Review

Cite This: Chem. Rev. 2018, 118, 3447−3507 pubs.acs.org/CR

Nonfullerene Acceptor Molecules for Bulk Heterojunction Organic

Solar Cells
Guangye Zhang,†,‡,∥ Jingbo Zhao,†,∥ Philip C. Y. Chow,†,‡,∥ Kui Jiang,†,‡,∥ Jianquan Zhang,†,‡
Zonglong Zhu,† Jie Zhang,§ Fei Huang,§ and He Yan*,†,‡,§
†
Department of Chemistry and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration &
Reconstruction, Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China
‡
HKUST-Shenzhen Research Institute, No. 9 Yuexing first RD, Hi-tech Park, Nanshan, Shenzhen 518057, China
§
Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South
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China University of Technology, Guangzhou 510640, P. R. China

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ABSTRACT: The bulk-heterojunction blend of an electron donor and an electron

acceptor material is the key component in a solution-processed organic photovoltaic
device. In the past decades, a p-type conjugated polymer and an n-type fullerene
derivative have been the most commonly used electron donor and electron acceptor,
respectively. While most advances of the device performance come from the design of
new polymer donors, fullerene derivatives have almost been exclusively used as electron
acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials,
particularly small molecules and oligomers, have emerged as a promising alternative
to replace fullerene derivatives. Compared to fullerenes, these new acceptors are
generally synthesized from diversified, low-cost routes based on building block materials
with extraordinary chemical, thermal, and photostability. The facile functionalization of
these molecules affords excellent tunability to their optoelectronic and electrochemical
properties. Within the past five years, there have been over 100 nonfullerene acceptor
molecules synthesized, and the power conversion efficiency of nonfullerene organic solar
cells has increased dramatically, from ∼2% in 2012 to >13% in 2017. This review summarizes this progress, aiming to describe
the molecular design strategy, to provide insight into the structure−property relationship, and to highlight the challenges the field
is facing, with emphasis placed on most recent nonfullerene acceptors that demonstrated top-of-the-line photovoltaic
performances. We also provide perspectives from a device point of view, wherein topics including ternary blend device,
multijunction device, device stability, active layer morphology, and device physics are discussed.

CONTENTS 5. A-D-A Type Acceptors 3464

5.1. Early Reports of A-D-A Type Acceptors 3465
1. Introduction 3448 5.2. A-D-A Type Acceptors with a Core Unit of
2. Brief Introduction to OPV Working Principle 3449 IDT or Its Derivatives 3468
2.1. Light Absorption and Exciton Generation 3449 5.2.1. Design of the Core Units 3468
2.2. Charge-Transfer State and Free Ccarrier 5.2.2. Side Chain Effects 3469
Generation 3450 5.2.3. Effect of the Spacer Unit 3470
2.3. Charge Transport 3452 5.2.4. Design of the “A” Unit 3470
3. Molecular Design Principle 3452 5.3. A-D-A Type Acceptors with Other Core Units 3471
4. Rylene Diimide-Based NFAS 3453 5.4. Summary 3472
4.1. PDI-Based NFAs 3453 6. Other NFAS 3472
4.1.1. PDI Monomers: Requirement for Twist- 6.1. DPP-Based NFAs 3472
ing 3454 6.2. Others 3475
4.1.2. Twisting Strategy-PDI Dimers 3454 6.2.1. Fused-Ring Aromatics 3475
4.1.3. Twisting Strategy-PDI Trimers and Tet- 6.2.2. Linear Oligomers 3475
ramers 3457 6.2.3. Twisted Dimers 3475
4.1.4. Discussion: How Much Twisting Is 6.2.4. Three Dimensional Structures 3476
Needed? 3459 7. Comparison among Different Core Units 3476
4.1.5. Fused-Ring PDI 3459 8. Nonfullerene All Small Molecule OPV 3477
4.1.6. α-Substituted PDI 3462
4.2. Other Rylene-Based NFAs 3463
4.3. Summary and Challenges 3463 Received: September 5, 2017
Published: March 20, 2018

