 0.3 0.845 20.88 75.87 13.39 Energy transfer 89
J61 BT-IC IDIC 0.9 : 0.8 : 0.2 0.88 17.91 68.37 10.76 Energy transfer 90
PTB7-Th COi8DFIC BDTThIT-4F 1 : 0.8 : 0.2 0.721 24.88 72.9 13.08 — 91
PTB7-Th F8IC IDT-2BR 1 : 1 : 0.2 0.687 25.1 69.9 12.1 Energy transfer 92
PM6 IT-4F N7IT 1 : 0.7 : 0.3 0.890 22.54 74.8 15.02 Energy transfer 93

and 16.53%, respectively. The introduction of 10% BTF into the

Fig. 10 Energy level diagram of materials used in ternary OSCs
(Y6 : BTP-M = 4 : 1, by wt). Reproduced with permission.21 Copyright
2020, Royal Society of Chemistry.
devices retained similar values (74.96%) to that of the PM6 : Y6
binary device, implying that the acceptor alloy had good
charge transport properties. The ternary device also presented
enhanced EQE over 86% at around 630 nm, much better than
those of the binary devices. As a result, the optimal ternary
device exhibited the best PCE of 17.03%. Moreover, the
authors found that ternary devices can maintain a PCE over
14% when the thickness of the active layers was varied from
120 to 300 nm. By incorporating a small molecule of 4,7-bis(5-
bromothiophen-2-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole (BTF)
into J71 : ITIC and PM6 : Y6 binary blends, Zheng et al.75 fabri-
cated efficient ternary OSCs with improved PCEs of 12.35%
J71 : ITIC blend improved light harvesting in the wavelength
region from 300 to 500 nm, which resulted in enhanced EQEs
for the ternary OSCs. Morphological studies illustrated that BTF
can enhance the crystallinity of J71 to form more distinct and
denser interpenetrating nano-fibrillar networks. As a result,
balanced µh (1.41 × 10−4 cm2 V−1 s−1) and µe (1.39 × 10−4 cm2
V−1 s−1) with a µh/µe ratio of 1.01 were observed, which contrib-
uted to the high Jsc (18.48 mA cm−2) and FF (70.03%).
Moreover, the Voc of J71 : ITIC : BTF ternary devices was
enhanced from 0.941 to 0.952 V, owing to the higher lying
LUMO energy level of BTF than that of ITIC. When BTF was
added into the PM6 : Y6 system, and the binary device also
showed an excellent PCE of 16.53% with an increased Voc of
0.853 V, a Jsc of 26.11 mA cm−2 and an FF of 74.22%.
In many studies, IDT-based acceptors were employed in
non-fullerene systems. Sun et al. incorporated two non-fuller-
ene small-molecule acceptors 3TP3T-4F and 3TP3T-IC as the
third component into PM6 : Y6 binary blends, respectively.76
Both the guest acceptors formed energy cascades with PM6
and Y6, which could promote charge transfer in ternary OSCs.
Compared with 3TP3T-IC, 3TP3T-4F showed a more excellent
compatibility with PM6 and Y6. AFM measurements indicated
that the incorporation of 3TP3T-4F led to a tendency of
forming well-mixed phases in the ternary blend without dis-
turbing the favorable morphology. The 2D GIWAXS patterns
showed that the intermolecular π–π stacking distance of
the PM6 : Y6 : 3TP3T-4F ternary blend was shorter than that of
the PM6 : Y6 film, leading to more favorable electron
transport. At the optimal blend ratio of 1 : 1.02 : 0.18 for
PM6 : Y6 : 3TP3T-4F, the corresponding ternary device showed