© 2018 American Chemical Society 3447 DOI: 10.1021/acs.chemrev.7b00535

Chem. Rev. 2018, 118, 3447−3507
Chemical Reviews Review

9. Ternary Blend Nonfullerene OPV 3478 fabricated using high-throughput processes at low temperatures,
9.1. Motivations to Use Ternary Blend 3478 making them considered as a promising candidate for the next
9.2. Benefits of NFAs in Ternary Blend OPVs 3478 generation PV technologies.
9.3. Utilizing NFAs in Ternary Blend OPVs 3480 Most OPV devices are fabricated using the blend of a
9.3.1. Pair of Miscible NFAs in Ternary Blend 3480 conjugated polymer and a fullerene derivative as the active
9.3.2. Blending NFA with a Pair of Polymer components, 7−9 with the maximum power conversion
Donors 3481 efficiency (PCE) over 11%.10,11 The majority of these
9.3.3. Combining NFA and Fullerene in a achievements are enabled by the design of new polymer
Ternary Blend 3481 donors. In contrast, the archetypal fullerene derivative,
10. Enhanced Device Stability of Nonfullerene OPV 3482 PC61BM,12 and its C70 analog, PC71BM,13 have been
10.1. Enhanced Stability of BHJ Solar Cells with dominantly used as the electron accepting materials ever
IDT Based A-D-A Type NFAs 3482 since the application of the former in 1995.7 Electronically,
10.2. Enhanced Stability of BHJ Solar Cells with fullerenes have a proficient electron withdrawing ability14 and a
PDI or DPP Based NFAs 3483 high electron mobility.15 The physical shape of fullerenes has
10.3. Enhanced Stability of Ternary Blend Non- also offered them three-dimensional electron transport property
fullerene Solar Cells 3484 and the capability of forming favorable blend morphology that
10.4. Semitransparent Nonfullerene Solar Cell balances charge generation and transport.16
with Enhanced Stability 3484 Despite these beneficial properties, fullerenes possess
10.5. Summary 3485 considerable limitations. First, fullerenes do not absorb strongly
11. Reducing Voltage Loss 3485 in the visible region of the solar spectrum. Meanwhile, chemical
12. Challenges and Perspectives 3486 modification of their backbone is not straightforward, rendering
12.1. Perspectives on Molecular Design Strategy a low structural flexibility and an elevated difficulty in tuning
and Synthetic Complexity 3486 the electronic/optical properties. This not only increases the
12.1.1. Molecular Design to Enhance Light synthetic complexity but also makes fullerenes less likely to gain
Absorption 3486 complementary light harvesting to the polymers. When made
12.1.2. Molecular Design to Balance Morphol- into devices, fullerenes have been shown to have poor
ogy and Charge Transport 3487 photostability in air in both pristine and blend films.17
12.1.3. Synthetic Complexity 3487 The demand for replacing fullerenes in OPVs has led to the
12.2. Studying Charge Transport 3488 rapid development of nonfullerene acceptors (NFAs), including
12.3. Understanding Morphology of Nonfuller- both polymeric and small molecular organic acceptors. In the
ene Active Layers 3488 past few years, dramatic progress has been made in the field of
12.3.1. Quantitative Morphology-Performance both branches. If not specified, NFAs throughout this review
Correlations 3488 refer to the small molecular organic nonfullerene electron
12.3.2. Molecular Miscibility 3489 accepting materials. Unlike fullerenes,18 NFAs have excellent
12.3.3. Solvent Additive Effect 3489 synthetic flexibility with more readily available source materials,
12.3.4. Vertical Phase Segregation 3490 which affords easily tunable optical/electronic properties and
12.4. Multijunction NFA OPVs 3491 improved solubility. In conjunction with their high absorption
12.5. Device Structure Engineering and New coefficients, NFAs can be easily tailored to work with novel
Interfacial Layers 3492 polymers in terms of both optical complementarity and
12.6. Thick Active Layer, Large-Area Devices, energetic compatibility, allowing the solar cell to attain broad
Environmentally Friendly Processing, and solar spectrum coverage. In addition, the low-cost cores, facile
Roll-to-Roll Printing 3493 synthesis and simplified purification can significantly reduce the
13. Concluding Remarks 3494 production cost of NFAs.
Author Information 3494 As a result of these advantageous properties, huge efforts
Corresponding Author 3494 have been devoted to designing novel NFAs and applying them
ORCID 3494 in organic solar cells. Particularly, dramatic progress has been
Author Contributions 3494 made in the NFA-based OPV field with over 400 publications
Notes 3494 in the past four years (Figure 1). Over 10% PCEs have been
Biographies 3494 reported for organic solar cells based on different combinations
Acknowledgments 3495 of polymer and NFA, with the best PCE up to 13.1% for single-
References 3495 junction device19 and 13.8% for tandem structure.20
Besides the high and fast-growing PCE (Figure 1), OPV
devices based on NFAs manifest other distinct features that
1. INTRODUCTION have not been widely recognized in fullerene based OPVs. For
The growing demand for renewable energy sources has caused example, the fraction of publications on NFA-based OPVs that
the rapid development in photovoltaic (PV) technologies. Solar mention a reduction in voltage loss is much higher than that on
energy is the largest carbon-neutral energy source available fullerene-based OPVs. 21−23 Evidence suggests that the
today1 and is the fastest-growing form of renewable energy.2 commonly believed energetic offset for generating free charge
Among various PV technologies, organic photovoltaics (OPVs), carriers in OPVs may not be a constraint in NFA-based
whose building blocks are based on earth abundant nontoxic systems.23,24 Such low voltage loss could significantly improve
materials, have demonstrated a short energy payback time the overall performance of OPVs. Besides low voltage loss,
(EPBT)3,4 and a great potential to reduce the levelized cost of enhanced device stability has also been reported for NFA solar
energy (LCOE).5,6 In addition, OPVs are flexible and can be cells.19,25−37
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Chemical Reviews
Figure 1. Nonfullerene organic solar cell publications each year (via
Web of Science) and the maximum power conversion efficiency
reported each year up to Aug 2017.
Despite these exciting results, problems and challenges
remain for this young field. For instance, molecular twisting is
introduced to prevent the molecules from overaggregation, but
it presumably hinders charge transport.23,35,38−43 This paradox
is prominent in NFAs as they are not as diffusive as fullerenes
and they do not have the three-dimensional charge transport
capability in general. A thorough understanding of both
intramolecular and intermolecular interactions for NFAs in
the pristine form as well as in the blend film is needed. Besides,
there lack systematic morphological studies on the general
morphology forming process and device physics studies on
exciton dissociation at the polymer/NFA interface, which are
key issues to be addressed for further advancement of
photovoltaic performance.
By the means of summarizing material property and
photovoltaic performance, this review aims to provide a
balanced assessment of the state-of-the-art molecular design
strategies, to facilitate discussions on how to better understand
the structure−property relationship for further optimizing
active layer morphology, to highlight the fundamental materi-
al/device properties that lack understanding, and to delineate
major challenges facing the NFA-based OPV field. The
emphasis of this review is the solution-processed BHJ organic
solar cell application of nonfullerene molecular electron
accepting materials. Consequently, polymeric electron accept-
ors44−53 and the design of novel polymer donors to be
compatible with NFAs are beyond the scope of this review.
Similarly, the application of NFAs in other organic electronics,
such as organic field effect transistors (OFETs), organic light
emitting diodes (OLEDs), and organic rectifiers, are not
covered in this review.
This review begins with a brief introduction to OPV working
principle (section 2), where light absorption, exciton
dissociation, charge generation, and charge transport are
covered and the concept of bulk-heterojunction is discussed.
As a consequence of the limited exciton diffusion length, BHJ
solar cells with specific morphology requirement are necessary
for realizing the full potential of the materials. In section 3, an
overview of the molecular design strategy is provided. Then we
categorize NFAs based upon structural similarities and provide
detailed material/device property summaries for each category
(sections 4−6), with a particular focus on recent materials
representing top-of-the-line performance in OPV devices. The
3449
Review
goal of sections 4−6 is to compare the effects of different
molecular design strategies on device performance, to generate
insights from previous work, and to outline directions for
further improvement, which are captured by a discussion
section (section 7). With sections 4−7 focusing on the
polymer:NFA based devices, section 8 summarizes the limited
but promising result on all small-molecule nonfullerene solar
cells, i.e., BHJ solar cells based on a small molecule donor and a
nonfullerene small molecule acceptor. In section 9, we extend
our discussion beyond binary single-junction BHJ and
summarize the role of NFA in ternary blend OPVs. As the
maximum reported PCE reached above 13%, OPV device’s
operational stability becomes increasingly vital for the objective
of commercialization. Therefore, section 10 summarizes the
results on the improved stability of NFA-based binary or
ternary BHJ solar cells with the topic semitransparent OPV also
covered. Section 11 delineates the voltage loss in OPV and
highlights the potential of using NFA to achieve a low voltage
loss system. Section 12 provides perspectives on molecular
design and synthetic complexity of NFAs and highlights the
problems and challenges facing the field, mainly from the
morphological and device physics points of view, where topics
such as energy loss, active layer morphology, multijunction
device, interface engineering, and roll-to-roll printing are
discussed, with perspectives and outlook provided. Concluding
remarks are given in section 13.
2. BRIEF INTRODUCTION TO OPV WORKING
PRINCIPLE
2.1. Light Absorption and Exciton Generation
In order to harvest sunlight for the generation of electrical
energy, a solar cell has to convert photons into free charge
carriers and be able to transport these carriers to the electrodes
to give photovoltage and photocurrent. Molecular electronic
materials such as π-conjugated polymers are ideal solar light-
harvesting systems due to their (1) large extinction coefficients
as a result of the large wavefunction overlap between the
electronic ground state and the lowest excited state54,55 and (2)
broad absorption bands as a result of the significant geometry
relaxations that take place in the excited state.55−57 The intense
absorption bands over a broad wavelength range enable a good
matching with a sizable portion of the solar spectrum for
efficient light harvesting in relatively thin layers (∼100−200
nm).
In a neutral organic molecule, the highest occupied molecular
orbital (HOMO) in the ground state configuration contains
two electrons with opposite spins. The absorption of an
incident photon promotes an electron in the HOMO into the
lowest unoccupied molecular orbital (LUMO), leaving behind a
hole to form an electron−hole pair (Figure 2). In an ideal
photovoltaic system, the electron−hole pair can easily separate
to form long-lived, free charge carriers with high quantum
yields, such that a large photocurrent is created when they are
collected by the electrodes. However, in practice such efficient
free carrier generation requires the electron−hole pair to
overcome their mutual Coulomb attraction, V, which is given
by
e2
V=
4πε0εrr (1)
where e is the electronic charge, ε0 is the permittivity of
vacuum, εr is the dielectric constant of the surrounding
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Chemical Reviews
Figure 2. Electronic state diagram describing the photoinduced
charge-carrier formation mechanism in an organic solar cell. Adapted
with permission from ref 55. Copyright (2009) American Chemical
Society.
medium, and r is the distance between the electron−hole pair.
In solar cells based on inorganic semiconductors, such as silicon
p−n junctions, electron−hole pairs can easily overcome their
Coulomb attraction to generate free charges due to the high
dielectric constant (εr ≈ 12 in silicon) and the highly
delocalized nature of the photoexcited states (corresponds to
a large r in eq 1).56,58,59 However, overcoming this Coulomb
attraction between electron−hole pairs is much more
challenging in organic materials due to the low dielectric
constant (εr ≈ 2−4) and the more localized nature of the
photoexcited states.
As a result of the strong Coulomb interaction between
electrons and holes, as well as strong electron−lattice and
electron−electron interactions, photoexcitation of organic
conjugated materials generates a tightly bound electron−hole
pair known as an exciton. These primary photoexcitations have
singlet (spin-zero) character due to the conservation of spin. In
order to facilitate efficient charge generation, it is necessary to
separate these singlet excitons by overcoming its binding
energy. Typical binding energies of singlet excitons in organic
materials have been reported to be ∼0.5 eV.55 This binding
energy is significantly greater than the thermal energy kBT at
room temperature (25 meV), and thus an additional driving
energy is required to create free charges.
The ubiquitous pathway to effectively separate excitons into
free carriers is by using a heterojunction between an electron-
donating (donor) and electron-accepting (acceptor) material.
The differing electron affinity (and/or ionization potentials)
between the two materials creates an energetic offset at their
interface and thereby provides a driving energy for exciton
dissociation. In 1986, Tang reported the first example of an
OPV device based on a vacuum-deposited CuPc/perylene
derivative planar bilayer heterojunction.60 However, despite
achieving relatively efficient exciton dissociation, the overall
efficiency of such a planar heterojunction device is limited by
the requirement of exciton migration to the donor−acceptor
interface. This is because the rate of photoinduced electron
transfer decreases exponentially with the separation between
the donor and acceptor molecule, and therefore excitons must
migrate to the interface in order to dissociate into charges.61−63
Due to the localized nature of excited states in organic
materials, photogenerated excitons typically migrate through
3450
Review
the material by random diffusion. This incoherent hopping
process is typically driven by both Förster resonance energy
transfer (FRET) and Dexter energy transfer and is unaffected
by electric fields due to the electrical neutrality of excitons. This
energy transfer process occurs either intramolecularly or
intermolecularly following a downhill energy gradient and
may lead to trapping of the exciton at trap or defect sites that
leads to inhomogeneous broadening of the density of states.
Further migration of the exciton energy relies on thermal
fluctuation. Organic films typically have short singlet exciton
lifetimes before they decay to the ground state, and thus they
have relatively short diffusion lengths (in the range of ∼5−20
nm). Therefore, a compromise with regards to the film
thickness is required to optimize both exciton dissociation
(favoring thin layers) and light absorption (favoring thick
layers).
A key breakthrough that overcomes the limitation of short
exciton diffusion lengths of organic materials was the
introduction of the bulk heterojunction.7,64 Bulk heterojunc-
tions comprise a bicontinuous interpenetrating network of the
donor and acceptor material, which can be formed by solution
processing or by coevaporation of the two materials. Due to the
large interfacial area between donor and acceptor, the distance
that the excitons have to travel before reaching an interface is
significantly decreased, and efficient harvesting of exciton
energies can therefore be achieved when the nanoscale phase
segregation between the two materials matches with the
corresponding exciton diffusion lengths. For planar hetero-
junctions, exciton harvesting can also be improved by means of
enhancing exciton diffusion lengths and/or using Förster
resonance energy transfer (FRET) in multilayer structures.65,66
Nevertheless, we will focus on bulk heterojunction device
structures in this review.
2.2. Charge-Transfer State and Free Ccarrier Generation
Although the charge generation process following exciton
dissociation is fundamental to the operation of organic solar
cells, its mechanism has remained a disputed topic in the
literature. In this section, we briefly summarize the key
experimental findings and theoretical models that help shed
light on this topic.
Upon reaching a donor−acceptor interface, excitons can
dissociate following the transfer of an electron (hole) from the
donor (acceptor) material to the acceptor (donor) material.
Historically, this charge transfer process of OPV is described
within a modified Marcus framework, which considers the
tunnelling of point like charges.56,67 This initial electron (or
hole) transfer process generates an electron−hole pair across
the interface, which is commonly known as a charge-transfer
state (CTS). Despite being on separate material domains, the
electron and hole are still 0.5−1 nm apart such that they remain
bound by Coulomb binding energy. Once formed, the CTS can
either overcome its binding energy and separate into free
charge carriers or undergo relaxation and recombine geminately
to the ground state resulting in energy loss. The dissociation of
CTS has often been described using the Onsager−Braun
framework, which considers hopping of charges within a
disordered density of states by thermal activation.
However, recent studies have challenged the application of
such a theoretical framework to describe charge generation
processes in high performance OPV devices. These include
experimental studies showing that charge generation yield is
independent of electric field and temperature, and dissociation
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Chemical Reviews
may happens on ultrafast generation time scales (within 100
fs).68 The difficulty in developing a general framework for
charge generation in OPV is in part due to the sheer variation
in material systems and blend combinations that have different
energetics, structural and morphological properties. In the
absence of a comprehensive theoretical framework for CTS and
its dissociation, material design of OPV has been primarily
driven by empirical design rules.69,70 It is generally believed that
a significant driving energy (>0.2 eV) provided by the
interfacial energy offset is required to facilitate efficient charge
generation. This rule was developed based on the observation
that many OPV material systems (particular those based on
fullerene acceptors) suffer from low charge generation yields in
the absence of this energetic offset.71
This general observation has led to the debate over whether
charge generation happens primarily through vibronically “hot”
or “cold” CTS. Given the driving (or excess) energy involved in
the initial charge transfer process, it is often thought that a hot
CTS may facilitate charge separation more easily compared to a
cold (relaxed) CTS by thermalizing into more loosely bound
electron−hole pairs. These hot states should intuitively be less
prone to geminate recombination compared to more tightly
bound, cold CTS, provided that they can separate before they
relax vibronically. Jailaubekov et al. have shown that the
relaxation time of hot CTS in a planar heterojunction of copper
phthalocyanine and fullerene acceptor happens within ∼1 ps.72
This concept implies that the dissociation yield should occur on
an ultrafast time scale and correlate with the amount of excess
energy involved in the charge transfer reaction, and this notion
is supported by a number of studies.73−76 However, this
concept has also been challenged by studies showing that the
charge generation yield is independent of the energy of the
absorbed photon, whether in the donor or acceptor, and thus
the excess energy does not play a significant role in promoting
charge generation.77,78 In particular, Vandewal et al.77 have
shown that the same charge generation yield can be achieved
even when the low-energy cold CTS is directly excited, which
strongly implies that free carriers are generated from the relaxed
intermolecular states without requiring any excess energies.
Apart from energetics, the importance of structural
morphology at the donor−acceptor interface on charge
generation is also highlighted in several studies. For instance,
for OPV blends based on fullerene acceptors it has been
proposed that charge separation efficiency is improved in the
presence of fullerene aggregates near the interface.79−82 These
aggregates promote the delocalization of electronic wave
functions, which may have a significant role on the charge
separation mechanism of OPV blends. In particular, Gelinas et
al.83 concluded that the control of the availability of states in
the fullerene phase by wavefunction delocalization can lead to
an ultrafast coherent electron motion in the fullerene via
ballistic transport, resulting in long-range electron−hole
separation (∼4 nm within 50 fs). Such a long-range charge
separation mechanism would also be less sensitive to interfacial
energetic offset than that predicted by the Marcus/Onsager
framework.84 However, while CTS delocalization favors charge
generation, excessive delocalization may also lead to reduced
device open-circuit voltage by providing more pathways
through which recombination can occur.85,86 This implies
that there may exist a trade-off between charge generation and
voltage loss and optimizing the delocalization of CTS is
necessary to balance photocurrent and photovoltage.
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Review
While charge generation in a wide range of OPV systems
based on fullerene acceptors has been studied over the years,
careful examination of those based on nonfullerene acceptors
has remained limited. This research topic is an area of great
interest driven by the rapid improvement of device efficiencies
reported with nonfullerene based systems in recent years. It is
possible that the charge generation process in fullerene systems
may not directly apply to nonfullerene systems. For instance,
recent studies have shown that very high charge dissociation
yields can be achieved in nonfullerene systems even in the
absence of a significant driving energy.87,88 These findings
represent a major advancement for OPV technology because
the requirement of a driving energy to generate free carriers in
turn limits the open-circuit voltage. A detailed discussion about
voltage loss in OPVs is discussed in section 11. We note that
the driving energy should not be simply determined by taking
the LUMO energy difference between the donor and acceptor
material because the energy of the frontier orbital is the
property of isolated material, which does not account for
exciton binding energy and other interfacial effects69 and are
typically estimated by electrochemical measurements. Instead,
to evaluate the energy loss, a meaningful driving energy should
be evaluated spectroscopically (e.g., PDS)89 or electrically (e.g.,
FTPS-EQE)69 using the blend film or better an actual OPV
device. (PDS and FTPS-EQE refer to photothermal deflection
spectroscopy and Fourier-transform photocurrent spectroscopy
external quantum efficiency, respectively.)
Due to the relatively weak and narrow absorption of fullerene
derivatives (the archetypal acceptors used in a BHJ),
historically, most discussions on charge generation focus on
the photoinduced electron transfer from the “donor” to the
“acceptor”, where the donor refers to the species with lower
ionization potential and the acceptor refers to that with higher
electron affinity. This charge generation process is termed
channel I. However, the mirror process, namely the channel II
charge generation, also occurs in a BHJ system, where the
photoexcitation of the acceptor is followed by a hole transfer
from the acceptor to the donor. With the rapid development of
nonfullerene acceptors, numbers of new small molecular or
polymeric acceptors have been realized with strong and
complementary absorption to the donor materials. Conse-
quently, equal attention needs to be placed on channel II
charge generation. Experimental methods for probing channel
I/II in a BHJ OPV system include device internal quantum
efficiency measurements, photoluminescence quenching meas-
urements, transient absorption spectroscopy measurements,
etc. For a detailed discussion on the charge generation
pathways, readers can refer to the review article by Stoltzfus
et al.90
It is important to note that CTS can also travel along the
donor−acceptor interface. Recent work by Deotare et al. shows
that the CTS can move over distances of 5−10 nm in a model
donor−acceptor system, driven by energetic disorder and
diffusion to lower energy sites.91 Such distance is comparable to
the exciton diffusion lengths in many organic materials and
phase segregation of BHJ blends, and therefore it is possible
that CTS diffusion also plays an important role in the charge
generation process in OPV. For instance, CTS formed in
blends with large density of low energy sites at the interface
may have a greater chance of being trapped in those sites,
followed by recombination. We will review the various charge
recombination pathways in OPV in the next section.
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2.3. Charge Transport
Free charge carriers are generated upon the dissociation of
excitons and/or CTS at the donor−acceptor interface, and they
move toward their respective electrodes driven by the applied
electric field. The efficiency at which the charges are
transported depends on their mobilities. While the ordered
nature of inorganic semiconductors lead to high charge
mobilities (typically ∼102 cm2 V−1 s−1), organic semi-
conductors tend to exhibit relatively low charge mobilities as
a result of disorder effects, weak electronic couplings, and large
electron-vibration couplings (leading to polaron formation).55
Charge transport thus relies on polarons hopping from site to
site, with carrier mobilities strongly depending upon morphol-
ogy that can range over several orders of magnitude from
10−6−10−3 cm2 V−1 s−1 (highly disordered amorphous films) to
above 1 cm2 V−1 s−1 (highly ordered materials). Photocurrent is
formed when the charge reaches the electrode, and efficient
charge extraction at the electrode is required to suppress
recombination.92,93
During the charge transport process, free electrons and holes
may encounter near an interface and form a CTS, which then
either recombines (through vibronic coupling to the ground-
state) or dissociates back into free carriers. This recombination
process is detrimental to OPV operation by limiting both
photocurrent and photovoltage. In the limit of Langevin
recombination, as in the case of organic light-emitting diodes
(OLED), every encounter leads to recombination to the
ground state with no probability of separating once again into
free carriers. However, it is well-known that the rate of
recombination in OPV is several orders of magnitude slower
than predicted by Langevin theory, leading to the need of
introducing a “reduced Langevin factor” to correctly model
charge kinetics in OPV.92 This raises the question of whether
Langevin theory mispredicts the recombination rate in OPV
because it overestimates the frequency of the electron−hole
encounter or because only a small fraction of encounters
eventually lead to recombination. As explained by Burke et al.,86
understanding the origin of this reduction factor has important
consequences for OPV design. For instance, will increasing
carrier mobility in order to improve fill-factor in turn reduce
open circuit voltage (VOC) by making carriers recombine
quicker? While it remains difficult to precisely control mobility,
higher OPV efficiencies are typically achieved with higher
carrier mobilities because the fill-factor improves without a
corresponding loss in VOC.94 This implies that the limiting
factor for recombination is not the frequency of electron−hole
encounters but instead the rate at which the CTSs recombine
to the ground state and how quickly they can dissociate back
into free carriers.77,86,95
Recombination can also occur through spin-triplet states.
Similar to excitons, CTS may have spin-singlet or spin-triplet
properties, with the difference being that the energy difference
(or exchange energy) between singlet and triplet states of CTS
is much smaller than that typically found for excitons. This is
due to the weak electronic coupling of CTS.75,96 The triplet
CTS states may be populated either geminately (following
intersystem crossing on nanosecond time scales) or bimolec-
ularly (following encounter of free carriers with opposite
charges). The detrimental role of triplet CTS on charge
dissociation yield of OPV is well documented.56 Previous
studies have shown that, in blends where there exists a lower-
lying triplet exciton state (say in the donor polymer domain),
the energy of the CTS can be transferred to the triplet exciton
3452
Review
state. Although triplet excitons have long lifetimes (up to μs)
and may be able to thermalize back into charges if given enough
time, it was found that, once formed, these triplet excitons are
rapidly quenched by surrounding charges (triplet-charge
annihilation) which subsequently lead to energy loss. It is
most likely that triplet recombination occurs in blends where
low-energy, relaxed CTS are formed.97−99 In the absence of
these relaxed CTS, the separation of CTS into free charge
carriers is kinetically more favorable compared to triplet exciton
formation, and thus triplet recombination is suppressed. On the
other hand, in systems where triplets are allowed to form,
bimolecular triplet recombination on subnanosecond time
scales represents a major loss pathway that limits device
efficiency.
It is thus clear that recombination events in OPV are
governed by microscopic details of the interface between donor
and acceptor molecules, and improved device performance can
be achieved by understanding the origins of these processes and
developing strategies to limit them.
3. MOLECULAR DESIGN PRINCIPLE
Historically, the main light absorber in a polymer/fullerene BHJ
blend is the p-type polymer because of the low absorptivity of
the fullerenes, which makes the use of the words “donor” and
“acceptor” specific to electrons. We follow this nomenclature as
it was widely recognized by the field. However, many NFAs
contain strong dye-based chromophores that could make them
an even stronger light absorber than polymers and achieve
significant photocurrent generation through hole transfer to the
electron donor material after photoexcitation.90 This is one of
the original motivations of utilizing NFAs, which could
significantly enhance the photocurrent as both channels
(donor and acceptor) can contribute to free carrier generation.
To maximize this effect, the BHJ should be designed using
donors and acceptors that have broad and complementary
spectral coverage. Thanks to the development of the polymeric
and small molecular donor materials in the past decades, there
exists a large library of donor materials to choose from or
modify to this end.
The design rules of conjugated polymers are also valuable for
the development of novel NFAs. Many approaches can be
employed to tailor the optical and electrochemical properties
such as adjusting the conjugation lengths to tune the spectral
response, using fluorination to alter the frontier energy levels,
and tuning the extent of the HOMO−LUMO overlap to
modify the extinction coefficients. As described in previous
sections, there has been evidence suggesting the traditionally
believed >0.2 eV excess energy might not be a strict restriction
for efficient free carrier generation. Therefore, BHJ design
should not be limited to a pair of materials with a specific
LUMO−LUMO (or HOMO−HOMO) offsets. Here, we
should note that we use the term LUMO level to indicate
the electron affinity energy, which follows the standard usage in
discussing organic electronics, but it needs to bear in mind that
the occupation of this level will cause the energy to change due
to a combination of Coulomb forces, exchange, and vibronic
interactions.100
In contrast to energetics, designing a BHJ with favorable
nanoscale phase separation is far more complicated. A planar
geometry with extended conjugation is typically beneficial for
light absorption of the molecule, but it could induce a strong
aggregation tendency that leads to excessively large domains
with an inadequate interface between the donor and acceptor
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Chemical Reviews
for efficient exciton dissociation. Therefore, a molecular design
strategy, e.g., reducing the coplanarity, must be considered to
introduce enough miscibility and solubility to the molecule.
However, reducing the coplanarity of the molecule is typically
accompanied by a reduction of the charge carrier mobility.
Therefore, in addition to energetics and absorption, the essence
of molecular design is to judiciously control the molecular
geometry to balance exciton dissociation and charge carrier
transport in a BHJ blend.
Furthermore, chemical modification needs to retain the
chemical, thermal, and photostability of the molecule. Mean-
while, enabling solution processability, preferentially in environ-
mentally friendly solvents, is another design consideration for
the eventual commercialization of this technology.
4. RYLENE DIIMIDE-BASED NFAS
Rylene diimides are a robust, versatile category of polycyclic
aromatic n-type (or ambipolar) materials with remarkable
electron mobility, high electron affinity, high absorption
coefficients, and outstanding oxidative/thermal stability,101,102
which make them ideal candidates for application in a wide
range of organic electronics.
Among various rylene dyes, perylene dyes have been known
for over a century. Perylene diimides (PDIs) have generally
been used as pigments and dyes. Owing to their rigid aromatic
core with multiple grafting sites, PDIs show strong propensity
to self-assemble into ordered bars, spheres, or ordered
structures in other shapes.104−109 Thanks to their exceptional
electronic and optical properties (Figure 3a) along with their
outstanding thermal, oxidative, and photostability, PDI-based
semiconductors have been widely applied to OLEDs,110,111
Figure 3. (a) Absorption spectra of PDI and its higher homologues.
Adapted with permission from ref 102. Copyright (2010) American
Chemical Society. 2D-WAXS patterns of (b) PDI 1, (c) TDI 2, and
(d) QDI 3. The numbers after PDI, TDI, and QDI refer to the original
names of the molecules given by the authors of ref 103. (b−d)
Adapted with permission from ref 103. Copyright (2006) American
Chemical Society.
3453
Review
OPVs, OFETs,112,113 light harvesting arrays,114 and even
sodium-ion batteries as organic electrodes.115
Compared to PDI, its higher homologues such as terrylene
and quaterrylene tetracarboxdiimides (TDIs and QDIs), have
relatively less flexible synthesis and a much higher propensity to
crystallize (Figure 3b−d) into a large domain with sizes of
hundreds of micrometers,103 which make them candidates for
organic transistor applications116 but less suitable for BHJ-type
OPV device applications.
In terms of OPV application, naphthalene diimides (NDIs)
and PDIs are the most widely studied rylene derivatives. The
earliest OPV application of PDIs can be traced back to the
pioneering work by Tang.60 Compared to PDIs, NDIs are less
crystalline in general and have relatively weaker absorption in
the visible, which make them more applied as building blocks in
polymeric acceptors.44−47,51−53 This section summarizes the
development of PDIs, NDIs, and other rylene derivatives as
electron accepting materials in BHJ type OPVs, with a
particular focus on the most recent publications.
4.1. PDI-Based NFAs
For BHJ OPV applications, shown in Figure 3b, the PDI
monomer still has too strong an aggregation for achieving
domain sizes small enough for efficient exciton dissociation.
Therefore, functionalization of PDI on various positions is
introduced to make the molecule twisted, which is essential for
reducing aggregation. Depending on the position of function-
alization, the PDI based NFAs can be categorized into bay, α,
and imide functionalized derivatives (Figure 4). Among them,
Figure 4. Functionalization positions on a PDI.
the bay position is the most explored grafting site due to the
feasible synthesis and effectiveness to reduce intermolecular
aggregation. Connecting different numbers of PDIs through a
central core has also been proved an effective approach to
introduce twisting to the molecule. These approaches have
caused differences in intramolecular twisting and/or intermo-
lecular interaction between neighboring PDIs, whereas an
expected outcome of the twisting approach is the hindered
charge transport within the less crystalline network. Natural
questions raised are how much twisting is needed? Were any of
the molecules overtwisted? Would there be alternative method
to maintain good intermolecular interaction while reducing the
domain size? These are concerns to bear in mind at this stage of
PDI research. On the other hand, α position functionalization
and fused-ring strategies emerge as promising approaches to
address the twisting-coplanarity paradox. Subsection 4.1 begins
with recapping the early application of PDI-based NFAs in
OPVs such as the monomeric PDIs, followed by summarizing
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Chemical Reviews
various twisting strategies, focusing on the bay-position
functionalized PDIs. Fused-ring strategies and α position
functionalization are then discussed. Chemical structures of
selected PDI-based materials are shown in each subsection with
their material properties and OPV device parameters
summarized in Table 1.
4.1.1. PDI Monomers: Requirement for Twisting.
Pioneering work employed unsubstituted PDI dyes in OPVs.
To enable solution processability, only imide-functionalized
PDIs were used in the beginning (Figure 5).117,118 Schmidt-
Mende et al. demonstrated using discotic liquid crystal hexa-
perihexabenzocoronene in combination with a monomeric PDI
dye to produce a thin film with vertically segregated donor and
acceptor materials.119 An EQE >34% was demonstrated for a
thickness of almost 490 nm. The low PCE, particularly the low
short circuit current (JSC) indicates the strong aggregation
problem. In 2013, Sharenko et al. reported the use of p-
DTS(FBTTh2)2 and PDI to fabricate all-small-molecule solar
cells with a PCE up to 3.0%.120 In a later report, mixing PDI
with PBDTTT-C-T (Figure 6) resulted in a PCE of 3.7%,
which was the best performance of PDI monomers function-
alized only at the imide position.121
To alleviate the overaggregation, substitutions at other
positions were introduced.122−126 One representative report
was a slip-stacked PDI by introducing substituents at the α
positions.127 The best-performing acceptor phenyl-PDI (Figure
5, molecule 4.3) was obtained by adding a phenyl group at each
α position, and the steric hindrance of the substituents caused a
slipped stack of the PDI planes. As a result, a PCE up to 3.67%
was obtained by combining with a large bandgap donor
polymer PBTI3T (Figure 6). In another report, introducing
phenyl groups at the bay region was also reported.128 The
acceptor TP-PDI (Figure 5, molecule 4.4) achieved a PCE of
4.1% when blended with PTB7-Th (Figure 6).
Despite increased PCE, the overaggregation is still one of the
key issues limiting the device performance in monomeric PDI-
based BHJ solar cells. To reduce the aggregation tendency,
various molecular design strategies have been developed that
led to dramatic improved photovoltaic performance ever since.
4.1.2. Twisting Strategy-PDI Dimers. Other than
functionalizing a PDI monomer, one straightforward approach
to reduce the planarity is to connect two PDIs together through
a single bond or the aid of a spacer unit (Figure 7).
Pioneering research in this area was reported by Rajaram et
al., who linked two PDIs with a single bond between the two
nitrogen atoms at each PDI’s imide region,129 forming a twisted
PDI dimer (Per 1). Compared to the PDI monomer (Per 2, see
Figure 5, molecule 4.2), the reduced planarity of Per 1 (Figure
7, molecule 4.5) suppressed the excessive aggregation and
boosted the photocurrent dramatically (Figure 8). A high PCE
of 2.77% was obtained for Per 1 with PBDTTT-C-T as a low-
bandgap donor polymer.
The similar strategy was also used by Zhang et al., who
presented a PDI dimer linked at the bay region with a
thiophene used as the spacer (Bis-PDI-T-EG, Figure 7,
molecule 4.6).130 Such dimerization, together with the side
chains at the bay region, suppressed the intermolecular
interaction and aggregation of PDI. An outstanding PCE of
4.03% was achieved using PBDTTT-C-T as the donor polymer.
In a follow-up study, a new acceptor with shortened side chains
at the bay region enabled a higher PCE of 4.34% in
combination with the same donor polymer through tuning
the fraction of additive in the solvent mixture.131
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Review
A simple PDI dimer linked at the bay region through a single
bond was reported later by Jiang et al.132 Among the PDI
dimers connected through one, two or three singles bonds, the
one with a single bond between two PDIs (s-diPBI, Figure 7,
molecule 4.7) resulted in a more twisted molecular structure
than those with two or three single bonds. Consequently, an
OPV device based on s-diPBI exhibited a high PCE of 3.63%
with PBDTTT-C-T as the donor polymer and a mixture of 1,8-
diiodooctane (DIO)/1-chloronaphthalene (CN) as solvent
additive whereas PDI dimers linked by two or three single
bonds displayed significantly lower device performance. Further
improvement of the device performance was achieved by Zang
et al. through combining s-diPBI with PTB7-Th. A high JSC of
11.98 mA cm−2 and a high fill factor (FF) of 59% contributed
to an excellent PCE of 5.9%.133 Later, Sun et al.134 and Meng et
al.135 reported two derivatives of s-diPBI with bay regions at
both ends of the dimer end-capped by either sulfur (SdiPBI-S,
Figure 7, molecule 4.8) or selenium (SdiPBI-Se, Figure 7,
molecule 4.9), rendering the PDI unit a planar structure.
Compared with s-diPBI, SdiPBI-S and SdiPBI-Se exhibited
larger dihedral angles between the two PDI units, as well as
larger optical bandgaps. When combined with a medium
bandgap donor polymer PDBT-T1 (Figure 6), SdiPBI-Se
achieved a high PCE of 8.42% while SdiPBI-S showed a PCE of
7.16%.
In terms of synthetic cost, Hendsbee et al. demonstrated the
gram-scale synthesis of three N-annulated PDI compounds and
a PDI dimer linked via a single bond at the bay position (Figure
7, molecule 4.10), without the need for purification using
column chromatography.136 One of the PDI dimers exhibited a
PCE of 7.55% in BHJ solar cell.
In addition to connecting two PDIs through a single bond, to
further tune the morphology of the active layer, Yan et al.
studied the effect of spacers on aggregation and thus phase
separation between PDI and polymer. A series of spacers
including thiophene, benzene, bithiophene and spirobifluorene
were inserted between the two PDI units.137 It was found that
the planar dimer with a phenyl ring as the spacer showed the
largest domain size and the worst solar cell performance due to
strong intermolecular interactions. In contrast, the best PDI
dimer in this report was the one with spirobifluorene as the
spacer (SF-PDI2), which led to a small domain size of the blend
film and a PCE of 2.35% with P3HT as the donor polymer.
In 2016, Liu et al. designed a new conjugated polymer,
P3TEA (Figure 6), and combined it with SF-PDI2 (Figure 7,
molecule 4.11) in a BHJ solar cell.87 The nonfullerene solar cell
demonstrated not only a 9.5% efficiency with nearly 90%
internal quantum efficiency but also an extremely high VOC
(1.11 V) and a decent FF (0.64). The authors quantified the
energy loss of the device by taking the difference between the
bandgap of the donor (obtained using the crossing point
between the absorption and emission spectra) and the VOC of
the device, and a low voltage loss (0.61 V) was determined.
Noticeably, subgap-EQE and electroluminescence measure-
ments exhibited almost overlapped spectra between the pure
polymer and the polymer:SF-PDI2 blend (Figure 9a,b), which
indicated a nearly zero driving force for charge separation in
this highly efficient OPV system. In addition, the authors
employed another polymer:NFA system with greater driving
force (PffBT4T-2DT:SF-PDI2) as a control group, and
demonstrated that P3TEA:SF-PDI2 showed roughly identical
exciton dynamics, indicating an ultrafast charge separation in
spite of its minimal driving force. Moreover, through analyzing
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 Table 1. Summary of Representative Rylene Diimide-Based Acceptors
mobility (cm2 V‑1 s‑1)
internal LUMO HOMO Eg,opt D:A PCE VOC JSC device
acceptor ref (eV) (eV) (eV) donor ratio processing solvent (%) (V) (mA cm‑2) FF (%) E (neat) E (blend) H (blend) structure ref
phenyl-PDI 4.3 −4.01b −6.02c 2.01 PBTI3T 1:1 CF+0.5%DIO 3.67 1.024 6.56 54.59 2.8 × 10−3e NR NR inverted 127
TP-PDI 4.4 −3.82a −5.69a 1.89 PTB7-Th 1:1 DCB+1%CN 4.1 0.87 10.1 46.4 NR NR NR inverted 128
Chemical Reviews