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a PCE of 16.7%, which was higher than that (15.6%) of the
device containing 3TP3T-IC. In 2019, Zhan et al. achieved a
new ternary system based on PBDB-T-SF : Y6 : ITCT, which
showed an impressive efficiency of 16.14%.77 ITCT has a
higher LUMO energy level than Y6, which contributed to a
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higher Voc when blended with the PBDB-T-SF : Y6 binary.
Therefore, Voc values of 0.98 V and 0.86 V were obtained from
the ITCT and Y6 binary devices, respectively. After a small
amount of Y6 was replaced with ITCT (PBDB-T-SF : Y6 : ITCT =
1 : 1.1 : 0.1), larger phase domains and increased phase crystal-
linity of the active layer were observed. The fine film mor-
phology enabled balanced charge mobilities and reduced
recombination, which resulted in improved FF (73.67%) and
Jsc (24.75 mA cm−2) values. When a non-fullerene acceptor
IT-4F was introduced as the third component into the
PBDB-T-2Cl : IXIC-4Cl binary blend, a high PCE of 14.96% was
achieved by Chen et al.79 IT-4F showed an absorption edge of
∼800 nm, complementing the absorption spectrum of
PBDB-T-2Cl and IXIC-4Cl. More importantly, IT-4F can sup-
press the excessive crystallization of IXIC-4Cl and decrease
the pure phase domain of the active layer, which reduced
charge recombination and balanced charge transport.
By using different ratios of the ternary blend, the enhance-
ment in Voc showed an almost linear dependence on the
content of IT-4F, indicating the suitable miscibility of the two
alloy-like acceptors. At a weight ratio of 1 : 0.3 : 0.7 for
PBDB-T-2Cl : IXIC-4Cl : IT-4F, the optimal ternary device exhibi-
ted a high PCE of 14.96%, together with a Voc of 0.847 V, a Jsc
of 23.655 mA cm−2 and an FF of 74.7%.
Zhang’s group also incorporated IT-4F into the J71 : T6Me
blend to fabricate a series of ternary OSCs.80 The EQE values
of ternary OSCs in the wavelength range from 600 to 750 nm
increased with the increase of IT-4F content, which was
derived from the contribution of IT-4F on photon harvesting
and optimized phase separation. Furthermore, the similar
LUMO energy levels of IT-4F (−3.99 V) and T6Me (−3.94 V)
could be beneficial for electron transfer in the ternary active
layers. After adding 50% IT-4F into the J71 : T6Me blend, the
RMS roughness values of the blend films slightly decreased
from 1.04 to 0.76 nm. As a result, the PCE of ternary OSCs
reached 13.16% with a constant Voc of 0.82 V, resulting from
the simultaneously optimized Jsc of 22.65 mA cm−2 and FF of
70.82%. Zhang’s group incorporated a non-fullerene acceptor
FTTCN into the PBDB-T-2F : IT2F blend to fabricate ternary
OSCs.78 The HOMO and LUMO energy levels of the blend
films (Fig. 11b) increased monotonically along with the
increase of FTTCN content, indicating that an FTTCN and
IT-2F alloyed acceptor (Fig. 11d) may be formed due to their
good compatibility. The increased LUMO energy levels can
well explain the increased Voc of ternary OSCs, illustrating the
formation of mixed energy levels for two acceptors.
Meanwhile, the nano-fibrillar structure was obviously
increased in the ternary blend films because the incorporation
of FTTCN content can finely adjust the molecular arrangement
of PBDB-T-2F. By blending 20% FTTCN in binary blends, the
optimized ternary OSCs achieved a high PCE of 12.99% along
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Fig. 11 (a) Vocs of PSCs’ dependence on FTTCN content in acceptors;
(b) HOMO and LUMO levels of FTTCN : IT-2F blend films’ dependence
on FTTCN content; (c) PL spectra of IT-2F : FTTCN blend films with
varied FTTCN contents in acceptors under 700 nm light excitation; and
(d) schematic charge transport process in ternary active layers.
Reproduced with permission.78 Copyright 2019, Elsevier.
with a Jsc of 18.18 mA cm−2, a Voc of 0.940 V and an FF of
76.03%.
Narrow bandgap non-fullerene acceptors could provide
complementary absorption and improve light harvesting
ability for ternary OSCs. Zhan and coworkers reported a high-
performance ternary OSC with a PCE of 14% by incorporating
IEICO-4F into a PBDBT : IEICF-DMOT binary blend.81
Compared with IEICO-4F, IEICF-DMOT possessed two shorter
side chains (methoxyl) on the π-bridge. As a result,
IEICF-DMOT exhibited much broadened absorption with a
larger absorption coefficient (2.9 × 10−5 M−1 cm−1), a higher
LUMO energy level (−3.85 eV), a larger optical bandgap (1.39
eV) and reduced crystallinity. When using the crystalline
IEICO-4F as the near infrared (NIR) absorber, the
PBDB-T : IEICF-DMOT : IEICO-4F (1 : 1 : 0.1) ternary blend
shows increased crystallinity for both donor and acceptor
phases, achieving an increased Jsc of 23.31 mA cm−2, an FF of
69.75%, and a promising PCE of 14%. Li et al. found that the
addition of a new small-molecule IBC-F into a PBDB-T : IE4F-S
blend can improve the efficiency and stability of the resulting
ternary devices.6 2D-GIWAXS patterns showed that the incor-
poration of 20% IBC-F could enhance the molecular inter-
actions to facilitate face-on orientation in the blend film. AFM
and TEM measurements illustrated that the ternary blend
exhibited more fibrillar textures than the binary blend.
Therefore, enhanced thermal and photoinduced stability was
realized in the ternary device. The PBDB-T : IE4F-S : IBC-F
based ternary device retained 81.0% and 85.5% of its initial
PCE (15.06%) after continuous thermal aging and illumination
under an inert atmosphere for 1000 h, respectively, while the
PBDB-T : IE4F-S based binary device retained 71.7% and 73.6%
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of its initial PCE (13.70%), respectively. Ge et al. introduced a
non-fullerene acceptor DTF-IC as the third component into a
PBDB-T : IT-M system.82 The addition of DTF-IC broadened the
absorption of the active layer in a range of 730–800 nm.
Moreover, the third component provided a cascaded energy
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between the host donor and acceptor, which was favorable for
efficient charge transfer between the acceptors and facilitating
exciton dissociation. Consequently, the PCE of the ternary
device increased from 10.90% to 12.14% when the content of
DTF-IC was 10%.
In 2019, Xie et al. fabricated ternary OSCs consisting of one
polymer donor PBDB-TF and two non-fullerene acceptors IT-4F
and O6T-4F.65 The third component O6T-4F exhibited strong
absorption in the near infrared region and could be used to
extend the absorption spectrum. The incorporation of 15%
O6T-4F into the PBDB-TF : IT-4F blend optimized the interpe-
netrating D/A morphology and improved the exciton dis-
sociation by energy transfer from IT-4F to O6T-4F. The ternary
OSC showed a Voc of 0.83 V, a Jsc of 21.60 mA cm−2 and an FF
of 74.6%, leading to a remarkable PCE of 13.37%. Chen et al.
selected a non-fullerene acceptor IDIC and its fluorinated
acceptor ID4F to combine with a polymer donor PBDBT-SF in
the construction of a ternary OSC.84 The structural similarity
between IDIC and ID4F enabled the formation of the acceptor
alloy, which was beneficial for charge transport. At the opti-
mized ratio of PBDBT-SF : IDIC : IT4F(1 : 0.6 : 0.4), the ternary
devices achieved a high PCE of 11.52%, a Voc of 0.917 V, a Jsc
of 16.89 mA cm−2 and an FF of 74.35%. The ternary OSCs also
showed good thickness tolerance with a PCE > 10% from 85 to
250 nm and better stability than the binary OSCs. Zhang et al.
reported a series of high-performance ternary OSCs based on
one polymer donor PBDB-T and two non-fullerene acceptors
Y16 and MeIC1.85 The compatible Y16 and MeIC1 preferred to
form alloyed acceptors with mixed energy levels, which was
beneficial for the formation of electron transport pathways.
The phase separation of the active layers can also be optimized
by incorporating 15% MeIC1 as a morphology regulator. As a
result, the champion device showed a high PCE of 14.11%, a
Jsc of 22.76 mA cm−2 and an FF of 68.22%. A fluorine-substi-
tuted small-molecule acceptor ITIF was synthesized and used
in a ternary OSC based on PBDB-T : ITIF : ITIC blends by Chen
et al.83 Due to the fluorinated and nonplanar structure on the
asymmetric terminal group, ITIF showed a higher LUMO level,
and a lower HOMO level than ITIC, leading to enhanced
absorption at 500–600 nm. As shown in Fig. 12a, the asym-
metric terminal groups led to a nonplanar structure of ITIF,
which could reduce its aggregation. The X-ray diffraction
(XRD) pattern of the blends (Fig. 12b) demonstrated the co-
crystal behavior of ITIC and ITIF, owing to their structural
similarity. Moreover, the decreased melting point of ITIF can
be observed in the differential scanning calorimetry (DSC)
curve (Fig. 12c and d), indicating that ITIF could reduce the
aggregation of ITIC. As a result, the ternary device loading 5%
of ITIF exhibited a PCE of 10.53%, a Voc of 0.865 V, a Jsc of
17.31 mA cm−2 and an FF of 70.3%. Wang et al. introduced a
narrow bandgap acceptor 4TIC as the third component into a
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Fig. 12 (a) Molecular geometry of ITIF and ITIC calculations by density
functional theory (DFT) at the B3LYP/6-31G(d,p) level. (b) X-ray diffrac-
tion (XRD) patterns of ITIC, ITIF and the mixed acceptors with 5% ITIF in
solid powders; DSC thermograms of ITIF, ITIC and the mixed acceptors
with 5%: (c) heat-only thermograms and (d) cool-only thermograms.
Reproduced with permission.83 Copyright 2019, Wiley.
PBDB-T : IEICO-4F binary blend.86 The efficient energy transfer
from PBDB-T to the alloyed acceptor enhanced the exciton util-
ization of the ternary active layer. 4TIC can act as a regulator to
adjust the molecular arrangement of PBDB-T, which sup-
pressed charge carrier recombination and optimized charge
carrier transport. The PCE of ternary OSCs increased from
10.02% to 11.63% when 40% IEICO-4F was replaced with
4TIC, together with an enhanced Voc of 0.82 V, a Jsc of
21.52 mA cm−2 and an FF of 65.9%. Yang et al. reported a
ternary OSC system using a wide bandgap polymer donor
(PBTA-PS) and two non-fullerene small-molecule acceptors
(IDIC-C4Ph and 6TIC).87 When 30% of 6TIC was incorporated
into a PBTA-PS : IDIC-C4Ph blend, the ternary OSC showed an
outstanding PCE of 14.24% with a high Voc of 0.84 V, an
improved Jsc of 22.33 mA cm−2, and an excellent FF of 75.94%.
The superior performance was mainly due to the complemen-
tary absorption of the active layer, suppressed energy loss in
the charge generation process and efficient charge transfer
between acceptors. Yang and coworkers used two structurally
similar acceptors (ITIC and IT-4F) to construct ternary OSCs
combining with a polymer donor PBTA-PS.88 They found that
the crystalline IT-4F could function as a morphology regulator
to enhance the molecular packing. Moreover, efficient energy
transfer from ITIC to IT-4F was observed, which could
promote the exciton dissociation process. After incorporating
20% IT-4F into a PBTA-PS : ITIC system, the ternary device
exhibited an outstanding PCE of 13.27% with a Jsc of 19.60 mA
cm−2 and an FF of 74.45%. Li and coworkers designed and
synthesized two small-molecule acceptors C8-SF and Y-MODF
for the construction of ternary OSCs.89 The addition of 25%
Y-MODF into a PM6 : C8-SF system could suppress monomole-
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cular recombination and improve the utilization of photons in
the 450–600 nm range. The optimal device achieved a high
PCE of 13.39%, with an enhanced Voc of 0.845 V, a Jsc of
20.88 mA cm−2 and an FF of 75.87%. Li and coworkers fabri-
cated ternary OSCs by introducing a highly crystalline IDIC
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into a low crystalline blend of J61 and BT-IC.90 The introduc-
tion of 20% IDIC can enhance the crystallinity of J61 in the
blend film, yielding higher hole mobility and achieving higher
Jsc and FF than those of binary OSCs based on a J61 : BT-IC
blend. At a J61 : IDIC : BT-IC ratio of 0.9 : 0.2 : 0.8, the opti-
mized device achieved a PCE of 10.76%, a Voc of 0.88 V, a Jsc of
17.91 mA cm−2 and an FF of 68.37%. Zhang and coworkers
incorporated a medium bandgap small-molecule acceptor
BDTThIT-4F as the third component to blend with a PTB7-
Th : COi8DFIC system.91 The introduction of BDTThIT-4F
could adjust the molecular arrangement of COi8DFIC to
enhance photon harvesting in the long wavelength range,
leading to improved EQE values from 550 to 1000 nm. By the
incorporation of 20% of BDTThIT-4F, the PCE of the ternary
devices reached 13.08%, which was higher than 11.47% for
COi8DFIC-based binary OSCs and 9.25% for BDTThIT-4F-
based binary OSCs. Zhan et al. fabricated ternary OSCs by
combining F8IC and IDT-2BR acceptors to improve device per-
formance.92 The higher LUMO energy level of IDT-2BR pre-
ferred to form an electron transport channel, which was ben-
eficial for exciton separation and reducing energy loss in the
charge transfer process. The ternary device with 20% IDT-2BR
content in the active layer yielded a PCE of 12.1%, a Voc of
0.687 V, a Jsc of 25.1 mA cm−2 and an FF of 69.9%.
Tang and coworkers employed a small-molecule acceptor
N7IT as the third component added into the PM6 : IT-4F blend
to fabricate ternary OSCs.93 The incorporation of N7IT into
IT-4F decreased the PL intensity of IT-4F, and increased the PL
intensity in the low energy region. This obviously indicated the
energy transfer from IT-4F to N7IT. Compared with PM6 : IT-4F,
the crystal coherence length of the PM6 : IT-4F : N7IT blend was
reduced, resulting in a higher electron mobility of 4.90 × 10−4
cm2 V−1 s−1. AFM images of the ternary blend showed clear
nanofiber network structures with an RMS of 1.66 nm, which
demonstrated good morphology compatibility between the
acceptors of IT-4F and N7IT. As a result, the optimal ternary
device (PM6 : IT-4F : N7IT = 1 : 0.7 : 0.3) gave an outstanding PCE
of 15.02%, which was higher than those of the binary devices
based on PM6 : IT-4F (13.62%) and PM6 : N7IT (13.91%).
In conclusion, when a non-fullerene small-molecule accep-
tor is introduced as the third component into host binary
devices, the resulting ternary devices often exhibit enhanced
photovoltaic performances. Firstly, compared with the host
acceptor, a slightly higher LUMO energy level of the guest
acceptor is beneficial for achieving a high Voc. Secondly, a
narrow bandgap non-fullerene acceptor as the NIR absorber
usually complements the absorption spectra of binary active
layers, which may contribute to an increased Jsc. Thirdly, a
small amount of the third component often acts as the mor-
phology regulator to optimize the phase separation of ternary
blend films, resulting in enhanced FFs of ternary OSCs.
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(c) Polymer donor/small-molecule donor/fullerene acceptor
OSCs. Polymer donor/small-molecule donor/fullerene acceptor
ternary systems have been investigated in recent years. The
introduction of a small-molecule donor into a polymer/fuller-
ene binary blend could tune the molecular orientation,
decrease π–π stacking distance and increase coherence length.
The structures of donors for polymer donor/small-molecule
donor/fullerene acceptor ternary OSCs are shown in Fig. 13,
and the photovoltaic parameters are summarized in Table 3.
In 2015, Wei et al. reported a high-performance ternary
OSC by introducing a small molecule 7,7-(4,4-bis(2-ethylhexyl)-
4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-
hexyl-[2,2′-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) ( p-DTS
(FBTTH2)2) into a PTB7-Th : PC71BM system.94 The results of
resonant soft X-ray scattering (R-SoXS) revealed that the posi-
tion of the scattering peaks at q = 0.2 nm−1 were unchanged
when 15% of p-DTS(FBTTH2)2 was incorporated into the PTB7-
Th : PC71BM blend film, indicating that p-DTS(FBTTH2)2 did
not influence bi-continuous phase separation in ternary
systems. GIWAXS measurements demonstrated that a face-on
π–π stacking peak became more obvious in the 2D images
through incorporating p-DTS(FBTTH2)2 into PTB7-Th, indicat-
ing the enhanced face-on orientation in the ternary blend.
Consequently, the hole mobilities were enhanced and the
charge recombination was decreased. With the incorporation
of 15% of p-DTS(FBTH2)2 in the ternary blend, the Jsc
increased from 17.53 to 18.44 mA cm−2, the FF increased from
65.26% to 75.27%, and the PCE increased from 9.2% to
10.5%. Yang et al. incorporated a benzo[1,2-b;4,5-b′]dithio-
phene-based small molecule DR3TSBDT into a PTB7-
Th : PC71BM blend to improve PCE in ternary devices.95 AFM
measurements revealed that incorporating up to 30% of
DR3TSBDT into the host blend could help achieve uniform
nano-scale phase separation. In addition, GIWAXS measure-
ments indicated that the addition of DR3TSBDT resulted in
the formation of (010) π–π stacking peaks in both in-plane and
out-of-plane directions, demonstrating the formation of mixed
face-on and edge-on orientations. At a low DR3TSBDT loading
of 25% into the host system, the ternary device exhibited a Jsc
of 23.31 mA cm−2, a Voc of 0.772 V, an FF of 70.44%, and a
high PCE of 12.10%. Yang’s group also incorporated
DR3TBDTT into a PTB7-Th : PC71BM blend to fabricate ternary
devices.96 The results of AFM indicated that a highly ordered
molecular compatibility could be achieved, and the addition of
DR3TBDTT improved the phase separation of the active layer.
Therefore, the ordered nano-morphology improved the hole
mobility from 5.385 × 10−5 cm2 V−1 s−1 to 1.221 × 10−4 cm2 V−1
s−1. With 10% DR3TBDTT in the ternary system, the PCE of
ternary devices increased from 7.53% to 9.25%.
Zhang et al. introduced a liquid-crystalline small-molecule
donor BTR into a PTB7-Th : PC71BM system as the third com-
ponent.97 With the incorporation of 10% BTR in the donors,
the correlation length of PTB7-Th crystallites increased from
11.23 to 15.22 nm, indicating that the crystallinity of PTB7-Th
was enhanced. In addition to enhancing the photon harvesting
of the active layers, Zhang et al. found that BTR could also act
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Fig. 13 The structures of donors for polymer donor/small-molecule donor/fullerene acceptor ternary OSCs.

Table 3 Photovoltaic parameters of ternary OSCs with polymer donor/small-molecule donor/fullerene acceptor blends

D2 (third Weight ratio Working

D1 component) A (D1 : D2 : A) Voc (V) Jsc (mA cm−2) FF (%) PCE (%) mechanism Ref.

PTB7-Th p-DTS(FBTTH2)2 PC71BM 0.85 : 0.15 : 1.1 0.755 18.44 75.27 10.50 — 94
PTB7-Th DR3TSBDT PC71BM 1 : 0.25 : 1.5 0.772 23.31 70.44 12.10 Energy transfer 95
PTB7-Th DR3TBDTT PC71BM 1 : 0.1 : 1.5 0.790 18.33 63.89 9.25 — 96
PTB7-Th BTR PC71BM 0.9 : 0.1 : 1.5 0.78 19.23 72.21 10.83 Energy transfer 97
PTB7-Th BTR PC71BM 0.75 : 0.25 : 1.1 0.751 21.4 70.0 11.40 Energy transfer 98
PBDTTPD-HT BDT-3T-CNCOO PC71BM 0.6 : 0.4 : 1 0.969 12.17 71.23 8.40 — 99
PBDTTT-C-T n-BDTT-3T-CNCOO ICBA 0.75 : 0.25 : 1 0.98 11.43 49.4 5.51 — 100
PTB7-Th PDT2FBT-ID PC71BM 0.8 : 0.2 : 1.1 0.770 18.92 76.14 11.10 Energy transfer 101
PBDB-T tBTI-IDT PC61BM 1 : 0.2 : 1 0.86 13.53 71.8 8.40 Energy transfer 43
Si-PCPDTBT SMPV1 PC71BM 0.96 : 0.04 : 1.5 0.56 18.22 63.1 6.44 Energy transfer 102

as a nucleating agent to adjust the PTB7-Th molecular arrange- 19.23 mA cm−2 and FF of 72.21%. Cao’s group also reported
ment and optimize the phase separation. Incorporating 10% ternary OSCs based on the same ternary blends.98 It was found
BTR in the donors, the PCE of ternary devices increased from that the addition of BTR into the PTB7-Th : PC71BM system
10.08% to 10.83%, resulting from the enhanced Jsc of could decrease the π–π stacking distance, enlarge the coher-