Per 1 4.5 −4.06b −6.12d 2.068 PBDTTT-C-T 1:1 CB 2.78 0.76 7.9 46 8 × 10−3e NR NR inverted 129
Bis-PDI-T- 4.6a −3.84b −5.65b 1.69 PBDTTT-C-T 1:1 DCB+5%DIO 4.03 0.85 8.86 54.1 3.9 × 10−3e 1.0 × 10−3 3.0 × 10−3 conventional 130
EG
s-diPBI 4.7 −3.87a −5.95a 2.08 PBDTTT-C-T 1:1 DCB+1.5%DIO 3.63 0.73 10.58 46.80 3.21 × 10−5e NR NR conventional 132
+1.5%CN
a c
SdiPBI-S 4.8 −3.85 −6.05 2.20 PDBT-T1 1:1 CB+0.75%DIO 7.16 0.90 11.98 66.1 3.2 × 10−3 2.8 × 10−3 1.2 × 10−3 conventional 134
SdiPBI-Se 4.9 −3.87d −6.09d 2.22 PDBT-T1 1:1 CB+0.25%DIO 8.42 0.96 12.49 70.2 6.4 × 10−3 4.8 × 10−3 3.6 × 10−3 conventional 135
7b 4.10 −3.8b −6.0b 2.2 P3TEA 1:1.5 TMB+2.5%ODT 7.55 1.13 11.03 61 NR >10−7 NR inverted 136
SF-PDI2 4.11 −3.71b −5.71c 2.03f P3HT 1:1 DCB 2.35 0.61 5.92 65 NR 7.1 × 10−5 NR inverted 137
IDT-2PDI 4.12 −3.83a −5.53a 1.54 BDT-2DPP 1:1 DCB 3.12 0.95 7.75 42.4 NR 2.3 × 10−6 2.0 × 10−5 conventional 138
P1TP 4.13 −3.72a −5.66a 1.8 PBDTTT-C-T 1:1 DCB+3%DIO 3.61 0.89 7.78 52.1 NR 2.4 × 10−4 2.0 × 10−5 conventional 139
i-Me2T2-PDI2 4.14 −3.57b −5.55c 1.98 PffBT4T-2DT 1:1.4 CB 4.1 0.91 8.0 56 NR 8.3 × 10−5 1.8 × 10−3 inverted 140
CP-V 4.15 −3.98a −6.16c 2.18 PPDT2FBT 1:2 CF+DPE 5.28 0.87 10.04 60.16 NR 1.39 × 10−5 1.07 × 10−4 inverted 141
F2B-T2PDI 4.16 −3.83a −5.94a 1.77 PTB7-Th 1:1.2 NR 5.05 0.84 10.60 57 NR 3.4 × 10−5 9.8 × 10−5 inverted 142
S(TPA-PDI) 4.17 −3.70a −5.40a 1.76 PBDTTT-C-T 1:1 DCB+5%DIO 3.32 0.88 11.92 33.6 3.0 × 10−5 2.32 × 10−5 7.17 × 10−4 conventional 143
H-tri-PDI 4.18 −3.93b −6.01b 2.09 PBDT-TS1 1:1 CB+7%DPE 7.25 0.732 16.52 60.03 NR 1.4 × 10−5 1.2 × 10−4 inverted 144
B(PDI)3 4.19 −3.86b −6.0b 2.03f PTB7-Th 1:1.5 CB+3%CN 5.65 0.83 13.12 52 NR 4.20 × 10−5 1.748 × 10−4 inverted 145