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ence length, and enhance the domain purity of the blend film,
which were beneficial for efficient charge transport and
reduced bimolecular recombination. Consequently, the hole
mobility was significantly increased up to 6.33 × 10−3 cm2 V−1
s−1 with 25% BTR content. When the active layer thickness
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was 250 nm, the ternary device exhibited a remarkable PCE of
11.40%, a Voc of 0.751 V, a Jsc of 21.4 mA cm−2 and an FF of
70.0%.
In 2015, Wei et al. reported a small molecule
BDT-3T-CNCOO as an additional donor component to blend
with a PBDTTPD-HT : PC71BM binary system.99 In the ternary
system, the diffraction peaks were gradually strengthened with
the increase of BDT-3T-CNCOO weight ratios, indicating that
the small molecule BDT-3T-CNCOO could promote the crystal-
lization and phase separation of donor materials. Therefore,
the optimized domain size enabled efficient charge transport
through favorable nano-structures. With the increase in small-
molecule ratios, hole mobility gradually became more
balanced, leading to reduced bimolecular recombination. As a
result, when 40% BDT-3T-CNCOO was introduced to the
binary blend, the PCE of the ternary device increased from
6.9% to 8.4%. In 2017, Wei’s group incorporated
n-BDT-3T-CNCOO into a PBDTTT-C-T : ICBA system.100
Compared with a PC71BM-based ternary system, the Voc of the
ternary device significantly increased from 0.77 to 0.98 V due
to the higher LUMO energy level of ICBA. The results of
GIWAXS revealed that the scattering intensity gradually
increased with the increase in the n-BDT-3T-CNCOO weight
ratio, indicating that the addition of the small molecule pro-
moted crystallization of the donors in the films. Such an
addition also enhanced the aggregation of ICBA, resulting in
enhanced charge carrier dissociation and improved charge
transport. The PCE was enhanced from 5.01% in binary OSCs
to 5.51% in ternary OSCs.
Another small molecule PDT2FBT-ID was applied in a
PTB7-Th : PDT2FBT-ID : PC71BM ternary system by Wei et al.101
PDT2FBT-ID exhibited a broad and strong emission range
from 650 to 850 nm covering the absorption range of PTB7-Th,
which indicated the potential energy transfer from
PDT2FBT-ID to PTB7-Th. There were no obvious PDT2FBT-ID
crystalline peaks in GIWAXS results, which demonstrated that
the small amount of PDT2FBT-ID was likely to disperse in the
PTB7-Th amorphous range, and induce the crystallinity of
PTB7-Th in the face-on direction. In addition, the alloy-like
structure and energy transfer mechanism coexisted in the
ternary system. As a result, the FF improved from 66.72% to
76.14% and the Jsc was improved from 17.90 to 18.92 mA
cm−2. A maximum PCE of 11.1% was obtained in the ternary
device. Welch et al. incorporated a benzothioxanthene-based
small-molecule donor tBTI-IDT as the third component to
blend with a PBDB-T : PC61BM system.43 The EQE spectra of
the ternary blend film indicated that the addition of tBTI-IDT
increased optical absorption from 400 to 450 nm. The Voc
values were slightly enhanced from 0.80 to 0.95 V with increas-
ing concentration of tBTI-IDT, indicating that the ternary
system was likely to work as a series connection of OSCs.
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Addition of 10% of the third component did not significantly
alter the film morphology. The optimal device achieved a PCE
of 8.40%, a Voc of 0.86 V, a Jsc of 13.53 mA cm−2, and an FF of
71.8%. Tang et al. reported a ternary system with a low
bandgap polymer Si-PCPDTBT as the host donor and a small
molecule SMPV1 as an additional donor.102 SMPV1 exhibited
strong absorption in the range of 450–650 nm, which was
complementary to the absorption of a Si-PCPDTBT : PC71BM
blend film. TEM measurements showed that the nano-fibrillar
networks of the active layers became more and more obvious
along with the increase of SMPV1 weight ratios up to 4%. The
results indicated that the addition of SMPV1 could adjust the
molecular arrangement of Si-PCPDTBT to form the more
efficient bi-continuous transport channels in the ternary active
layers. As a result, the champion PCE of ternary devices was
increased from 5.73% to 6.44% by adding 4% of SMPV1 in
donors with solvent vapor annealing treatment.
In general, the conjugated small molecules can exhibit
broad absorption spectra in ternary blend films, resulting in
improved light harvesting ability. Owing to the high crystalli-
nity and hole mobility of the conjugated small molecules, the
incorporation of small molecules could enhance the crystalli-
nity of the polymer donor and hence suppress bimolecular
recombination. As a result, the better morphology of ternary
OSCs could be achieved through the synergistic effect of small
molecules and polymers.
(d) Polymer donor/small-molecule donor/non-fullerene
acceptor OSCs. To overcome the weak absorption of fullerene
derivatives, polymer donor/small-molecule donor/non-fuller-
ene acceptor OSCs were investigated. The structures of
donors and acceptors for polymer donor/small-molecule
donor/non-fullerene acceptor ternary OSCs are shown in
Fig. 14, and the photovoltaic parameters are summarized in
Table 4.
In 2019, Zhan and coworkers reported the first example of
ternary OSCs based on a polymer donor/small-molecule
donor/non-fullerene acceptor, in which a mid-bandgap small-
molecule donor TR was introduced as a third component into
a PTB7-Th : FOIC system.23 The high crystallinity of TR could
enhance the ordered molecular packing and hole mobility of
PTB7-Th by regulating the morphology of blend films. The
optimized PTB7-Th : TR : FOIC blend exhibited an increased
hole mobility of 6.8 × 10−4 cm2 V−1 s−1, which was higher than
those of PTB7-Th : FOIC (4.0 × 10−4 cm2 V−1 s−1) and TR : FOIC
(3.4 × 10−4 cm2 V−1 s−1) binary blend films. The results of AFM
measurements showed that the RMS roughness of the ternary
blend was reduced from 3.52 to 1.41 nm, which was beneficial
for efficient charge transport and suppressing bimolecular
recombination. GIWAXS measurements demonstrated the
good miscibility between PTB7-Th and TR, due to the lack of
the (010) peak of PTB7-Th in the ternary blend film. When the
weight ratio of TR was 25% in the ternary system, the best-per-
forming device yielded a remarkable PCE of 13.1%, with a Voc
of 0.734 V, a Jsc of 25.1 mA cm−2 and an FF of 70.9%. Tao and
coworkers introduced a small molecule DIBC as the third com-
ponent into a PTB7-Th : IEICO-4F system.103 The DIBC exhibi-
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Fig. 14 The structures of donors and acceptors for polymer donor/small-molecule donor/non-fullerene acceptor OSCs.
Table 4 Photovoltaic parameters of ternary OSCs with polymer donor/small-molecule donor/fullerene acceptor blends
D2 (third Weight ratio
D1 component) A (D1 : D2 : A)
PTB7-Th TR FOIC 1 : 0.25 : 1.5
PTB7-Th DIBC IEICO-4F 1 : 0.1 : 1.5
ted strong absorption in the range of 400–600 nm, which was
complementary to the absorption of PTB7-Th. When 10% of
DIBC was doped in the PTB7-Th : IEICO-4F blend, the absorp-
tion spectrum of the ternary film showed an obvious enhance-
ment in the range of 300–900 nm, which was desirable for har-
vesting more photons. The PL spectrum of DIBC overlapped
with the absorption spectrum of PTB7-Th, suggesting efficient
energy transfer between DIBC and PTB7-Th. More importantly,
the formation of an intermolecular hydrogen bond between
DIBC and IEICO-4F was confirmed from the Fourier transform
infrared (FT-IR) spectra. This hydrogen-bond interaction can
enlarge the π–π stacking distance and suppress oversize aggre-
gation of PTB7-Th, leading to an improved morphology of the
ternary film. As a result, the PTB7-Th : IEICO-4F : DIBC-based
ternary device showed a high PCE of 13.53% with excellent
shelf-life. After 90 days of storage, the ternary device still
retained 85.02% of the original PCE, which was almost two
times higher than that for the PTB7-Th : IEICO-4F-based
binary device.
The use of crystalline small molecules as the third com-
ponent could enhance the crystallinity of the polymer donor
and optimize phase separation. The high mobility of small
molecules could also provide another channel for efficient
charge transport and thereby reduce bimolecular recombina-
tion. In particular, the formation of hydrogen bonds between
the small molecule and non-fullerene acceptor could suppress
the excessive aggregation of the polymer donor, which
improved the morphology of the ternary blend.
2.2. Polymer/polymer/small-molecule OSCs
Due to the narrow absorption spectra of conjugated polymers,
the use of two donor polymers can broaden the light absorp-
tion of the active layer and facilitate charge dissociation and
transport via the cascade energy structure and optimized mor-
phology.104 Thus, much research work has been focused on
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Working
Voc (V) Jsc (mA cm−2) FF (%) PCE (%) mechanism Ref.
0.734 25.1 70.9 13.1 Energy transfer 23
0.70 26.80 71.36 13.53 Energy transfer 103
the utilization of polymer donors as guest donors in fullerene-
free ternary OSCs aiming at improving the performance of the
binary blend system. The structures of donors and acceptors
for polymer/polymer/small-molecule ternary OSCs are shown
in Fig. 15, and the photovoltaic parameters are summarized in
Table 5.
Zhang’s group designed ternary OSCs by introducing a
polymer donor J71 into a blend of PF2 and Y6.105 They found
that the Elosss of OSCs gradually decreased from 0.68 to 0.53
eV with increasing J71 content in donors, which may be an
important factor for PCE improvement of ternary OSCs. The
photoluminescence (PL) spectra (Fig. 16a) of the ternary blend
showed that the PF2 emission intensity increased monotoni-
cally with the increase of J71 content, indicating the existence
of energy transfer from J71 to PF2. The energy transfer can be
further confirmed from the decreased 635 nm emission life-
time and increased 745 nm emission lifetime in blend films,
as shown in time-resolved photoluminescence (TRPL) spectra
(Fig. 16b). When the J71 content was up to 30% in donors, the
Jsc increased from 23.17 to 24.97 mA cm−2 and the FF
increased from 62.35% to 64.70%. As a result, a PCE of 12.12%
was obtained. The same group also introduced J71 as the
second donor into the PM6 : J71 binary blend to fabricate
ternary OSCs.24 PM6 and J71 may form an alloyed donor due
to the good compatibility, which was beneficial for optimizing
photon harvesting and phase separation of ternary active
layers. When using TEM measurements to characterize the
morphology of blend films, the fibrillar structures were found
to be well maintained in ternary blend films with 20% J71
content, suggesting an ideal phase separation for sufficient
charge transport. It was found that some excitons on J71 may
transfer their energy onto PM6 and then are dissociated into
free carriers at PM6/Br-ITIC interfaces. Consequently, a PCE of
14.13% was achieved in the optimized ternary OSCs with
improved Jsc (19.39 mA cm−2) and FF (78.4%).
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Fig. 15 The structures of donors and acceptors for polymer/polymer/small-molecule ternary OSCs.

Table 5 Photovoltaic parameters of ternary OSCs with polymer/polymer/small-molecule blends

D2 (third Weight ratio Working

D1 component) A (D1 : D2 : A) Voc (V) Jsc (mA cm−2) FF (%) PCE (%) mechanism Ref.

PF2 J71 Y6 0.7 : 0.3 : 1.5 0.75 24.97 64.7 12.12 Energy transfer 105
PM6 J71 Br-ITIC 0.8 : 0.2 : 1 0.930 19.39 78.4 14.13 Energy transfer 24
FTAZ PBDB-T ITM 0.8 : 0.2 : 1 0.95 18.1 73.6 13.2 — 106
PTB7-Th PBDTm-T1 FOIC 0.8 : 0.2 : 1.5 0.762 24.0 73.5 13.4 Energy transfer 107
PTB7-Th PBDB-T O-IDTBR 0.7 : 0.3 : 1.5 1.02 17.07 66.52 11.58 — 108
PBDB-T PTB7-Th FOIC 0.5 : 0.5 : 1 0.73 24.61 65.51 12.02 Energy transfer 109
PBDB-T PTB7-Th IEICO-4F 0.8 : 0.2 : 1 0.74 24.14 65.03 11.62 Energy transfer 110
J51 PTB7-Th ITIC 0.8 : 0.2 : 1 0.81 17.75 67.82 9.70 Energy transfer 111
PBDB-T PTB7-Th SFBRCN 0.3 : 0.7 : 1 0.93 17.86 73.9 12.27 Energy transfer 112
PDCBT PTB7-Th PC71BM 0.5 : 0.5 : 1.5 0.78 17.53 74 10.12 Energy transfer 113
PTB7-Th PBT1-S PC71BM 0.9 : 0.1 : 1.5 0.82 16.8 72.2 10.3 Energy transfer 114
PTB7-Th PffBT4T-2OD PC71BM 0.85 : 0.15 : 1.2 0.776 19.02 72.62 10.72 Energy transfer 115
PTB7-Th PBDTTS-FTAZ PC71BM 0.8 : 0.2 : 1.5 0.816 16.4 67.3 9.2 Energy transfer 116
PPDT2FBT PPDT2CNBT PC71BM 0.9 : 0.1 : 1.5 0.76 18.7 67 9.46 Energy transfer 117

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Fig. 16 (a) PL spectra of neat PF2, J71 and blend PF2 : J71 films under
540 nm light excitation. (b) TRPL spectra of neat PF2, J71 and blend
PF2 : J71 films obtained by probing 635 nm and 745 nm light emission.
Reproduced with permission.105 Copyright 2019, Royal Society of
Chemistry.
To study the morphological and mechanical stability of
ternary OSCs, Ade et al. reported a highly efficient ternary OSC
based on a non-fullerene acceptor IT-M and two polymer
donors (FTAZ and PBDB-T).106 Due to the rigid polymer chains
of PBDB-T, the crystallization behavior of ITM was significantly
suppressed in the FTAZ : PBDBT : IT-M (0.8 : 0.2 : 1) blend film
even after thermal annealing at 180 °C. Consequently, the
corresponding ternary device still retained 90% (Fig. 17) of the
initial efficiency (13.2%) after a storage time of ∼1000 h in a
glovebox. Another ternary OSC was fabricated by employing
PTB7-Th as the donor, FOIC as the acceptor, and a PBDTm-T1
polymer donor as the third component.107 Incorporating 20%
PBDTm-T1 in the host PTB7-Th : FOIC blend led to more
balanced charge mobilities (µh = 8.9 × 10−4 cm2 V−1 s−1, µe =
6.6 × 10−4 cm2 V−1 s−1). GIWAXS patterns showed that the
incorporation of PBDTm-T1 had negligible influence on the
π–π stacking and face-on orientation of the blends. As a result,
an improved PCE of 13.8% with a decreased non-radiative
recombination loss of 0.271 eV in ternary OSCs was achieved.
Chen et al. designed a ternary blend based on two polymer
donors of PTB7-Th and PBDB-T with comparable HOMO
energy levels and a non-fullerene acceptor O-IDTBR, which
exhibited a high Voc of 1.02 V.108 With an optimized ratio of
0.7 : 0.3 : 1.5 for a PTB7-Th : PBDB-T : O-IDTBR blend, the
ternary device displayed a PCE of 11.58%. The ternary device
retained good PCEs of 9.37% after 168 h thermal annealing at
85 °C, much higher than 6.27% and 5.33% for PTB7-
Th : O-IDTBR and PBDB-T : O-IDTBR binary devices, respect-
ively. In addition, the authors also studied the photovoltaic
performances of larger area devices of 0.37, 0.57, and
0.91 cm2. The corresponding devices exhibited PCEs of
10.12%, 9.51%, and 9.01%, respectively.
Ma et al. fabricated ternary OSCs based on PBDB-T : PTB7-
Th : FOIC blends by blade coating in ambient environment.109
Upon the addition of PTB7-Th into PBDB-T : FOIC blends, the
crystallinity of FOIC decreased owing to the better miscibility
of PTB7-Th and FOIC than that of PBDB-T and FOIC, which
exhibited more efficient charge transport. Consequently, the
optimal ternary device based on PBDBT : PTB7-Th : FOIC
blends (0.5 : 0.5 : 1) provided the best PCE of 12.02% with a
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Fig. 17 Normalized PCE of devices based on FTAZ : IT-M (1 : 1) and
FTAZ : PBDB-T : IT-M (0.8 : 0.2 : 1) (annealed at 150 °C for 10 min) as a
function of storage time in nitrogen under darkness. Reproduced with
permission.106 Copyright 2019, Wiley.
high FF of 65.78%. By incorporating 20% PTB7-Th into a
PBDB-T : IEICO-4F binary blend, Tang et al. fabricated efficient
ternary OSCs with PCEs as large as 11.62%.110 The combi-
nation of three materials can cover a large photon harvesting
range from 300 to 1000 nm. The energy transfer between
PBDB-T and PTB7-Th may enhance exciton utilization
efficiency. Thus, the two factors resulted in a high Jsc of
24.14 mA cm−2. Due to the similar HOMO energy levels of the
two donors, the Voc of 0.74 V for ternary OSCs can remain
unchanged. Moreover, PTB7-Th can also act as a regulator to
adjust the PBDB-T molecular arrangement for more efficient
charge transport, and a high FF of 65.03% was obtained. Li
et al. investigated ternary OSCs with PTB7-Th as the second
donor in J51 : ITIC blends.111 When the blend ratio of
J51 : PTB7-Th : ITIC was 0.8 : 0.2 : 1, the ternary device achieved
a PCE of 9.7% together with a Jsc of 17.75 mA cm−2. The
enhanced absorption in the wavelength region of
∼650–750 nm, reduced phase separation and energy transfer
between J51 and PTB7-Th were the reasons for the improved
Jsc and high efficiency. Peng et al. reported ternary OSCs based
on PBDBT : PTB7-Th : SFBRCN blends.112 Such ternary devices
exhibited a broad composition tolerance over the whole D1 : D2
weight ratios (from 1 : 0 to 0 : 1), due to the good miscibility
and desirable nano-phase morphology of the two donor
materials when blending with acceptors. To explore the device
stability with different ternary compositions, the OSCs were
treated thermally from room temperature to 140 °C. From the
results, OSCs based on the ternary blend with a 0.5 ratio of
PTB7-Th showed the best thermal stability (over 0.8 at 140 °C).
At the optimized weight ratio of 0.3 : 0.7 : 0.8 for a
PBDB-T : PTB7-Th : SFBRCN ternary blend, the resulting
devices exhibited an improved Voc of 0.93 V, a Jsc of 17.86 mA
cm−2 and an FF of 73.9%, delivering a high PCE of 12.27%.
Ameri et al. introduced PTB7-Th as the third component
into a PDCBT : PC71BM system.113 The high intermolecular
affinity between PDCBT and PTB7-Th endowed the two
polymer donors with a particular blend microstructure, which
notably improved the charge transport mechanism. The result-
ing ternary device yielded a PCE of 10.12% with a high FF of
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74%. Sun et al. fabricated semitransparent ternary OSCs using
a wide bandgap polymer donor PBT1-S as the third com-
ponent.114 PTB7-Th and PBT1-S showed complementary
absorption, which contributed to extending the absorption of
active layers. Moreover, the addition of 10% PBT1-S did not
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significantly change its average visible transmittance. The
champion ternary devices showed a high PCE of 10.3%. A
ternary system based on PTB7-Th : PffBT4T-2OD : PC71BM was
reported by Wang and coworkers.115 It was found that the
energy transfer from PffBT4T-2OD to PTB7-Th enhanced light
harvesting. After incorporating 15% PffBT4T-2OD, the blend
film showed hierarchical phase separation within 25 nm and
improved phase purity, which was beneficial for achieving
sufficient exciton separation and charge transport. Therefore,
an improved PCE of 10.72% and Jsc (19.02 mA cm−2) as well as
FF (72.62%) were obtained in the ternary device. Fahlman
et al. used two polymer donors PBDTTS-FTAZ and PTB7-Th to
fabricate fullerene-based ternary OSCs.116 Due to the well-
matched PL and absorption spectra of the two polymers, the
energy transfer from PBDTTS-FTAZ to PTB7-Th was realized.
Moreover, adding PBDTTS-FTAZ into the ternary blend
could promote the exciton dissociation of PC71BM and the
donors. The ternary device with 20% PBDTTS-FTAZ exhibited a
PCE of 9.2%, a Voc of 0.816 V, a Jsc of 16.4 mA cm−2 and an FF
of 67.3%. Kim et al. reported high-performance ternary OSCs
by adding PPDT2CNBT into a PPDT2FBT : PC71BM binary
blend.117 The fluorine atoms on the benzothiadiazole moiety
of PPDT2CNBT were replaced with nitrile groups, which over-
came the poor solubility in processing solvents. The additional
donor extended the light absorption of the active layer in a
range of 700–850 nm and improved the Voc because of its deep
HOMO energy level. As a result, the best-performing devices
showed a PCE of 9.46%, a Jsc of 18.7 mA cm−2, a Voc of 0.76 V,
and an FF of 67%.
The use of two compatible polymer donors may suppress
the crystallization behavior of acceptors, and the energy trans-
fer between them will enhance the exciton utilization of the
active layer. However, the introduction of the additional
polymer donor usually leads to interrupted crystallization of
the host donor. Consequently, controlling the interactions
between two polymer donors should be further investigated.
2.3. All-polymer ternary OSCs
To overcome the limited sunlight absorption in most of the
binary all-polymer solar cells, all-polymer ternary OSCs have
been gradually developed in recent years. The introduction of
the third component will lead to difficulty in controlling the
morphology of ternary blend films. Therefore, careful selection
of the ternary components is important for optimizing all the
photovoltaic parameters. The structures of donors and accep-
tors for all-polymer ternary OSCs are shown in Fig. 18, and the
photovoltaic parameters are summarized in Table 6.
Introducing a second polymer donor with appropriate
absorption, energy levels and crystallinity into a binary all-
polymer system is one of the promising strategies for achieving
high-performance all-polymer ternary OSCs. In 2016, Li and
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coworkers incorporated a moderate bandgap polythiophene
derivative PBDD-ff4T into a low bandgap PTB7-Th : N2200
blend to complement the absorption of the host blend.118
PBDD-ff4T also exhibited high crystallinity, which can promote
charge transport and suppress geminate recombination in all-
polymer ternary OSCs. The introduction of 10% PBDD-ff4T in
the ternary blends significantly improved the µh from 5.47 ×
10−4 to 1.23 × 10−3 cm2 V−1 s−1, increasing the PCE from 5.9%
to 7.2%. Another example based on PBDTTT-EF-T : N2200 and
a wide bandgap polymer donor PCDTBT was reported by Ito
et al.119 When the PCDTBT loading amount in the ternary
blend was 10%, the EQEs at visible wavelengths were success-
fully increased up to 65–70%. In addition, the excitons of
PCDTBT can be directly transported to PBDTTT-EF-T and
N2200 via resonant Förster energy transfer, contributing to
efficient charge generation. Therefore, the ternary device
achieved an improved Jsc of 14.4 mA cm−2 and a PCE of 6.65%.
Wang and coworkers improved the photovoltaic performance
of PTB7-Th : PNDI-T10-based all-polymer solar cells by introdu-
cing a high bandgap polymer PBDTTS-FTAZ as the second
donor.120 PBDTTS-FTAZ served as a sensitizer in the visible
region of 450–650 nm, broadening the absorption of the
ternary blend film. The PL spectrum of PBDTTS-FTAZ was
found to overlap well with the absorption spectra of PTB7-Th
and PNDI-T10, suggesting that a Förster energy transfer from
PBDTTS-FTAZ to PTB7-Th and PNDI-T10 can occur at D/A
interfaces and thereby improve charge generation in all-
polymer ternary OSCs. These advantages enabled an outstand-
ing PCE of 9.0% in the optimized 1 : 0.15 : 1 ternary device.
In 2018, Cao et al. performed a series of excellent research
studies on all-polymer ternary OSCs. For example, they syn-
thesized a wide bandgap polymer donor PBTA-Si to blend with
a PTzBI-Si : N2200 system.121 PBTA-Si contained a difluoroben-
zotriazole building block with a siloxane-terminated side
chain, which can be dissolved in green solvent 2-methyl-
tetrahydrofuran (MeTHF) at room temperature. The good com-
patibility between PBTA-Si and PTzBI-Si could drive the mole-
cular stacking of N2200 in the ternary blend, leading to
reduced structure defects and enhanced charge transport.
Therefore, the ternary blend with a ratio of 1 : 1 : 1 for
PBTA-Si : PTzBI-Si : N2200 showed a slightly higher µe (1.02 ×
10−3 cm2 V−1 s−1) than the PBTA-Si : N2200 blend (µe = 8.76 ×
10−4 cm2 V−1 s−1) and the PTzBI-Si : N2200 blend (µe = 5.63 ×
10−4 cm2 V−1 s−1). The corresponding ternary devices exhibited
a high PCE of 9.56% with an impressive FF of 75.7%. Further
investigations showed that the all-polymer OSCs achieved a
PCE of 9.17% with an active layer of 350 nm and maintained a
PCE of 8.34% with a 420 nm thickness active layer. A wide
bandgap copolymer PEG-2%, which had the benzodithio-
phene-alt-difluorobenzotriazole as the backbone and a poly-
ethylene glycol (PEG) modified side chain, was designed by
Cao et al. to fabricate all-polymer ternary OSCs.122 The flexible
side chains made PEG-2% soluble in the green solvent of
MeTHF. At the optimal weight ratio (1.4 : 0.6 : 1) of the
PEG-2% : PTB7-Th : N2200 blend, the resulting device achieved
the highest μh (9.51 × 10−4 cm2 V−1 s−1) and μe (5.68 × 10−4
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Fig. 18 The structures of donors and acceptors for all-polymer ternary OSCs.
cm2 V−1 s−1) with a balanced μh/μe of 1.67, contributing to its
enhanced Jsc (16.89 mA cm−2) and favorable FF (66.13%). AFM
measurements suggested that the incorporation of PTB7-Th
increased the miscibility of PEG-2% and N2200, resulting in a
reduced RMS roughness (0.90 nm) compared with the
PEG-2% : N2200 blend film (RMS = 1.30 nm). As a result, the
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PEG-2% : N2200 binary device’s PCE of 5.98% was increased to
9.27% in the PEG-2% : PTB7-Th : N2200 all-polymer ternary
OSC. Cao’s group used a narrow bandgap conjugated copoly-
mer (PNTB) containing the naphtho[1,2-c:5,6-c′]bis([1,2,5]thia-
diazole) unit to blend with the PBTA-BO : N2200 film.123 The
increased weight ratio of PNTB gradually improved the EQE
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Table 6 Photovoltaic parameters of ternary OSCs with all-polymer blends