3455
Ta-PDI 4.20 −3.81a −6.03a 2.05 PTB7-Th 1:1 CB+0.5%CN 9.15 0.78 17.10 68.5 NR 2.7 × 10−4 3.6 × 10−4 inverted 38
TPE-PDI4 4.21 −3.72b −5.77c 2.05 PTB7-Th 1:1.4 CB 5.53 0.91 11.7 52 1 × 10−3 NR NR inverted 146
Tetra-PDI 4.22 −4.00b −5.97c 1.97 PTB7-Th 1:1.2 DCB+3%CN 3.54 0.86 8.39 49 1.4 × 10−3e 8.66 × 10−5 1.88 × 10−3 inverted 147
TPC-PDI4 4.23 −3.75b −6.00c 2.25 PffBT4T-2DT 1:1.5 CB 4.3 0.96 9.2 49 2.8 × 10−4 NR NR inverted 148
TPPz-PDI4 4.24 −3.76b −5.86c 2.10 PffBT-T3(1,2)-2 1:1.5 CB+DCB(7:3) 7.1 0.987 12.5 56 2.3 × 10−3 NR NR inverted 35
Me-PDI4 4.25 −3.82b −5.96c 2.14 PBDTTT-C-T 1:1 DCB+3%DIO 2.73 0.77 7.83 45.0 NR 1.78 × 10−6 5.55 × 10−5 inverted 149
SF-PDI4 4.26 −3.78a −5.97a 2.05 PV4T2FBT 1:0.8 CB+2%DIO 5.98 0.90 12.02 54.2 NR 1.93 × 10−5 2.46 × 10−4 inverted 150
P4N4 4.27 −3.69a −5.97a 2.11 PDBT-T1 1:1 DCB+0.5%DIO 5.71 0.958 9.40 63.4 2.69 × 10−3 1.90 × 10−3 1.21 × 10−3 conventional 151
PBI-Por 4.28 −3.68a −5.46a 1.48 PBDB-T 1:1 CB+1%DIO 7.4 0.78 14.5 66 1.0 × 10−2e NR NR inverted 152
helical PDI 1 4.29 −3.77d −6.04d 2.14f PTB7-Th 3:7 CB+1%DIO+1% 6.05 0.803 13.3 56.6 NR 3.4 × 10−4 2.9 × 10−4 inverted 155
CN
FPDI-T 4.30 −3.77d −5.98d 2.22 PTB7-Th 1:2 CB+2%CN 6.72 0.94 12.48 58 NR 1.63 × 10−4 5.92 × 10−2 inverted 156
Ph2a 4.32 −4.03b −6.36b 2.10f PTB7-Th 1:2.25 CF+1%DIO 3.89 0.93 7.68 54.3 NR 4.6 × 10−5 NR inverted 157
FITP 4.34 −3.75b −5.48b 1.77f PTB7-Th 1.2:1 CB+2%CN 7.33 0.99 13.24 56 NR 3.66 × 10−4 5.60 × 10−4 inverted 158
hPDI4 4.35 −3.91d −6.26d 2.00f PTB7-Th 1:1 CB+1%DIO 8.27 0.802 15.1 68.2 NR 1.5 × 10−5 1.2 × 10−4 inverted 160
hPDI3-Pyr- 4.36 −3.76b −5.77c 2.01 PTB7-Th 1:1 CB 7.6 0.80 15.1 62.9 NR 7.1 × 10−4 3.9 × 10−4 inverted 161
hPDI3
TPH-Se 4.37 −3.80b −5.97c 2.17 PDBT-T1 1:1 DCB+0.75%DIO 9.28 1.0 12.99 71.5 3.2 × 10−2e 2.2 × 10−3 1.7 × 10−3 conventional 162
βTPB6-C 4.38 −3.75d −6.21d 2.14f PTB7-Th 1:1.5 CB+2.5%DIO 7.69 0.92 14.9 56 NR 4.67 × 10−5 2.67 × 10−4 inverted 163
+2.5%DPE
Fused-TriPDI 4.39 −3.73b −5.95b 2.20 PTB7-Th 1:1.5 CB 6.19 0.91 12.39 55 1.26 × 10−3e 2.83 × 10−4 4.17 × 10−4 inverted 164
FTTB-PDI4 4.40 −3.58a −5.74a 1.88 P3TEA 1:1.5 TMB+2.5%ODT 10.58 1.13 13.89 65.9 2.2 × 10−4 1.1 × 10−4 1.5 × 10−4 inverted 165
αPBDT 4.41 −3.78b −5.60b 2.18f PTB7-Th 1:1.5 CB+3%CN 4.92 0.81 12.74 46 NR 8.00 × 10−4 1.79 × 10−5 inverted 166
TPB 4.42 −3.89d −5.71d 2.14f PTB7-Th 1:1 CB+8%DPE 8.47 0.79 18.40 58 NR 6.10 × 10−6 1.08 × 10−5 inverted 167
Review

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Chemical Reviews Review

Measured by CV using NFA films. bMeasured by CV in solutions. cCalculated using measured LUMO/HOMO and the optical bandgap. dDetailed method was not reported. eMeasured using OFET
devices. fDetermined from the film absorption onset by the authors of this review; NR Not reported. CF: chloroform; DIO:1,8-diiodooctane; DCB: 1,2-dichlorobenzene; CN: 1-chloronaphthalene; CB:
chlorobenzene; TMB: 1,2,4-trimethylbenzene; ODT: 1,8-octanedithiol; DPE: diphenyl ether; CV: cyclic voltammetry; E (neat): electron mobility in NFA neat films; E (blend): electron mobility in
168
173
174
ref

conventional
structure
device

inverted

inverted
3.40 × 10−5
H (blend)
NR
NR
mobility (cm2 V‑1 s‑1)

1.73 × 10−5
1.59 × 10−7
E (blend)
2.2 × 10−5

Figure 5. Chemical structures of monomeric PDIs.

the electroluminescence external quantum efficiency (EL-EQE)

of four combinations of polymer:NFA with different driving
forces (Figure 9c), the authors showed that a decreased driving
E (neat)

force corresponded to an increased EL-EQE. The increased EL-

0.365e

EQE can be further translated into a small nonradiative

NR

NR

recombination loss, which also contributed to the overall low

energy loss. Further details of the detailed balance theory that
FF (%)
52.36
59.1
46

the authors employed to delineate energy loss are discussed in

section 11). These results were the first example of efficient
(mA cm‑2)

charge separation on a small driving force in a nonfullerene

12.57

10.77
5.47

organic solar cell, which manifested the great potential of using

JSC

NFAs to achieve a low energy loss system.

The spacer approach stimulated the design of many other
0.78
0.75
0.73
VOC
(V)

PDI dimers with different spacers. For instance, when a bulky

IDT unit was utilized as the spacer, the PDI dimer named IDT-
2PDI138 (Figure 7, molecule 4.12) demonstrated different
PCE

5.43
2.41
3.64
(%)

performance in combination with different donors: IDT-2PDI

exhibited a higher electron mobility in the P3HT blend, which
processing solvent

resulted in an excellent FF of 67%. When a molecular donor,

DCB+0.5%DIO

BDT-2DPP (Figure 6), was employed, a higher PCE (3.12%)

CB+2%DIO

was achieved due to a more compatible electronic structure

between the donor and acceptor. In another report by Wang et
al., the authors studied the structure−property relationship
CB

among PDI dimers containing oligothiophene spacers with

different lengths.139 A longer spacer provided the PDI dimers
ratio
D:A

1:1.5

donor:NFA blend films; H (blend): hole mobility in donor:NFA blend films.

1:1
1:1

with lower bandgaps, stronger absorption, and higher energy

levels. Using the same donor polymer PBDTTT-C-T, the
dimer with one thiophene (P1TP, Figure 7, molecule 4.13)
exhibited the best OPV performance (3.61% PCE). It was
PBDT-TS1
donor
PTB7-Th

hypothesized that the dimer with no spacer had a highly twisted

PTB7

structure and a large domain size. On the other hand, too long a
spacer led to an overmixed morphology that was detrimental to
charge transport. In another report, Zhao et al. synthesized PDI
2.18f
Eg,opt
(eV)

2.39
1.68

dimers containing methyl substituted bithiophene spaces

(Figure 7, molecule 4.14) and compared the effect of
substitution position on film morphology.140 The dimer
HOMO

−5.71a
(eV)

−6.6b
−5.9c

whose substitution offered a head-to-head geometry exhibited

a better blend morphology with a smaller domain size and thus
a higher PCE (4.1%) in the BHJ device with PffBT4T-2DT (c)
LUMO

−3.88a
−3.7a
−4.0b

as the donor polymer. Park et al. reported a V-shape PDI dimer

(eV)

(CP-V, Figure 7, molecule 4.15) where the two PDIs were

connected through the imide position.141 Compared to an M-
Table 1. continued

internal

shape dimer connected through the bay position, CP-V

4.43
4.44
4.45
ref

exhibited a larger bandgap, a higher electron mobility, and a

better solar cell device performance (PCE up to 5.28%).
Hadmojo et al. inserted a 2,5-difluorobenzene unit into a
2,2′-Bi(PDI)
acceptor

bithiophene-bridged PDI dimer and investigated the effect of

BTDI3
BiNDI

this unit on material property.142 The resultant acceptor F2B-

T2PDI (Figure 7, molecule 4.16) exhibited a larger bandgap, a
a

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Figure 6. Chemical structure of selected p-type polymers used in combination with NFAs.