D2 (third Weight ratio Working

D1 component) A (D1 : D2 : A) Voc (V) Jsc (mA cm−2) FF (%) PCE (%) mechanism Ref.

PTB7-Th PBDD-ff4T N2200 1.5 : 0.25 : 1 0.82 15.7 56 7.2 Charge transfer 118
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PBDTTT-EF-T PCDTBT N2200 1 : 0.1 : 1 0.790 14.4 58.3 6.65 Energy transfer 119
PTB7-Th PBDTTS-FTAZ PNDI-T10 1 : 0.15 : 1 0.84 14.4 74 9.0 Energy transfer 120
PTzBI-Si PBTA-Si N2200 1:1:1 0.85 14.89 75.65 9.56 Energy transfer 121
PEG-2% PTB7-Th N2200 1.4 : 0.6 : 1 0.83 16.89 66.13 9.27 — 122
PBTA-BO PNTB N2200 1.7 : 0.3 : 1 0.84 15.77 74.98 10.09 Energy transfer 123
PTzBI PBTA-BO N2200 1.7 : 0.3 : 1 0.836 15.64 78.33 10.12 Energy transfer 25
J51 PTB7-Th N2200 1.4 : 0.6 : 1 0.81 17.17 66.36 9.6 — 124
PTB7-Th PCDTBT N2200 1 : 0.15 : 1 0.78 11.44 56 5.11 — 125
PTB7-Th PF12TBT P(NDI2OD-T2) 1 : 0.15 : 1 0.81 12.28 61 6.07 Energy transfer 126
PTB7-Th PBClT NDP-V-C7 0.85 : 0.15 : 1 0.78 16.77 68.07 9.03 — 127

response in the 650–800 nm region, and the ternary blend film
containing 30% PNTB exhibited the optimum EQE response,
contributing to the highest Jsc of 15.77 mA cm−2. Upon adding
PNTB to a PBTA-BO : N2200 binary blend, a reduced RMS
roughness of 1.4 nm was observed, demonstrating a smoother
surface morphology than that of the binary blend film (RMS =
4.67 nm). A larger (100) crystal coherence length was also
observed from ternary blends compared with two binary
blends, indicating improved crystallinity. Such an optimized
morphology enabled good charge transport of ternary blends,
resulting in a high PCE of 10.09% and a desirable FF of
74.98%. Another high-performance all-polymer ternary OSC
achieving a PCE of 10.12% and a high FF of 78% was reported
by Cao et al.25 The ternary systems comprised PTzBI : PBTA-BO
donors and N2200 as an acceptor. AFM showed that the
PTzBI : N2200 binary blend films exhibited granular aggregates
with an RMS roughness of 1.37 nm, while the ternary blend
films with 30% PBTA-BO formed smoother fibrous structures
with a decreased RMS roughness of 1.29 nm. In addition,
when the weight ratio of PBTA-BO increased from 0% to 30%,
a strong face-on orientation was observed in GIWAXS patterns,
which can help reduce the structural disorder and thereby
enhance the charge transport. Both enhanced charge mobility
and the desirable morphology accounted for the superior PCE
and FF.
In 2019, Han and coworkers reported a high-performance
all-polymer ternary OSC using PTB7-Th as an additional
polymer donor to blend with a J51 : N2200 system.124 The EQE
of the ternary blend exhibited a dramatic improvement in the
range from 640 to 850 nm, suggesting that the addition of
PTB7-Th contributed to the light absorption in the long-wave-
length regions. The increased PTB7-Th content in the ternary
blend may enhance the crystallinity of N2200, resulting in the
improvement of electron transport. At a ratio of 1.4 : 0.6 : 1 for
J51 : PTB7-Th : N2200, the ternary blend film exhibited
balanced electron–hole mobility (µh = 3.54 × 10−4 cm2 V−1 s−1,
µe = 3.17 × 10−4 cm2 V−1 s−1), which was consistent with an
enhanced Jsc of 17.17 mA cm−2 and an FF of 66.3%, and hence
the PCE reached 9.60%. More importantly, the authors used a
green solvent cyclopentyl methyl ether (CPME) to fabricate the
ternary devices, which was profitable for practical applications.
Han et al. chose PCDTBT as a sensitizer of PTB7-Th : N2200
binary blend to fabricate ternary OSCs.125 The HOMO and
LUMO energy levels of PCDTBT were located between those of
PTB7-Th and N2200, resulting in an energy cascade level for
efficient charge transfer. The addition of PCDTBT also broad-
ened the absorption of PTB7-Th : N2200 in the 300–420 nm
range, which enhanced light harvesting. More importantly, the
interaction between PTB7-Th and PCDTBT promoted the
aggregation of PTB7-Th, leading to decreased domain sizes
and enlarged D/A interfaces. As a result, the ternary device
with a 15% PCDTBT content gave a PCE of 5.11%, a Voc of 0.78
V, a Jsc of 11.44 mA cm−2, and an FF of 56%. Liu et al. devel-
oped a novel principle of dual FRET in a PTB7-Th : PF12TBT : P
(NDI2OD-T2) system, in which the third component
(PF12TBT) could transfer energy to both the donor and accep-
tor.126 The photocurrent generation process for the PTB7-
Th : P(NDI2OD-T2) : PF12TBT blend system is illustrated in
Fig. 19. The introduction of PF12TBT could provide a nucleus
to induce more and smaller microcrystals in the blend film,
leading to decreased phase separation for efficient photon
absorption and exciton dissociation. In addition, 3-hexylthio-
phene was selected as a solvent additive to improve the disper-
sity of PF12TBT, enabling efficient dual FRET. The corres-
ponding ternary devices yielded a PCE of 6.07%, a Voc of 0.81
V, a Jsc of 12.28 mA cm−2, and an FF of 61%.
He et al. reported an efficient all-polymer ternary OSC by
introducing a chlorinated polymer donor PBClT as the third
component into PTB7-Th : NDP-V-C7 blend films.127
Compared with PTB7-Th, the LUMO and HOMO energy levels
of PBClT decreased due to the strong electrophilic effect of the
two chlorine atoms. The formed cascade energy levels were
beneficial for charge transfer. Moreover, the introduction of
PBClT could also enhance miscibility and suppress crystalliza-
tion in ternary blends, resulting in a favorable film mor-
phology. As a result, the best-performing device with 15%
PBClT exhibited a PCE of 9.03%, a Voc of 0.78 V, a Jsc of
16.77 mA cm−2, and an FF of 68.07%.
To improve the performance of all-polymer ternary OSCs,
wide bandgap polymer donors are often incorporated into the
host blend to complement the absorption of narrow bandgap
polymer acceptors. But all-polymer blend films often exhibit

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Fig. 19 Steps in the photocurrent generation process for a PTB7-Th : P
(NDI2OD-T2) : PF12TBT blend system: ① exciton formation, ② energy
transfer, ③ exciton separation, and ④ carrier transport. Reproduced
with permission.126 Copyright 2017, Royal Society of Chemistry.
large phase separation, which may lead to decreased FFs of
the resulting devices. Therefore, improving the miscibility of
polymers is a crucial issue in all-polymer systems.
2.4. All-small-molecule ternary OSCs
Compared with all-polymer OSCs, all-small-molecule OSCs
have attracted increasing attention and achieved significant
improvement due to the unique features of small molecules,
such as their well-defined structure and molecular weight,
high purity, and less batch-to-batch variation.128–133 The struc-
tures of donors and acceptors for all-small-molecule ternary
OSCs are shown in Fig. 20, and the photovoltaic parameters
are summarized in Table 7.
In 2016, Deng et al. fabricated a series of all-small-molecule
ternary OSCs with DRCN5T and DR3TSBDT as donors and
PC71BM as the acceptor.134 DRCN5T exhibited a wider absorp-
tion range than DR3TSBDT, showing a complementary absorp-
tion in the range from 300 nm to 800 nm. The two donors
with good compatibility preferred to form an alloy state, which
would provide efficient hole transport channels in ternary
active layers. Moreover, the nano-scale phase separation and
bi-continuous interpenetrating network were well maintained
in the optimized ternary blend films, which were beneficial for
efficient exciton dissociation and charge transport, resulting in
improved Jsc and FF. By incorporating 30% DR3TSBDT in a
DRCN5T : PC71BM blend, a champion PCE of 10.16% was
obtained with a Jsc of 16.5 mA cm−2, an FF of 67.0% and a Voc
of 0.92 V. Another all-small-molecule ternary OSC consisting of
DR3TBDTT and DR3TBDTT-E as donors and PC71BM as the
acceptor was fabricated by Wei and coworkers.135 The energy
levels of DR3TBDTT-E were lowered due to the introduction of
ester functional side chains, and thus energy cascades were
formed in the LUMO and HOMO energy levels of three com-
pounds, which was beneficial for charge transfer. As shown in
Fig. 21, after thermal and solvent vapor annealing (TSA), the
alloy-like model transformed to a cascade model because
DR3TBDTT-E shifted from the mixed region to D/A interfaces,
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which facilitated the charge separation process. At the optimized
ratio of DR3TBDTT : DR3TBDTT-E : PC71BM (0.9 : 0.1 : 0.8), the
ternary solar cell exhibited a maximum PCE of 10.26%.
In 2019, the same group synthesized a small molecule
DR3TBDTT-S-E as a donor to blend with DR3TBDTT : PC71BM
and DCAO3TBDTT : IDIC systems, respectively.136 They found
that two ternary devices presented a much higher PCE over
10%, but the related mechanisms are different. In a
DR3TBDTT : DR3TBDTT-S-E : PC71BM system, DR3TBDTT-S-E
could serve as a charge relay to facilitate hole extraction from
PC71BM to DR3TBDTT, derived from the cascade energy levels
of three materials, while in a DCAO3TBDTT : DR3TBDTT-S-
E : IDIC system, the ternary blend film exhibited a mixed face-
on and edge-on orientation by incorporating 5% DR3TBDTT-S-
E, indicating that the formed 3D charge pathways could
promote efficient charge transport. A small molecule
DPP-2TTP containing porphyrin and diketopyrrolopyrrole
units was designed by Zhu et al. to fabricate ternary OSCs.26
As expected, the DPP-2TTP exhibited a very strong absorption
in ranges of 400–550 nm and 700–900 nm, and the weak
absorption in the range of 550–650 nm was compensated by
a wide-bandgap small molecule DR3TBDTTF. The large
overlap between the emission spectrum of DR3TBDTTF and
the absorption spectrum of DPP-2TTP suggested efficient
energy transfer from DR3TBDTTF to DPP-2TTP, which
was helpful in achieving high photocurrents in ternary OSCs.
Moreover, the addition of 20% DR3TBDTTF in a
DPP-2TTP : DR3TBDTTF : PC71BM blend film can slightly
reduce the RMS from 2.35 to 2.08 nm; such a smoother
surface was beneficial for more efficient exciton dissociation
and charge transport. Thus the corresponding ternary device
showed a remarkable PCE of 11.15% with a significant FF of
77.1%, which was much better than that the
DPP-2TTP : PC71BM binary device (PCE = 9.30%).
Cao’s group reported a highly efficient ternary OSC
using two porphyrin derivatives (DPPEZnP-TBO and
DPPEZnP-BzTBO) as donors and PC61BM as the acceptor.137 By
replacing the alky-thiophene with alky benzothiophene units
at two of the porphyrin meso positions, DPPEZnP-BzTBO
showed deeper HOMO and LUMO energy levels than
DPPEZnP-TBO, forming a cascade structure to facilitate charge
transportation. With 20% incorporation of DPPEZnP-TBO, the
EQE values of the ternary devices improved significantly in the
region of 630–810 nm and up to 65% in the 700–800 nm wave-
length range. Compared with DPPEZnP-BzTBO : PC61BM
binary devices, the µh of the resulting ternary device was
enhanced from 3.93 × 10−4 to 5.52 × 10−4 cm2 V−1 s−1, and the
µh was slightly enhanced from 2.38 × 10−4 cm2 V−1 s−1 to 2.53
× 10−4 cm2 V−1 s−1, contributing to the higher Jsc and FF. As a
result, the ternary device achieved a PCE up to 10.17% with an
improved Jsc of 18.60 mA cm2 and an FF of 70.10%.
Liu et al. incorporated a small molecule DIB-SQ into a
BTR : PC71BM system.138 The 2,4-bis[4-(N,N-diisobutylamino)-
2,6-dihydroxyphenyl] squaraine (DIB-SQ) was selected as the
third component to enhance photon harvesting of the active
layer due to its high extinction coefficient of 4.5 × 105
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Fig. 20 The structures of donors and acceptors for all-small-molecule ternary OSCs.

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Table 7 Photovoltaic parameters of ternary OSCs with all-small-molecule blends

D2 (third Weight ratio Voc Jsc (mA FF PCE

D1 component) A (D1 : D2 : A) (V) cm−2) (%) (%) Working mechanism Ref.

DRCN5T DR3TSBDT PC71BM 0.7 : 0.3 : 0.8 0.92 16.5 67 10.16 Alloy model 134
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DR3TBDTT DR3TBDTT-E PC71BM 0.9 : 0.1 : 0.8 0.896 14.97 76.5 10.26 Alloy model 135
DR3TBDTT DR3TBDTT-S-E PC71BM 0.95 : 0.05 : 0.8 0.91 14.89 76.9 10.38 — 136
DCAO3TBDTT DR3TBDTT-S-E IDIC 0.95 : 0.05 : 1 0.91 16.37 67.4 10.04 — 136
DPP-2TTP DR3TBDTTF PC71BM 1 : 0.2 : 1.5 0.85 17.89 77.1 11.15 Energy transfer 26
DPPEZnP-BzTBO DPPEZnP-TBO PC61BM 0.8 : 0.2 : 1.2 0.78 18.60 70.10 10.17 Charge transfer 137
BTR DIB-SQ PC71BM 0.94 : 0.06 : 1 0.90 15.44 73.8 10.3 Energy transfer 138
DRCN5T BTR PC71BM 0.985 : 0.015 : 0.8 0.90 16.54 67.5 10.05 Energy transfer 139
DPPEZnP-TEH DPP(TBFu)2 PC61BM 0.8 : 0.2 : 1 0.79 14.5 62 7.1 — 140
DR3 ICC6 PC71BM 1 : 1 : 0.4 0.87 16.3 72 10.8 Energy transfer and charge transfer 141