stronger twisting between the two PDI units, and a better 4.1.3. Twisting Strategy-PDI Trimers and Tetramers.
device performance than the original dimer. To further explore the twisting strategy and design NFAs that
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Figure 7. Chemical structures of selected PDI dimers.
could form three-dimension (3D) or quasi-3D molecular
structures, other routes such as combining three or more
PDIs in a molecule were explored (Figure 10). A pioneering
study was reported by Lin et al., who synthesized a PDI trimer
named S(TPA-PDI) (Figure 10, molecule 4.17), in which three
PDI units were connected by a triphenylamine core.143 Due to
the existence of a sp3 hybridized nitrogen atom at the center,
the whole molecule possesses a quasi-3D nonplanar structure.
Due to the suppressed intermolecular interaction and molecular
aggregation, an efficiency of 3.32% was achieved when the PDI
tetramer was combined with a low bandgap polymer PBDTTT-
C-T. However, the electron mobility of S(TPA-PDI) in the
blend film was only 2.32 × 10−5 cm2 V−1 s−1, which may explain
the low FF (33.6%) of the device. In another study, a trimer by
elongation of Per 1 (H-tri-PDI, Figure 10, molecule 4.18)
achieved a PCE of 7.25% and an excellent JSC of 16.52 mA cm−2
with a high-performance donor polymer PBDT-TS1 (c).144
Later, a trimeric PDI (B(PDI)3, Figure 10, molecule 4.19) with
the three PDI arms connected to a central benzene core was
designed by Li et al.145 The nonplanar molecule, when
combined with the prototypical polymer PTB7-Th, exhibited
a PCE of 5.65%. In a more recent report by Duan et al., a PDI
trimer with triazine as the core unit (Ta-PDI, Figure 10,
molecule 4.20) was reported and compared with a benzene-
core analogue.38 It was found that the triazine-based trimer had
a less twisted structure and thus higher aggregation propensity,
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which leads to a higher electron mobility in the blend. With
PTB7-Th as the donor polymer, the Ta-PDI based OPV device
showed an outstanding PCE of 9.18% with a high JSC of 17.1
mA cm−2 and a high FF of 68.5%.
Besides trimeric PDIs, tetrameric PDIs were developed by
connecting four PDI arms to a central core. Liu et al. designed a
tetrameric PDI molecule with a tetraphenylethylene core (TPE-
PDI4, Figure 10, molecule 4.21).146 As a result of the highly
twisted nature of the TPE core, the molecule exhibited a weak
aggregation, which enabled a suitable phase separation and thus
a high PCE of 5.53% with PffBT4T-2DT as the donor polymer.
Akin to this approach, a PDI tetramer based on a
tetraphenylsilane core was developed (Figure 10, molecule
4.22).147 The compact core made the PDIs interlocked, and a
proof-of-concept device showed a PCE of 3.54% when blended
with PTB7-Th. Another study investigated the effect of the
central atom of the tetrahedron core on film morphology and
device performance, including carbon (TPC-PDI4, Figure 10,
molecule 4.23), silicon (TPSi-PDI4), and germanium (TPGe-
PDI4).148 It was shown that, using the same donor polymer
PffBT4T-2DT, both TPC-PDI4 and TPSi-PDI4 could achieve a
high efficiency of >4%, while the germanium-based one showed
an inferior performance (1.6%). Motivated by the PDI tetramer
TPE-PDI4,146 Lin et al. made a further modification to the
molecule by using a tetraphenylpyrazine core, which reduced
the extent of twisting compared with TPE-PDI4, enhanced the
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Chemical Reviews
Figure 8. (a, b) Optical images illustrating the overaggregation of
monomeric PDI (Per 2, molecule 4.2) and the reduced stacking of a
dimerized PDI (Per 1). (c) J−V characteristics of BHJ solar cells made
with PBDTTT-C-T:Per 1 (Figure 7, molecule 4.5) and PBDTTT-C-
T:Per 2. Adapted with permission from ref 129. Copyright (2012)
American Chemical Society.
electron mobility of the acceptor TPPz-PDI4 (Figure 10,
molecule 4.24), and improved the efficiency to 7.1% with
PffBT-T3(1,2)-2 (Figure 6) as the donor polymer.35 In
addition to connecting the PDI units at the bay region, four
PDIs connected to a tetraphenylcarbon core unit via the imide
region was also reported (Me-PDI4), which showed a PCE of
2.35% combined with the donor polymer PBDTTT-C-T.149
Another PDI tetramer with spirobifluorene as the core unit
(Figure 10, molecule 4.26) was also developed, exhibiting a
PCE of 5.98% when PV4T2FBT (Figure 6) was used as the
donor polymer.150 Liu et al. reported another PDI tetramer
with 2,3,7,8-tetraphenylpyrazino[2,3-g]quinoxaline as the core
unit (Figure 10, molecule 4.27),151 which enabled a PCE up to
5.71% with PDBT-T1 as the donor polymer. Later, a porphyrin
Figure 9. (a) Normalized FTPS-EQE spectra of pure P3TEA and blend P3TEA:SF-PDI2 blend devices. (b) Normalized electroluminescence spectra
pure P3TEA and P3TEA:SF-PDI2 blend devices. (c) EL-EQE of P3TEA:SF-PDI2 (blend A), PffBT4T-2DT:SF-PDI2 (blend B), P3TEA:diPDI
(blend C), and PffBT4T-2DT:diPDI (blend D)-based solar cells at different voltages. The value of the driving force for blend A is negligible; for
blend B it is 160 meV; for blend C it is 200 meV; and for blend D it is 370 meV. Adapted with permission from ref 87. Copyright 2016 Nature
Publishing Group.
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was used as the core by Zhang et al. to construct a PDI
tetramer PBI-Por (Figure 10, molecule 4.28), which had a
significantly lower bandgap and weaker crystallinity than most
other PDI acceptors.152 A polymer donor PBDTBDD with
complementary absorption was used and a PCE of 7.4% was
achieved.
4.1.4. Discussion: How Much Twisting Is Needed? The
structure−property relationship discussed in refs 38 and 35 has
stimulated the demand to reexamine the twisting strategy.
Specifically, through examining the effect of the twisting angle
on device performance for the series of structurally similar PDI
tetramers35 (Figure 11), it is not difficult to conclude that the
enlarged nonplanarity does not necessarily correspond to an
enhanced device performance. These results indicate that when
the nanoscale phase separation is within a reasonable range, i.e.,
not too large for efficient exciton dissociation, the essential
intermolecular π−π stacking that could dramatically change the
local or long-range charge transport property starts to play a
dominant role in determining the overall device performance.
This indication bears substantial importance to the PDI-based
NFA research, where the majority of effort has been focused on
introducing nonplanarity in the past.
Similarly, regarding the comparison between Ta-PDI and Ph-
PDI in ref 38, the Ph-PDI molecule bears resemblance to a
“three-wing propeller” with large twisting angles (76°, 54°, and
42°) between the PDI units; in contrast, two of the three PDI
units in Ta-PDI displayed a more coplanar geometry (19°)
while the third PDI unit showed a large twisting angle with
respect to the other two (83° and 74°; Figure 12). Nonetheless,
the blend films did not exhibit significant variation in terms of
phase separation, but the Ta-PDI demonstrated higher electron
mobility and considerably higher PCE than Ph-PDI when
combined with the same polymer.
4.1.5. Fused-Ring PDI. Ring fusion is an effective route to
enhance coplanarity of a molecule,153,154 which could lead to
enhanced molecular order that is beneficial for charge carrier
transport. As the previous work has demonstrated that the
chemists were able to introduce sufficient (in some cases even
too much) twisting,35,38 a proper extent of ring-fusion within
the molecule could potentially improve charge transport while
maintaining adequate donor/acceptor interface for charge
generation. Chemical structures of selected fused-ring PDIs
are shown in Figure 13. An example was given by Zhong et al.,
who designed a helical PDI dimer with an ethylene spacer
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Chemical Reviews
Figure 10. Chemical structures of trimerized and tetramerized PDIs.
(Figure 13, molecule 4.29). The rigid yet nonplanar structure
enabled an appropriate phase separation when blended with
PTB7-Th.155 An ultrafast electron transfer from the donor to
the acceptor and hole transfer from the acceptor to the donor
(∼0.2 ps) were revealed (Figure 14). As a result, an excellent
efficiency of 6.05% was achieved. In another report, three fused
analogue PDI dimers were developed using furan, thiophene, or
selenophene as the spacer.156 The dimer with thiophene as the
spacer was found to have the strongest intermolecular packing,
the highest electron mobility, and the best performance
(6.72%) with PTB7-Th.
Hartnett et al. studied the effect of ring-fusing between the
PDI unit and the spacer for three series of PDI dimers with
different spacers, namely thiophene (Figure 13, molecule 4.30),
benzene (Figure 13, molecule 4.31−4.33), and thienothio-
phene.157 They found that, compared to nonfused PDI dimers,
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ring-fusion between the spacer and PDI increased the
intramolecular electronic coupling, which, in general, resulted
in an upshifted LUMO and therefore a blue-shifted absorption
with sharp peaks (Figure 15). Along with increased electron
mobilities, the molecule with a fused benzene spacer achieved
the highest PCE of 3.89%, with PTB7-Th as the donor
polymer. In a later report, two PDI units were fused with an
IDTT bridge, which resulted in a fully planar dimer (Figure 13,
molecule 4.34).158 Nevertheless, the PCE when combined with
PTB7-Th reached 7.33%, which was likely the result of the
suppressed aggregation caused by the four bulky alkylphenyl
side chains.
In addition to PDI dimers, linear PDI oligomers were
reported and have been used to further improve the
photovoltaic device performance. In 2014, Zhong et al.
synthesized a series of PDI helical structures by fusing the
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Figure 11. Structures of TPC-PDI4, TPE-PDI4, and TPPz-PDI4 with a decreasing extent of intramolecular twisting. Reprinted with permission from
ref 35. Copyright 2016 John Wiley and Sons.
Figure 12. Calculated optimal molecular geometries of Ta-PDI and
Ph-PDI (top). Bottom: (a,b) atomic force microscopy (AFM) height
images and (c,d) phase images of PTB7-Th:Ta-PDI (a,c) and PTB7-
Th:Ph-PDI films. (b,d) Image size: 5 × 5 μm2. Reprinted with
permission from ref 38. Copyright 2017 John Wiley and Sons.
neighboring PDIs.159 Shown in Figure 16 below, different
ribbon lengths corresponded to different conformations. For
instance, the PDI tetramer showed two conformers while the
PDI tetramer had four isoenergetic conformations. Electroni-
cally, ring-fusion not only narrowed the bandgap (Figure 16g,h)
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Review
but also introduced more absorption bands with a signature
intense absorption peak in the higher-energy region, e.g., peak
at ∼385 nm for the dimer 2. Through DFT calculations and
femtosecond transient absorption spectroscopical studies, the
high-energy absorptions were attributed (at least partially) to
the electron being promoted from the olefinic bridges to the
LUMO situated on the PDI framework and/or the electron
being promoted from the HOMO situated on the PDI subunits
to the olefinic bridges.
The elongation of helical PDI 1 to fused PDI trimer and
tetramer increased the efficiency to over 8%.160 Similar to the
dimer, the trimer and tetramer were also nonplanar and rigid,
and their bandgaps decreased slightly with increasing number
of PDI units due to an extended conjugation. The strong
absorption and high mobility of h-PDI4 (Figure 13, molecule
4.35) enabled a PCE up to 8.3% with PTB7-Th as the donor.
Recently, a linear PDI oligomer with a pyrene connecting two
PDI trimers was developed (hPDI3-Pyr-hPDI3, Figure 13,
molecule 4.36).161 The ribbon had a molecular length of ∼5
nm and showed broad and strong absorption in the range of
300−650 nm, and the initial test with PTB7-Th achieved a PCE
of 7.6%.
Recently, a PDI trimer that combined design strategies
including (i) spacer fusion, (ii) functionalization of the end bay
regions, and (iii) construction of a 3D structure was reported
by Meng et al. (Figure 13, molecule 4.37).162 The three PDI
units, with selenium-annulated bay regions, were fused to a
benzene core. Due to a strong steric hindrance, the acceptor
TPH-Se exhibited a highly twisted three-bladed propeller
structure (Figure 17). The strong intermolecular interaction
contributed to a high electron mobility, which further led to an
excellent FF (71.5%) in the device when blended with PDBT-
T1. In addition, a broad and strong absorption enabled a high
JSC of 12.99 mA cm−2, and properly matched energy levels
contributed to a high VOC (1.0 V). Finally, an outstanding PCE
of 9.28% was achieved. Two other reports used a similar
strategy. The first example was an acceptor βTPB6-C (Figure
13, molecule 4.38) with four PDI units fused to a BDT-Th unit,
which also showed a 3D structure.163 Compared to its nonfused
analogue acceptor, βTPB6-C exhibited a larger bandgap, higher
VOC and JSC, and a higher PCE with PTB7-Th as the donor
polymer. The second example was the fused PDI trimer with
benzotrithiophene as the core unit developed by Wang et al.164
It was shown that the fused-TriPDI (Figure 13, molecule 4.39)
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Figure 13. Chemical structures of selected fused-ring PDIs. The blue color highlights the nonfused structure, while the green highlights the fused
structure.
Figure 14. Exciton generation and charge separation in the PTB7:1
blend at high excitation energy. Adapted with permission from ref 155.
Copyright (2014) American Chemical Society.
exhibited a larger bandgap, higher mobility, and better solar cell
device performance than the nonfused analogue molecule.
More recently, Zhang et al. used the ring-fusion strategy to
obtain a novel PDI tetramer named FTTB-PDI4 (Figure 13,
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Review
molecule 4.40) with a “double-decker” molecular shape, which
demonstrated an outstanding PCE of 10.58% when combined
with the polymer P3TEA.165 Compared to the nonfused PDI
tetramer, ring-fusion provided FTTB-PDI4 with a strong
intermolecular stacking, a high electron mobility, a blue-shifted
absorption (more complementary with the polymer), and
energy levels that are more compatible to the polymer. This
result further highlights the effectiveness of the ring-fusion
strategy in modulating the intramolecular property.
4.1.6. α-Substituted PDI. The α-position, or sometimes
referred as the nonbay or ortho-position, is another grafting site
that has been shown to have a different effect on the coplanarity
of the functionalized molecule in comparison to the bay-
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Figure 15. UV−vis absorption of Ph1, Ph2a, and Ph2b in ref 157.
Reproduced from ref 157 with permission from the Royal Society of
Chemistry.
position.147 Introducing substitution at the α-positions has
therefore been considered as an alternative route to address the
twisting-coplanarity problem and develop efficient PDI-based
NFAs (Figure 18).
Two pairs of PDI dimers, with benzodithiophene (BDT) or
pyrene diimides (PID) as the spacers connected at either bay or
α-position, were synthesized and studied by Zhao et al.166 For
both cases, the α-substituted PDIs (Figure 18, molecule 4.41)
showed a stronger aggregation, a higher electron mobility, and
finally a better PV performance. The best efficiency (4.92%)
was achieved with αPBDT when PTB7-Th was used as the
donor polymer. Recently, a BDT based core named TPB
(Figure 18, molecule 4.42) was employed by Wu et al. to
construct α-substituted PDI tetramers.167 Due to a comple-
mentary absorption and carefully optimized film morphology,
the JSC of the device surpassed 18 mA cm−2. Although the low
mobilities led to a moderate FF, the overall efficiency reached
8.47%. In another report, Fan et al. compared PDI dimers
connected directly to each other via different positions.168 DFT
calculations showed that the dimer connected at the α-position
(2,2′-bi(PDI), Figure 18, molecule 4.43) had a higher dihedral
angle between the two PDI units than that of the dimer
connected at the bay-position (1,1′-bi(PDI)). The absorption
spectrum of 1,1′-bi(PDI) was broader than that of 2,2′-
bi(PDI), indicating a stronger inter-PDI electronic coupling. In
Figure 16. DFT molecular geometries of PDI helical ribbons for the PDI dimer 2 (a), trimer 3 (b, c), and tetramer 4 (d, e, f) from ref 159. UV−vis
absorption (g) and photoluminescence spectra (h) for 2−4 along with a PDI monomer in solution. Adapted with permission from ref 159.
Copyright (2014) American Chemical Society.
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Review
addition, 2,2′-bi(PDI) exhibited a higher LUMO level and thus
a higher VOC of its BHJ solar cell. The overall PCEs were
similar for the two NFAs, when PTB7-Th was used as the
donor polymer.
4.2. Other Rylene-Based NFAs
In addition to PDI, its lower homologue NDI and higher
homologue such as TDI have also been employed to build
NFAs.169−172 A recent NDI-based NFA example was reported
by Liu et al. in 2015.173 The authors connected two NDI units
with a vinyl group. The NDI dimer, named BiNDI (Figure 19,
molecule 4.44), exhibited a near-planar structure and achieved
a PCE of 2.41% with PTB7 as the donor polymer.
In 2017, Feng et al. reported the first application of terrylene
derivatives as NFAs in organic solar cells.174 Similar to the
twisting strategy used to decrease the coplanarity of PDI-based
NFAs, a dimerized TDI and a trimerized TDI were synthesized
with a best PCE of 3.64% achieved using the BTDI3 (Figure
19, molecule 4.45) as the acceptor and PBDT-TS1 as the
donor polymer.
Compared to PDI, NDI-based NFAs typically exhibit a low
absorption coefficient in the visible as well as low electron
mobilities due to the shortened conjugated backbone. There-
fore, NDI is often used as the electron-withdrawing moiety to
design polymeric acceptors. On the other hand, TDI consists of
more conjugated aromatic rings than PDI, which typically leads
to red-shifted, intense absorption, and a high electron mobility.
However, too strong an aggregation tendency may be
detrimental for efficient free carrier generation. Besides, the
synthetic complexity may be another reason limiting TDI’s
application.
4.3. Summary and Challenges
Rylene diimides and their derivatives are the earliest electron
acceptors applied in organic solar cells and are still being widely
studied by many research groups. Among various rylene
diimides, PDI is the workhorse material to construct small
molecular NFAs owing to their capability of being function-
alized into derivatives that could be solution-processed into
nanoscale structures while retaining a relative high electron
mobility and a strong absorption coefficient. Most PDI
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Figure 17. (a) X-ray molecular structures of TPH 4b and TPH-Se 6a (top view and side view). (The alkyl chains and hydrogen atoms are omitted
for clarity.) (b) The slipped 3D stacking mode of TPH 4b (top) and TPH-Se 6a (down). (c) Se···O (3.0 Å) interactions between different PBI
subunits of TPH-Se 6a. Adapted with permission from ref 162. Copyright (2016) American Chemical Society.

acceptors have bandgaps over 1.9 eV, and therefore low
bandgap donor polymers were generally used to complement
the absorption. Electrically, electron mobilities of recent high-
performance PDI acceptors are typically on the order of 10−5 to
∼10−3 cm2 V−1 s−1, which, despite further enhancement still
being required, are able to enable a high FF in solar cell devices
in general. Another advantage of PDI-based acceptors is the
facile funtionalization of PDI. Substitution at different positions
has been realized to construct different acceptors. Nevertheless,
an important consideration of PDI acceptors is to control the
coplanarity, which is important to balance electron mobility and
3464
exciton dissociation. Meanwhile, most PDI-based organic solar
cells (OSCs) need to be processed with solvent additives.
Several reports showed that the device performance was
sensitive to the amount of additives, which is an issue to be
addressed since solvent additives may affect the large-scale
production and device longevity.
5. A-D-A TYPE ACCEPTORS
In addition to the development of rylene-based NFAs, the
successful strategy of using a conjugated “push-pull” structure
in designing semiconducting polymers has also been applied to
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Figure 18. Chemical structures of selected α-substituted PDIs.
Figure 19. Chemical structures of the NDI and TDI-based NFAs.
constructing NFAs. The electron-rich and electron-deficient
moieties combined can extend conjugation and reduce
bandgap. An A-(π)-D-(π)-A backbone (hereafter denoted as
A-D-A) is typically employed when designing novel NFAs,
where “A” and “D” represent the electron-withdrawing and
electron-donating moieties, respectively, which are sometimes
linked by a π conjugated spacer unit or a second “A” or “D”
moiety, to further extend the conjugation (Figure 20). Despite
Figure 20. Cartoon representing a chemical structural template for
designing the A-D-A type push−pull NFAs.
the fact that other types of NFAs have also been developed,
e.g., a D-A-D small molecular acceptor,175,176 most high
performance NFAs are synthesized using this structural
template. Besides the easily tuned absorption for spectral
breadth and the rigid backbone for reduced reorganization
energy that benefits charge conduction, the A-D-A molecules
have the electron-rich and electron-deficient moieties located at
different parts of the molecule, allowing possible contact
between the electron-deficient part of the donor material and
the LUMO of the NFA to facilitate charge transfer. Owing to
their strong intramolecular charge transfer, the A-D-A back-
bone typically exhibits strong and broad absorption that can be
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easily extended to the near-infrared (NIR) that could
substantially improve photocurrent generation and in the
meantime allows the design of semitransparent devices. To
tune the solubility and film morphology, alkyl or aromatic side
chains are typically introduced on the central fused-rings.
Overall, the synthetic flexibility, easily tuned electronic/optical
property, and rigid backbone make the A-D-A type small
molecules promising acceptor materials for nonfullerene OPV
applications. Chemical structures and properties of representa-
tive materials are summarized in Figure 21 and Table 2.
5.1. Early Reports of A-D-A Type Acceptors
One of the first NFAs of this type, named FEHIDT (Figure 21,
molecule 5.1), was reported in 2013 by Winzenberg et al.,
where the “A” and “D” units are indan-1,3-dione and fluorene,
respectively, and a thiophene was used as the spacer.177 The
spacer thiophene and the flanking indan-1,3-dione are coplanar,
but they have a dihedral angle of ∼20° with the central fluorene
unit. The acceptor molecule has a large bandgap similar to that
of PDI, with a strong absorption in the range of 400−600 nm.
A PCE of 2.43% was obtained by using FEHIDT in
combination with P3HT (Figure 6) as the donor polymer. In
a later study by Kim et al., the indan-1,3-dione (“A” unit) of
FEHIDT was replaced by 3-ethylrhodanine, and a new acceptor
named Flu-RH (Figure 21, molecule 5.2) was obtained.178 In
addition, the alkyl chains on the central fluorene unit were n-
octyl instead of 2-ethylhexyl. Overall, Flu-RH showed a similar
optical bandgap and absorption range to FEHIDT, but a higher
LUMO level offered it a high VOC of 1.03 V with P3HT, which
led to a best efficiency of 3.08% despite a lower FF (0.52).
Another early work on push−pull NFA was represented by
the report of FBR (Figure 21, molecule 5.3) by Holliday et al.
FBR was obtained by replacing the thiophene spacers in Flu-
RH by benzothiadiazole units.179 The bandgap and absorption
range of FBR was similar to those of Flu-RH. The spacer,
benzothiadiazole, and flanking rhodanine were coplanar, while a
dihedral angle of ∼35° between them and the central fluorene
unit was exhibited. The nonplanar structure could provide the
molecule with nonanisotropic electron transport and reduced
tendency to overaggregate, which contributed to an excellent
PCE of 4.1% with P3HT as the donor polymer.
A major breakthrough in the design of A-D-A type acceptor
is the introduction of an indacenodithiophene (IDT) building
block as the central “D” unit. The first example, a NFA named
DC-IDT2T (Figure 21, molecule 5.4), was reported by Bai et
al., where the “A” unit was 1,1-dicyanomethylene-3-indanone
(DCI).180 A small optical bandgap with a strong absorption
extended to the NIR region was demonstrated. The overall
device performance with a low bandgap donor polymer
PBDTTT-T-C was 3.93%.
Two milestone A-D-A type acceptors were soon reported by
modifying DC-IDT2T. The first one, IEIC (Figure 21,
molecule 5.5), reported by Lin et al., was obtained by adding
a 2-ethylhexyl alkyl chain on each spacer thiophene.181 Properly
matched energy levels and strong absorption ensured a high
VOC of 0.97 V and a good JSC of 13.55 mA cm−2, which led to
an excellent PCE of 6.31% when IEIC was blended with the
low bandgap polymer PTB7-Th. Later, Lin et al. reported
another milestone molecule named ITIC (Figure 21, molecule
5.6), where the IDT core was fused with the thiophene spacer
in DC-IDT2T.182 This modification slightly downshifted the
energy levels and enlarged the bandgap. In combination with
PTB7-Th, the BHJ solar cell (PTB7-Th:ITIC) exhibited PCE
DOI: 10.1021/acs.chemrev.7b00535
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Chemical Reviews Review

Figure 21. Chemical structures of A-D-A type NFAs.

3466 DOI: 10.1021/acs.chemrev.7b00535

Chem. Rev. 2018, 118, 3447−3507
 Table 2. Summary of Representative A-D-A Type Acceptors Materials
mobility (cm2 V‑1 s‑1)
internal LUMO HOMO Eg,opt D:A processing PCE VOC JSC FF device
acceptor ref (eV) (eV) (eV) donor ratio solvent (%) (V) (mA cm‑2) (%) E (neat) E (blend) H (blend) structure ref
FEHIDT 5.1 −3.95d −5.95c 2.00 P3HT 1.2:1 DCB 2.43 0.95 3.82 67 NR NR NR conventional 177
Flu-RH 5.2 −3.53a −5.58a 2.10 P3HT 1:1.5 DCB 3.08 1.03 5.70 52 NR NR NR conventional 178
Chemical Reviews

FBR 5.3 −3.57b −5.70b 2.14 P3HT 1:1 CF+DCB 4.11 0.82 7.95 63 NR 2.6 × 10−5 NR inverted 179
(4:1)
DC-IDT2T 5.4 −3.85a −5.43a 1.55 PBDTTT-C-T 1.2:1 DCB+15%CF 3.93 0.90 8.33 52.3 3.3 × 10−4 1.5 × 10−3 2.0 × 10−3 conventional 180
IEIC 5.5 −3.82a −5.42a 1.57 PTB7-Th 1:1.5 NR 6.31 0.97 13.55 48 2.1 × 10−4 1.0 × 10−4 4.5 × 10−4 conventional 181
ITIC 5.6 −3.83a −5.48a 1.59 PTB7-Th 1:1.3 NR 6.80 0.81 14.21 59.1 3.0 × 10−4 1.1 × 10−4 4.3 × 10−5 conventional 182
IDTT-2BM 5.7 −3.8a −5.5a 1.54 PBDTTT-C-T 1.5:1 DCB+CF 4.81 0.851 9.87 57.2 1.0 × 10−5 1.3 × 10−5 4.1 × 10−4 conventional 183
(6:4)+3%
DIO
IDT-2BR 5.8 −3.69a −5.52a 1.68 P3HT 1:0.6 DCB+3%CN 5.12 0.84 8.91 68.1 3.4 × 10−4 2.6 × 10−4 2 × 10−4 conventional 184
O-IDTBR 5.9 −3.88a −5.51d 1.63 P3HT 1:1 CB 6.30 0.72 13.9 60 NR 3−6 × 10−6 NR inverted 25
IDTIDT- 5.10 −3.82a −5.42a 1.53 PTB7-Th 1:1.5 DCB 6.48 0.94 14.49 47.5 NR 4.54 × 10−5 NR conventional 185
IC
IDTIDSe- 5.11 −3.81a −5.41a 1.52 J51 1:1 CF 8.02 0.91 15.16 58.0 1.27 × 10−5 7.87 × 10−5 7.21 × 10−5 conventional 186
IC
IDSe-T-IC 5.12 −3.79a −5.45a 1.52 J51 1:1 CF 8.58 0.91 15.20 62.0 NR 7.72 × 10−5 8.25 × 10−5 conventional 187
IC-C6IDT- 5.13 −3.91a −5.69a 1.62 PDBT-T1 1:1 CF 8.71 0.89 15.05 65 1.1 × 10−3 2.9 × 10−4 5.1 × 10−5 inverted 188
IC
IC-1IDT- 5.14 −3.83a −5.91a 1.70 PDBT-T1 1:1 CF 7.39 0.92 13.39 60 4.5 × 10−4 1.4 × 10−4 3.4 × 10−5 inverted 189

3467
IC
ITIC-Th 5.15 −3.93a −5.66a 1.60 PDBT-T1 1:1 CF+1%CN 9.6 0.88 16.24 67.1 6.1 × 10−4 4.2 × 10−4 3.0 × 10−4 inverted 190
m-ITIC 5.16 −3.82a −5.52a 1.58 J61 1:1 CF 11.77 0.912 18.31 70.55 2.45 × 10−4 1.30 × 10−4 1.54 × 10−4 conventional 191
IDT-BOC6 5.17 −3.78a −5.51a 1.63 PBDB-T 1:1 DCB+1%DIO 9.60 1.01 17.52 54 NR 4.99 × 10−4 5.31 × 10−4 inverted 192
ATT-1 5.18 −3.63b −5.50b 1.54 PTB7-Th 1:1.5 CB+1%DIO 10.07 0.87 16.48 70 NR 2.40 × 10−4 5.13 × 10−4 conventional 190
ATT-2 5.19 −3.90b −5.50b 1.32 PTB7-Th 1:1.8 CB+2%CN 9.58 0.73 20.75 63 NR 3.69 × 10−4 5.10 × 10−4 inverted 191
IEICO 5.20 −3.95a −5.32a 1.34 PBDTTT-E-T 1:1 CB+2%DIO 8.4 0.82 17.7 58 1.40 × 10−4 4.6 × 10−4 1.5 × 10−3 conventional 193
IEICO-4F 5.21 −4.19a −5.44a 1.24 PTB7-Th 1:1.5 CB 10.0 0.739 22.8 59.4 1.14 × 10−4 NR NR conventional 194
IT-M 5.22 −3.98a −5.58d 1.60 PBDB-T 1:1 CB+1%DIO 12.05 0.94 17.40 73.5 NR 1.10 × 10−4 3.33 × 10−4 inverted 195
INIC3 5.23 −4.02a −5.52a 1.48 FTAZ 1:1.5 CF+0.25% 11.5 0.852 19.68 68.5 1.7 × 10−4 1.4 × 10−4 2.0 × 10−4 inverted 196
DIO
ITIC-Th1 5.24 −4.01a −5.74a 1.55 FTAZ 1:1.5 CF+0.25% 12.1 0.849 19.33 73.73 NR 7.6 × 10−3 2.7 × 10−2 inverted 33
DIO
IT-4F 5.25 −4.14c −5.66c 1.52h PBDB-T-SF 1:1 CB+0.5%DIO 13.0 0.88 20.50 71.9 5.05 × 10−4 4.32 × 10−4 3.25 × 10−4 inverted 19
ITCC 5.26 −3.76a −5.47a 1.67 PBDB-T 1:1 CB+1%DIO 11.4 1.01 15.9 71 9.26 × 10−4 6.74 × 10−4 NR conventional 197
ITCPTC 5.27 −3.96b −5.62b 1.58 PBT1-EH 1:1 CF 11.8 0.95 16.5 75.1 3.2 × 10−3 2.69 × 10−3 1.71 × 10−3 conventional 198
DTBTF 5.28 −3.62b −5.68b 2.03 DR3TSBDT 1:0.5 CF 3.84 1.15 7.42 45 NR 4.13 × 10−5 1.14 × 10−4 conventional 199
DICTF 5.29 −3.79b −5.67b 1.82 PTB7-Th 1:1.4 CF 7.93 0.85 16.33 55 NR 1.93 × 10−4 3.82 × 10−4 conventional 200
FDICTF 5.30 −3.71b −5.43b 1.63 PBDB-T 1:1.2 CB+0.3%DIO 10.06 0.94 15.81 66 NR 2.40 × 10−5 3.37 × 10−5 conventional 201
CBM 5.31 −4.13b −6.05b 2.02 PTB7-Th 3:7 CB+2%DIO 5.3 0.88 10.6 53 NR 1.9 × 10−6 1.0 × 10−4 inverted 202
IDFBR 5.32 −3.70a −5.75a 2.0 P3HT 1:1 CB 4.5 0.89 7.4 68 NR NR NR inverted 26
SFBRCN 5.33 −3.86a −5.93a 2.05 PTB7-Th 1:1.2 CB+0.75% 10.12 0.90 17.25 65.2 NR 2.2 × 10−4 1.5 × 10−4 inverted 203
DIO
Review

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NFBDT 5.34 −3.83b −5.40b 1.56 PBDB-T 1:0.8 CF 10.42 0.868 17.85 67.2 NR 1.38 × 10−4 3.68 × 10−4 conventional 204
Chemical Reviews Review

up to 6.8%, comparable to PC61BM-based OSCs. A remarkable

Measured by CV using NFA films. bMeasured by CV in solutions. cMeasured by other methods. dCalculated using measured HOMO/LUMO and the optical bandgap. eDetailed method was not
205
ref
improvement was recently reported by using a large bandgap
polymer PBDTBDD for ITIC.29 Benefiting from suitable

conventional
structure energy levels, complementary absorption, and high mobilities, a
device

high VOC of 0.899 V, an excellent JSC of 16.81 mA cm−2, and a

FF of 74.2% were obtained, respectively, which resulted in an
outstanding efficiency of 11.21%.
5.2. A-D-A Type Acceptors with a Core Unit of IDT or Its
1.07 × 10−3
H (blend)

Derivatives
5.2.1. Design of the Core Units. Following the success of
IEIC and ITIC, new acceptors based on IDT and its derivatives
mobility (cm2 V‑1 s‑1)

have been developed. On the basis of ITIC, an NFA with

1.86 × 10−3
E (blend)

indacenodithieno[3,2-b]thiophene (IDTT) as the core unit,

named IDTT-2BM (Figure 21, molecule 5.7) was reported by
Bai et al.183 Compared to ITIC, the flanking units were changed
to 2-(benzo[c][1,2,5]-thiadiazol-4-ylmethylene)-malononitrile
(BM), leading to a reduced bandgap and a rigid, coplanar
2.17 × 10−3

backbone along the entire molecule. However, the electron

E (neat)

mobility of IDTT-2BM appeared to be lower than that of ITIC,

which caused a largely imbalanced hole/electron mobility and
reported. fMeasured using OFET devices. hDetermined from the film absorption onset by the authors of this review; NR Not reported.

could partially explain the modest FF (∼57%) and PCE

(4.81%) with PBDTTT-C-T as the donor polymer.
56.2
(%)
FF

The IDT core has also been introduced to FBR, and the
resulting NFA was named IDT-2BR (Figure 21, molecule
(mA cm‑2)

5.8).184 It adopted a planar backbone, while the hexylphenyl

11.23
JSC

side groups displayed a dihedral angle of 115° (Figure 22),

which facilities charge transport while preventing large phase
separation in the blend film. With P3HT as the donor polymer,
0.95
VOC
(V)

an excellent performance (5.12%) was achieved.

PCE
(%)
6.0
processing

CF+1%CN
solvent
ratio
D:A

1:1
donor
PTB7-Th

Figure 22. (a, b) Optimized molecular geometries of IDT-2BR. (c, d)

Molecular orbitals of IDT-2BR. Reproduced from ref 184 with
Eg,opt
(eV)
1.59

permission. Copyright 2015 Royal Society of Chemistry.