Zhu et al. improved the performance of all-small-molecule

Fig. 21 Diagrammatic sketch of the phase transformation before and
after TSA. Reproduced with permission.135 Copyright 2018, American
Chemical Society.
M−1 cm−1 in the long wavelength range. The PL emission
intensity was obviously decreased along with increasing con-
tents of DIB-SQ, indicating efficient energy transfer from BTR
to DIB-SQ. The incorporation of 6% DIB-SQ decreased the crys-
tallinity of BTR in the ternary blend film, forming an opti-
mized morphology with a fibrillar structure. Therefore,
balanced charge transport (µh/μe = 1.07) can be achieved in the
ternary active layer. The optimized ternary device with 6%
DIB-SQ in the active layer yielded a champion PCE of 10.3%
with a Jsc of 15.44 mA cm−2, a Voc of 0.90 V and an FF of
73.8%. Tang et al. selected a high-crystallinity small molecule
BTR as the second donor and morphology regulator to prepare
ternary OSCs.139 The EQE values of ternary devices improved
in the whole spectral range due to enhanced photon harvest-
ing in the short wavelength range on mixing 1.5% BTR. The
crystal BTR may induce the ordered packing of DRCN5T in a
DRCN5T : BTR : PC71BM ternary blend, leading to the uniform
nano-fibrillar structure for efficient charge transport.
Consequently, more balanced charge mobility with a µh/µe of
1.12 was obtained in the ternary active layer, resulting in an
increased FF. The optimal ternary device achieved a PCE of
10.05% with a Jsc of 16.54 mA cm−2, a Voc of 0.90 V and an FF
of 67.5%.
ternary OSCs through controlling the morphology of blend
films.140 In their work, a crystalline compound DPP(TBFu)2
was selected as the third component to blend with a
DPPEZnP-THE : PC61BM system. The addition of DPP(TBFu)2
could lead to phase separation with PC61BM due to accelerated
crystallization under thermal annealing, which enhanced the
crystallinity and domain purity of the host donor. The ternary
device with a 20% DPP(TBFu)2 content showed the best PCE of
7.1% with a Voc of 0.79 V, a Jsc of 14.5 mA cm−2, and an FF of
62%.
Laquai et al. revealed the complex photophysics of
DR3 : ICC6 : PC71BM-based ternary OSCs for the first time.141 It
was found that the excitation of donor DR3 or acceptor ICC6
resulted in fast charge transfer, while the excitation of PC71BM
led to fast singlet energy transfer to ICC6. The incorporation of
PC71BM increased the crystallinity of ICC6, resulting in an
improved charge carrier mobility. This improvement enhanced
the EQE across the entire absorption range of the ternary
blend. The optimized ternary devices yielded an average PCE
of 10.8%, with an FF of 72%, a Voc of 0.87 V, and a Jsc of
16.3 mA cm−2.
As discussed above, the introduction of high-crystallinity
small molecules could induce the ordered molecular packing
of the host donor, leading to the formation of a uniform fibril-
lar structure for efficient charge transport in the ternary blend
film. However, small molecules would prefer to form large
crystalline domains due to the strong molecular interactions,
which is unfavorable for exciton dissociation and charge trans-
port. To optimize the morphology of ternary blends, manipu-
lating the complicated molecular interactions plays a key role
for enhanced efficiencies.
3. Challenges and strategies
Although ternary OSCs have achieved remarkable PCEs, there
are still some key issues and challenges that should be noted
and addressed to further enhance the photovoltaic
performance.
(i) Designing and synthesizing new donor materials are
crucial to promote the performance of ternary OSCs. Narrow

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bandgap non-fullerene acceptors have strong absorption in the
long wavelength region (700–950 nm) with high absorption
coefficients. Devices based on non-fullerene acceptors have
exhibited very impressive photovoltaic performance with PCEs
over 17% in binary solar cells. Therefore, there is an urgent
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need to develop high-performance medium bandgap and wide
bandgap donor materials having matched energy levels and
complementary absorption with non-fullerene acceptors.
(ii) Increasing the miscibility of each component is required
for optimizing the active layer morphology, which is vital to
photovoltaic performance. Due to the high crystallinity of non-
fullerene acceptors, the tendency to achieve severe phase sep-
aration may prevent efficient exciton dissociation and charge
transport. Furthermore, a poor miscibility between polymers
and small molecules would limit the composition tolerance of
ternary systems. These issues could be addressed through the
rational design of photovoltaic materials and the optimization
of processing conditions.
(iii) Investigating the Voc behavior of ternary devices is of
equal importance. In a binary OSC, the Voc is related to the
difference between the HOMO energy level of the donor and
the LUMO energy level of the acceptor. But it will become com-
plicated when it comes to ternary solar cells. The Voc of a
ternary device is dependent on the ratios of used materials
and is sensitive to the morphology of the ternary blend. More
studies are needed to provide a deep understanding of the Voc
for ternary solar cells.
(iv) Compared with the numerous studies on improving the
PCE of OSCs, the research on device stabilities has attracted
much less attention. Achieving long-term stability is a crucial
issue for realizing commercial applications. Although some
studies have reported better stabilities of ternary OSCs than
binary devices, there is still a long way to go to achieve long-
term stabilities. To improve the device stabilities, the following
aspects need to be paid attention. (a) Enhance the chemical
stabilities of photovoltaic materials, such as the resistance to
photodegradation and heat degradation.142 (b) Improve the
morphological stability of the active layer, such as cross-
linking to increase intermolecular interactions which may
stabilize the active layer morphology.143 (c) Make the encapsu-
lation technology of OSC devices perfect to avoid exposure to
oxygen and/or water vapor.144
To realize commercial applications of OSCs, other chal-
lenges also need to be focused on. To date, manufacturing
large-area OSC devices with high PCE has been a huge
challenge.145–147 The efficiency of large area devices is much
lower than that of small area counterparts. Roll-to-roll compa-
tible printing techniques are usually used to fabricate large
area OSCs, such as inkjet printing,148 screen printing,149 pad
printing,150 gravure printing,151 and offset printing.152 The
processing techniques are of vital importance to enhance the
efficiency of large area OSCs, and they need to be further
improved to realize competitive PCEs with small area counter-
parts. To achieve commercialization, it is also a big challenge
to enhance the thickness tolerance of active layers transform-
ing from the lab-scale to industry-scale.
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4. Conclusions and prospects
Overall, the recent advances in ternary OSCs based on
polymer/small molecule/small molecule, polymer/polymer/
small molecule, all-polymer and all-small-molecule classifi-
cations were thoroughly studied. The characteristics of each of
the four categories of ternary OSCs were systematically sum-
marized and analyzed. The ternary strategy is an efficient
approach to enhance the photovoltaic performance of binary
OSCs. Incorporating the third component into a binary blend
can broaden the absorption spectra, facilitate exciton dis-
sociation and charge transport, as well as adjust the mor-
phology of the blend. As a result, the device performance and
stability can be simultaneously enhanced. The main advan-
tages of utilizing the ternary strategy in OSCs are listed as
follows.
Firstly, the available solar spectrum for OSCs usually ranges
from ultraviolet to near-infrared, and a wider spectral coverage
is beneficial for obtaining a higher Jsc. Compared with binary
OSCs, the introduction of the third component into ternary
OSCs could easily broaden the absorption and improve the
light harvesting ability, which is beneficial for enhancing the
Jsc. For example, introducing the third component with a wide
bandgap may enhance absorption in the short-wavelength
region, and introducing the third component with a narrow
bandgap may enhance absorption in the long-wavelength
region.
Secondly, cascade charge transfer is an important process
in ternary OSCs. When the third component with suitable
energy levels is introduced into a binary blend to form a
cascade energy alignment, it is possible for the third com-
ponent to transfer holes and electrons to the host donor and
acceptor, respectively. As a result, efficient charge transfer and
suppressed charge recombination could be realized.
Thirdly, morphology control has a significant impact on the
Voc, Jsc, and FF, which determine the photovoltaic performance
of OSCs. The third component could act as a morphological
modulator to improve miscibility and compatibility with the
binary blend, resulting in better stability, optimized phase separ-
ation, and appropriate crystallinity of the ternary blend.
Moreover, the crystallization, domain size, and purity can easily
be tuned by controlling the weight ratio of the third component.
Several key issues toward further development were also
pointed out, including rational materials design, optimization
of the active layer morphology, and in-depth understanding of
complicated mechanisms in ternary systems. To further
improve the device performance, efforts should focus on devel-
oping high-performance donors and acceptors, increasing the
miscibility of the third component with the binary blend, and
controlling the favorable morphology with better stability by
device engineering. Owing to the advantages of broad and
strong absorption, cascade energy levels, and easily adjustable
morphology, ternary OSCs have great potential in the field of
organic electronics. The ternary strategy could provide bright
prospects to boost the development of OSCs for commercial
applications.
This journal is © The Royal Society of Chemistry 2021

Nanoscale
Conflicts of interest
There are no conflicts of interest to declare.
Published on 23 December 2020. Downloaded by National Institute of Technology - Calicut on 8/22/2022 10:14:49 AM.
Acknowledgements
This work was supported by (1) the National Natural Science
Foundation of China (51703104, 51773220, 51802169, and
52073122), the Shandong Provincial Natural Science Foundation
(ZR2017BEM035), the China Postdoctoral Science Foundation
(2017M612198), and the Qingdao Innovation Program Applied
Basic Research Fund (18-2-2-8-jch), (2) the State Key Project of
International Cooperation Research (2017YFE0108300 and
2016YFE0110800), (3) the Shandong Double-Hundred Project
(2018), (4) the National Plan for Introducing Talents of
Discipline to Universities (“111” plan), and (5) the 1st Class
Discipline Program of Shandong Province.
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