Later, Holliday et al.25 reported another effort to introduce

HOMO

−5.50a
(eV)

IDT core to FBR with n-octyl as the side chains on the IDT
core instead of the n-hexylphenyl used in IDT-2BR. This
acceptor, O-IDTBR (Figure 21, molecule 5.9), exhibited a red-
LUMO

−3.87a

shifted absorption and a more ordered nanostructure than both

(eV)

FBR and IDT-2BR due to an enhanced intermolecular packing,

especially after thermal annealing, which emphasized the
Table 2. continued

importance of side chains. The downshifted LUMO level

internal

5.35
ref

resulted in a smaller VOC of 0.72 V with P3HT, but the

broadened absorption boosted the JSC to 13.9 mA cm−2. An
overall PCE of 6.30% was achieved for P3HT:O-IDTBR, which
DTCC-IC
acceptor

was much higher than P3HT:PCBM based solar cells.

Li et al. showed an acceptor, IDTIDT-IC (Figure 21,
molecule 5.10), with a fused IDTIDT as the central donor unit
a

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Chemical Reviews
and DCI as the end-capping.185 The 10-heterocyclic fused ring
backbone of IDTIDT-IC extended its absorption into the NIR
(λedg ∼ 810 nm) region, which gave rise to a high JSC of 14.49
mA cm−2 in combination of PTB7-Th. In spite of the high JSC,
the BHJ device was able to achieve a high VOC of 0.94 V with a
low energy loss (∼0.59 eV, calculated by subtracting eVOC from
the optical bandgap of IDTIDT-IC) and a high IQE (>80%)
throughout nearly the entire absorption range. The electron
mobility for IDTIDT-IC in the blend film was lower than that
of IEIC or ITIC, which was likely the source of a relatively low
FF (47.5%). Overall, the best efficiency of PTB7-Th:IDTIDT-
IC reached 6.48%. On the basis of this work, Li et al. replaced
the two sulfur atoms at the end of the IDTIDT core with
selenium (Figure 21, molecule 5.11).186 The large Se atoms
increased the ground state quinoid resonance character, which
improved the electron mobility and lowered the bandgap.
When a medium bandgap donor polymer (J51; Figure 6) with
an intense absorption in the range of 400−600 nm was used to
complement the absorption, and a high efficiency of 8.02% was
achieved.
The strategy of replacing sulfur with selenium has also been
applied to modifying IEIC, which produced a planar acceptor
IDSe-T-IC (Figure 21, molecule 5.12) with a slightly lower
bandgap than IEIC.187 In combination with J51, a high
efficiency up to 8.58% was demonstrated.
One marked advantage of the A-D-A type NFA is their facile
synthesis. The “A” and “D” units could be distinctly prepared
before being connected together. As an example, Lin et al.
synthesized a facile planar fused ring molecule named IC-
C6IDT-IC (Figure 21, molecule 5.13), where an IDT core was
directly flanked with DCI units, and the side chains were simple
alkyl instead of alkylphenyl groups.188 The BHJ of PDBT-
T1:IC-C6IDT-IC, where the polymer and NFA showed
complementary absorption and compatible electronic property,
provided a PCE as high as 8.71%. To understand the
structure−property relationship, the authors synthesized a
series of structurally similar derivatives with 1−3 IDT as
cores and studied the morphological evolution of the series.189
An acceptor IC-1IDT-IC (Figure 21, molecule 5.14) was first
obtained by removing the alkyl thiophene spacer in IEIC, and
two analogues with 2 or 3 IDT in the cores were developed. It
was shown that, with increasing number of IDT in the core, the
bandgap as well as the tendency to crystallize of the acceptor
decreased, which was consistent with the trend for the electron
mobility. Two donor polymers, PTB7-Th and PDBT-T1, were
used to construct 6 different BHJs, among which, the best
performance (7.39% efficiency) was obtained with PDBT-
T1:IC-1IDT-IC due to a fine balance among energy level,
carrier mobility and film morphology. The aforementioned IC-
C6IDT-IC was achieved by replacing the alkylphenyl side
chains with simple alkyl chains on the IDT core unit.
Compared to IC-nIDT-IC (n = 1−3), IC-C6IDT-IC showed
a bathochromic shift in its absorption, ordered crystal packing,
and an improved electron mobility of 1.1 × 10−3 cm2 V−1 s−1 in
neat films and 2.9 × 10−4 cm2 V−1 s−1 in the blend with PDBT-
T1. These improvements resulted in a high FF and JSC, and an
excellent overall performance of 9.20%. It is also worth noting
that all of these devices were fabricated from as-cast films
without solvent additives in the solution or solvent/thermal
annealing after film formation.
5.2.2. Side Chain Effects. Akin to its role in the design of
polymeric donor materials, the side chains of A-D-A type NFA
are critical in determining the solubility and morphology. In
3469
Review
general, the “D” moiety consists of multiple conjugated
aromatic rings and is typically larger in size than the “A”
moiety. Therefore, in most high-performance A-D-A type
NFAs, the side chains are substituted on the “D” moiety, to
prevent excessive steric hindrance between the “A” units of the
acceptor and the electron deficient fragment of the polymer.
Drawing on the accomplishment of the IDT-based backbones,
engineering the side chains could further improve the device
performance and/or offer wider applicability to more donor
materials. For instance, Lin et al. replaced the alkylphenyl
chains of ITIC with alkylthienyl chains (ITIC-Th, Figure 21,
molecule 5.15).190 Compared to phenyl, the thienyl side chains
could enhance the nanoscale molecular order induced by the
sulfur−sulfur intermolecular interaction, which was beneficial
for electron transport. As a result, a PCE as high as 9.6% was
achieved in an optimized PDBT-T1:ITIC-Th BHJ, with an
excellent JSC of 16.24 mA cm−2 and a high FF of 67.1%.
In addition to using structurally different side chains, the
position of the side chain can also dramatically vary material
properties and device performance. For example, Yang et al.
relocated the alkyl chains on the phenyl rings of ITIC, forming
an isomer named m-ITIC (Figure 21, molecule 5.16).191 The
isomerization caused little effect on the electronic structure of
the acceptor but enhanced its intermolecular self-assembly. In
the two-dimensional grazing-incidence wide-angle X-ray
scattering (2D-GIWAXS) patterns (Figure 23), sharper and
Figure 23. (a) Line cuts of the 2D-GIWAXS patterns of neat m-ITIC
and ITIC films. 2D-GIWAXS patterns of (b) m-ITIC film and (c)
ITIC film. Adapted with permission from ref 191. Copyright (2016)
American Chemical Society.
more intense π−π stacking peaks were observed in the out-of-
plane direction for m-ITIC in both pure and blend films with a
medium bandgap polymer (J61; Figure 6). The enhanced
intermolecular interaction resulted in an increased electron
mobility, which in turn gave rise to an outstanding OPV
performance with a PCE of 11.77%, a VOC of 0.912 V, a JSC of
18.31 mA cm−2, and a FF of 70.55%. In addition, the authors
demonstrated that the PCE of the device was less sensitive to
thickness of the active layer, e.g., a PCE of >8% was maintained
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Chemical Reviews
even at a thickness of 360 nm, which further illustrated the
strong impact of a seemingly minor structural modification.
5.2.3. Effect of the Spacer Unit. Besides creating large
fused ring systems, another strategy to rigidify the backbone of
the acceptor was to use “conformational locks”, which utilizes
noncovalent interaction such as intramolecular hydrogen
bonding to lock the coplanar conformation. This strategy has
previously been employed to design polymers with high charge
carrier mobilities. Since the neighboring aromatic rings are
connected by a single bond, the synthesis of such conforma-
tional locked NFAs should be more facile than ring fusion. The
first attempt was reported by Liu et al.,192 who used
dihexyloxybenzene as the spacers to replace the thiophene in
IEIC. The new NFA, IDT-BOC6 (Figure 21, molecule 5.17),
was compared with an analogue acceptor without oxygen (IDT-
BC6). It was shown that IDT-BOC6 possessed a more planar
structure than IDT-BC6, which offered it a smaller bandgap, a
higher electron mobility, and a higher fluorescence quantum
yield. When PBDB-T (Figure 6) was used as the donor
polymer, a high PCE of 9.6% was achieved.
Liu et al. designed two acceptors with thieno-[3,4-b]-
thiophene as the spacer to replace the thiophene in IEIC,
namely ATT-1 (Figure 21, molecule 5.18)190 and ATT-2
(Figure 21, molecule 5.19).191 ATT-2 had the same electron
accepting moiety (DCI) as IEIC, while ATT-1 featured a new
“A” moiety, 2-(1,1-dicyanomethylene)rhodanine. In addition,
the direction of the thieno-[3,4-b]thiophene spacer was
different from each other for ATT-1 and ATT-2. Due to a
stronger electron-withdrawing ability of DCI, ATT-2 exhibited
a smaller optical bandgap, with absorption edge extended to
∼900 nm. Both acceptors were combined with PTB7-Th and
achieved PCEs of ∼10% in their BHJ solar cells. In addition,
benefiting from efficient photon harvesting in the NIR region,
semitransparent PTB7-Th:ATT-2 devices were fabricated and a
very promising PCE of 7.74% was achieved, while maintaining
an average transmittance of 37% in the visible with good color
rendering property.
The attempt to further reduce the optical bandgap of these
IDT-based A-D-A acceptors and harvesting more photons in
the NIR region was reported by replacing alkyl side chains with
alkoxy chains on the spacer units of IEIC.193 The new acceptor
IEICO (Figure 21, molecule 5.20) has an absorption edge of
∼925 nm due to an upshifted HOMO level compared with
IEIC. Consequently, when combined with a low bandgap
donor polymer PBDTTT-E-T, IEICO achieved a much higher
JSC (17.7 mA cm−2) and PCE (8.4%) than IEIC (JSC = 11.7 mA
cm−2 and PCE = 4.9%). Using the optical bandgap of IEICO,
g − eVOC) was as low as 0.52
the energy loss of this system (Eopt
eV.
5.2.4. Design of the “A” Unit. In addition to the central
“D” moiety, the side chains, and the spacer unit, the property of
the end-capping “A” moieties is essential for determining the
overall electron affinity and bandgap.
To be better energetically compatible with narrow bandgap
donor polymers, the energy levels of IEICO were downshifted
by introducing fluorine atoms on the end-capping DCI units,
which also narrowed its optical bandgap to 1.24 eV as a result
of the enhanced intramolecular charge transfer effect.194 When
the new acceptor, IEICO-4F (Figure 21, molecule 5.21), was
combined with the low bandgap polymer (PTB7-Th), an
outstanding JSC of 22.8 mA cm−2 was achieved, resulting in an
overall efficiency of 10.0%. Similar to IEICO, the device based
on PTB7-Th:IEICO-4F also demonstrated a small energy loss
3470
Review
g − eVOC) of ∼0.5 eV, indicating a high potential of the
(Eopt
PCE.
The increasingly smaller energy loss observed in these recent
NFA-based systems triggered research to further reduce the
energetic offsets between the donor and the NFA. Due to the
high PCE and wide applicability of the polymer PBDB-T in the
ITIC family NFAs, in order to further reduce energy loss, one
facile idea would be to slightly increase the energy levels of the
NFA on the basis of ITIC. By introducing one or two methyl
groups as the substituents to the end-capping groups
(dicycanovinylindan-1-one) of ITIC, Li et al. were able to
obtain two novel methyl-modified NFAs named IT-M (Figure
21, molecule 5.22) and IT-DM, respectively.195 Compared to
ITIC, incorporation of the methyl groups was found to slightly
upshift both the HOMO and LUMO levels, which enhanced
the VOC with the same donor polymer and improved the
nanoscale morphology in the meantime. Taking all of these
effects into account, the best device performance was achieved
using PBDB-T:IT-M, which showed a PCEmax of 12.05%, with a
VOC of 0.94 V, a JSC of 17.40 mA cm−2, and a FF of 73.5%.
Inspired by the success of IDTT as the core and fluorinated
DCI as the “A” moiety, Dai et al. constructed a series NFAs
using 6,6,12,12-tetrakis(4-hexylphenyl)-indacenobis(dithieno-
[3,2-b;2,3-d]thiophene) (IBDT) as the core, which had a
further extended, rigid and coplanar structure, as well as a
stronger electron donating ability than IDT and IDTT. DCI or
fluorinated DCI were used as the end-capping groups.196 The
resulting acceptor INIC had a larger rigid plane and stronger
electron-donating ability, which enhanced the optical absorp-
tion and electron transport. Fluorination on the DCI end
groups further enhanced charge transport ability, and lowered
the LUMO levels without significantly affecting the HOMO
levels. With two fluorine atoms on each DCI unit, the acceptor
INIC3 (Figure 21, molecule 5.23) showed the strongest
tendency to crystallize, which led to the tightest polymer
packing during the cocrystallization of FTAZ (Figure 6) and
INIC3. More importantly, the extended coherence length did
not result in an excessively large phase separation and a
reasonably small domain size in the FTAZ:INIC3 blend was
obtained. All of these factors contributed to excellent JSC and
FF of 19.68 mA cm−2 and 68.5%, respectively. Although the
lower LUMO level led to a relatively smaller VOC of 0.852 V
among the acceptors, the overall efficiency of FTAZ:INIC3
reached 11.5%.
Furthermore, fluorination of the DCI unit was also applied to
ITIC-Th and ITIC.33 Similar to the previous reports, a
monofluorinated acceptor, namely ITIC-Th1 (Figure 21,
molecule 5.24), exhibited lower energy levels, slightly red-
shifted absorption, improved intermolecular interaction, and
better electron mobility than ITIC-Th. When FTAZ was used
as the donor polymer, the blend FTAZ:ITIC-Th1 showed a
slightly higher crystallinity and a smaller domain size than
FTAZ:ITIC-Th. As a result, a high JSC of 19.33 mA cm−2 and a
FF of 73.73% of FTAZ:ITIC-Th1 led to an outstanding
efficiency of 12.1%, which was much higher than that base on
ITIC-Th. In a recent report, difluorination of each DCI unit of
ITIC led to a new acceptor IT-4F (Figure 24).19 To match the
downshifted energy levels of IT-4F, a derivative of PBDB-T was
developed by fluorinating the BDT building block. In
comparison to fullerene-based organic cells where the newly
designed polymers must meet the energy level requirement set
by PCBM, the capability of synergistically adjusting the energy
levels for both donor and acceptor clearly shows the design
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Chemical Reviews
Figure 24. (a) Chemical structures of ITIC and PBDB-T, along with
their fluorinated derivatives IT-4F and PBDB-T-SF, respectively. (b)
Absorption spectra of neat polymer and NFA films. (c) Energy
diagrams of the materials. Adapted with permission from ref 19.
Copyright (2017) American Chemical Society.
flexibility of materials for nonfullerene organic solar cells.
Compared to ITIC, the red-shifted absorption edge of IT-4F
allowed photon harvesting in the NIR, which resulted in a JSC of
20.50 mA cm−2 for the PBDB-T-SF:IT-4F BHJ and a
benchmark PCE of 13.0%. In addition, the device exhibited a
remarkable PCE of >12% at an active layer thickness of 200
nm.
Besides fluorination, Yao et al. reported another strategy to
modify the “A” unit by tailoring the aromatic ring of the DCI
building block.197 The new acceptor ITCC (Figure 21,
molecule 5.26) had a fused thiophene ring, instead of a phenyl
ring (ITIC), at each end of the molecule. The stronger electron
donating nature of the thiophene than phenyl provided ITCC
with a higher lying LUMO level than ITIC. Morphological
characterization revealed a denser π−π stacking for ITCC than
ITIC, which led to a higher electron mobility. With PBDB-T as
the donor polymer, the blend of PBDB-T:ITCC exhibited a
higher domain purity than PBDB-T:ITIC, which was
responsible for the suppressed bimolecular recombination and
enhanced FF of the former blend. Overall, the higher FF and
VOC led to a PCE of 11.4% for the PBDB-T:ITCC BHJ device,
despite a slightly reduced JSC due to the narrow absorption
range relative to ITIC. In another report by Xie et al., the
thiophene ring on the “A” unit was fused with the cyclopentane
ring at its 3- and 4-positions, which altered the double bond
arrangement and thus the electronic structure of the whole
molecule.198 The molecule ITCPTC (Figure 21, molecule
5.27) exhibited a slightly smaller bandgap and higher mobility
than ITIC. In combination with a large bandgap donor polymer
PBT1-EH (Figure 6), the overall PCE reached 11.8%.
5.3. A-D-A Type Acceptors with Other Core Units
In addition to IDT and IDTT, A-D-A type molecules with
other core units were also developed as promising NFAs. Ni et
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al. used the weak electron-donating unit fluorene as the
building block and introduced thiobarbituric acid as the end-
capping “A” unit to replace the rhodanine in Flu-RH.199 The
acceptor DTBTF (Figure 21, molecule 5.28) showed a large
optical bandgap with strong absorption in the range of 400−
600 nm. When blended with a medium bandgap molecular
donor DR3TSBDT (Figure 6), the BHJ device demonstrated a
high VOC of 1.15 V benefiting from the high LUMO level of the
acceptor. However, both the JSC and FF of the optimized device
were relatively low, which could be attributed to the relatively
low electron mobility and large domains observed in the
transmission electron microscopy (TEM) images, leading to an
efficiency of 3.84%. In a later report by Li et al., the “A” unit
was further replaced by DCI, and a new acceptor DICTF
(Figure 21, molecule 5.30) was obtained. The DCI end-group
lowered the LUMO level without significantly altering the
HOMO level.200 With PTB7-Th as the donor material, the
blend PTB7-Th:DICTF showed a higher JSC and FF than those
of DR3TSBDT:DTBTF. Overall, the PCE was improved to
7.93%. On the basis of these NFAs, Qiu et al. synthesized a new
acceptor FDICTF by rigidifying the core unit and the spacer in
DICTF, forming a ladder type large core unit.201 FDICTF
possessed two additional alkyl chains on each “lock” sitting
between the original core unit and spacer of DICTF. This
structure evolution flattened the molecule, slightly up-shifted
the LUMO level, and significantly elevated the HOMO level,
together causing the absorption to red-shift by ∼65 nm. To
complement the red-shifted absorption and modified energy
levels, the donor polymer PBDB-T was chosen to form a BHJ.
Compared to PBDB-T:DICTF, a significantly improved
efficiency up to 10.06% was achieved by PBDB-T:FDICTF.
Using 2-(benzo[c][1,2,5]thiadiazol-4-ylmethylene)-
malononitrile (BM) as the end-capping groups, Wang et al.
designed A-D-A NFAs with three core units including fluorine,
carbazole, and cyclopenta-[2,1-b:3,4-b′]dithiophene.202 The
three acceptors were named FBM, CBM (Figure 21, molecule
5.31), and CDTBM, respectively. They exhibited comparable
solar cell performance when PTB7-Th was used as the donor
polymer, with CBM showing the best PCE of 5.3%.
Baran et al. replaced the IDT core in O-IDTBR with
indacenodibenzene, which enlarged the bandgap.26 Although
the new acceptor IDFBR (Figure 21, molecule 5.32) showed
only a 4.5% PCE with P3HT, it showed strong and
complementary absorption to O-IDTBR. The ternary blends
using IDFBR and IDTBR as the acceptors and P3HT or PTB7-
Th as the donor demonstrated largely improved photovoltaic
performance (see section 9.3.1 for details) and device stability
(see section 10.1 for details).
Recently, Zhang et al. introduced spirobifluorene as the core
unit to FBR. Flanked with BT, the new acceptor, namely
SFBRCN (Figure 21, molecule 5.33), contained a strong
electron withdrawing unit, 2-(1,1-dicyanomethylene)rhodanine,
as the end-capping “A” moiety.203 The acceptor maintained a
similarly large bandgap (2.03 eV) to FBR, while the strong
electron deficient nature of BT and the end-groups afforded
SFBRCN a deep LUMO. Furthermore, the authors showed
that the 3D structure of the BT flanked spirobifluorene core
prevented the molecule from overaggregation. In combination
with the low bandgap polymer PTB7-Th, which provided a
complementary absorption to SFBRCN, the BHJ device
showed a high PCE of 10.12%.
Replacing the benzene unit in the IDT core by a BDT was
reported by Kan et al.204 The acceptor NFBDT (Figure 21,
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Figure 25. Chemical structures of DPP-based NFAs.
molecule 5.34) possessed the same conjugation length as
IDTT. Consequently, they showed similar bandgaps. When
PBDB-T was used as the donor polymer, a high PCE of 10.42%
was achieved by performing solvent vapor annealing to the
active layer prior to electrode deposition.
In another report by Cao et al., the IDT core in IC-1IDT-IC
was replaced by DTCC, which had seven fused rings and five
side chains.205 The acceptor DTCC-IC (Figure 21, molecule
5.35) had four alkoxyphenyl and one linear octyl side chains.
DTCC-IC had a smaller bandgap than IC-1IDT-IC and
showed a high SCLC mobility (∼10−3 cm V−1 s−1), which
gave rise to a 6.0% PCE in its BHJ solar cell with PTB7-Th as
the donor.
5.4. Summary
Although A-D-A type NFAs were developed much later than
PDIs, tens of new structures with excellent performance have
been reported to date. The best performance of this type has
surpassed those of both fullerenes and PDIs. Similar to PDIs,
A-D-A type NFAs are easy to synthesize and modify. The
functionalization of the end-groups, spacers, core units, and side
chains could be independently realized, which enables
numerous structure possibilities. In addition, the HOMO and
LUMO levels of A-D-A type NFAs can be easily tuned by
adjusting the electron rich and deficient strength of the “D” and
“A” building blocks, respectively. As a result, a large number of
NFAs with absorption edges in the NIR region have been
developed by using strong electron donating “D” units and/or
withdrawing “A” units, which is a challenging objective for PDI-
based NFAs.
6. OTHER NFAS
Despite the fact that most top-of-the-line PCEs were achieved
by either PDI-based or IDT/IDTT-based NFAs, research on
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NFAs with other cores and shapes had never halted. For
example, the diketopyrrolopyrrole (DPP) based NFAs continue
to emerge, and the subphthalocyanine (SubPc) type NFAs have
demonstrated planar heterojunction OPV devices with PCEs
over 8%.65 We note that phthalocyanine (Pc) dyes are widely
employed to design NFAs due to their high extinction
coefficient and relatively long exciton diffusion length. Most
of the Pc-based NFAs were deposited using vacuum deposition
techniques, and the OPV devices were based on planar
heterojunction structures. Since this review focuses on solution-
processed BHJ solar cells, the details of the Pc-based
nonfullerene planar heterojunction solar cells are not discussed.
Reviews on this topic are available.39,43,206−208 Nonetheless,
other NFAs with different structures can inspire the design and
application of new moieties in the state-of-the-art molecules.
This section surveys these NFA classes and summarize their
performance in BHJ OPVs.
6.1. DPP-Based NFAs
DPP, with a high polarity and a strong electron-withdrawing
ability, has been commonly used to construct NFAs.
Conjugated NFAs based on DPP typically features (i) easy
synthesis and modification, (ii) strong absorption profiles and
readily tunable energy levels, (iii) a strong tendency to
crystallize, and (iv) high carrier mobilities. Here we summarize
recent reports on DPP-based NFA materials (Figure 25 and
Table 3). It is worth noting that most of the DPP-based NFAs
were studied in combination with P3HT in BHJ solar cells,
partially due to the NFAs’ high-lying LUMO levels.
Similar to the development of PDI dimers, structure
engineering of the spacers of DPP dimers is an effective
method to construct different acceptor materials. The first
DPP-based acceptor with a PCE above 2% was reported in
2013 by Lin et al. with a structure of 5H-dibenzo[b,d]silole
(DBS) flanked by two DPP units (DBS-2DPP, Figure 25,
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 Table 3. Summary of Other Representative NFAs
mobility (cm2 V‑1 s‑1)
internal LUMO HOMO Eg,opt D:A processing PCE VOC JSC FF device
acceptor ref (eV) (eV) (eV) donor ratio solvent (%) (V) (mA cm‑2) (%) E (neat) E (blend) H (blend) structure ref
DBS-2DPP 6.1 −3.28a −5.30a 1.83 P3HT 1.2:1 DCB 2.05 0.97 4.91 43 3.3 × 10−4 2.8 × 10−5 6.1 × 10−4 conventional 209
Chemical Reviews

F(DPP)2B2 6.2 −3.39b −5.21b 1.77g P3HT 1:1 CF 3.17 1.18 5.35 50.2 2.8 × 10−4 NR NR conventional 210
F8-DPPTCN 6.3 −3.65b −5.31b 1.64 P3HT 1:3 CF+0.4% 2.37 0.97 6.25 39 NR 2.68 × 10−3 9.49 × 10−5 conventional 439
DIO
DPP 1b 6.4 −3.53b −5.29b 1.70 P3HT 2:1 NR 2.69 0.90 5.88 51 NR 2.05 × 10−5 5.87 × 10−4 conventional 211
SF-DPPEH 6.5 −3.60b −5.26b 1.79 P3HT 1:1 CF 3.63 1.10 6.96 47.5 NR NR NR conventional 212
SF(DPPB)4 6.6 −3.51b −5.26b 1.77g P3HT 2:1 CF 5.16 1.14 8.29 55 NR 1.292 × 10−4 1.480 × 10−4 conventional 36
DTDfBT(TDPP)2 6.7 −4.33d −5.85e 1.52 PTB7 1:2 DCB+1% 5.00 0.81 12.10 51 NR 8.2 × 10−4 3.1 × 10−3 inverted 213
CN
DTI 6.8 −3.9e −6.1e 2.21g PBDTTPD 1:1 CB+2% 1.47 1.051 4.6 30 NR NR NR conventional 214
CN
Cor-NI 6.9 −3.24b −6.28d 3.04 P3HT 1:1 NR 1.03 0.82 2.75 46 NR 1.32 × 10−4 NR inverted 215
DIR-2EH 6.10 −3.30b −5.38b 1.97 P3HT 1:4 DCB 3.05 1.22 4.29 58.2 NR 1.26 × 10−4 NR conventional 216
BNIDPA-BO 6.11 −3.6a −5.8d 2.22 PTB7 1:3 CB+DCB 3.08 0.98 8.13 39 NR 5.2 × 10−5 2.4 × 10−4 inverted 217
(9:1)
SubPc (2) 6.12 −3.5c −5.6c 2.03g PTB7 1:1.5 DCB+1% 3.51 0.935 7.8 48 NR NR NR conventional 207
DIO
BT(TTI-n12)2 6.13 −3.53e −5.99e 1.89 DPP-Py 1:2 CF 2.40 1.05 3.72 60 NR NR NR conventional 175
NIDCS 6.14 −3.42b −5.90b 2.22 P3HT 1:2.5 CF 2.71 0.73 8.04 46 NR 5.65 × 10−8 2.00 × 10−5 conventional 218

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S4 6.15 −3.73b −5.61b 1.74 p- 1:1 CB+0.4% 1.93 0.87 5.27 42 NR NR NR inverted 220
DTS(FBTTh2)2 DIO
NTz-Np 6.16 −3.60b −6.01c 1.73 P3HT 1:1 CB+DCB 2.81 0.90 5.18 60 NR 1.6 × 10−5 3.8 × 10−5 conventional 221
(4:1)
Ph-MH 6.17 −3.31b −6.01d 2.70 P3HT 1:1 CF 2.05 0.76 5.59 48 5.0 × 10−7 3.3 × 10−6 1.1 × 10−5 conventional 222
Zn(WS3)2 6.18 −3.85b −5.60b 1.55 P3HT 1:0.7 DCB 4.10 0.77 9.1 59 NR 1.9 × 10−4 2.1 × 10−4 inverted 227
DBFI-T 6.19 −3.8a −5.8a 1.73 PSEHTT 1:2 CF 5.04 0.86 10.14 58 0.006f 1.2 × 10−4 2.8 × 10−4 inverted 224
DBFI-DMT 6.20 −3.66a −5.82a 1.91 PSEHTT 1:2 CB+3% 6.4 0.92 12.56 55 0.056f 3.32 × 10−2 1.57 × 10−4 inverted 225
DIO
DBFI-EDOT 6.21 −3.65a −5.72a 1.70 PSEHTT 1:2 CB 8.10 0.93 13.82 63 NR 6.80 × 10−2 7.53 × 10−3 inverted 226
SF-OR 6.22 −3.25b −5.50b 2.15 P3HT 1:0.5 CF 4.66 0.96 7.44 65.0 NR 6.71 × 10−6 8.49 × 10−5 conventional 228
a
Measured by CV using NFA films. bMeasured by CV in solutions. cMeasured by other methods. dCalculated using measured LUMO/HOMO and the optical bandgap. eDetailed method was not
reported. fMeasured using OFET devices. gDetermined from the film absorption onset by the authors of this review; NR = not reported.
Review

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Figure 26. Chemical structures of selected NFAs with other core units.
molecule 6.1).209 The high LUMO level of DBS-2DPP led to a
high VOC (0.97 V) for the P3HT:DBS-2DPP device, and an
optical bandgap of 1.83 eV was beneficial for harvesting the
low-energy photons. By changing the spacer to dipropyl
fluorene and adding a phenyl end-group at each side of the
dimer, a new DPP acceptor F(DPP)2B2 (Figure 25, molecule
6.2) was developed.210 F(DPP)2B2 had a similar absorption
range with DBS-2DPP. With an even higher VOC of 1.18 V, the
overall PCE reached 3.17%. Later, Li et al. used cyanothio-
phene to replace the benzene as end-group and used octyl alkyl
chains to replace the propyl ones on the central fluorene
core.439 The new acceptor F8-DPPTCN (Figure 25, molecule
6.3) showed a lower LUMO level and a narrower bandgap than
F(DPP)2B2. As a result, in comparison with P3HT:F(DPP)2B2,
an increased JSC but a decreased VOC and FF were observed in
P3HT:F8-DPPTCN, leading to a slightly reduced PCE.
Constructing tetramers with a 3D or quasi-3D structure was
also reported for DPP-based NFAs. For example, a two-layer
structured DPP tetramer with [2,2]paracyclophane as the core
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unit (1b, Figure 25, molecule 6.4) was developed by Yang et
al., showing a PCE of 2.7% with P3HT.211 Another DPP
tetramer with spirobifluorene as the core unit was reported later
by Wu et al.212 Among several acceptors with different alkyl
chains, SF-DPPEH (Figure 25, molecule 6.5) with a branched
alkyl chain showed the highest crystallinity after annealing and a
PCE of 3.63%. In a later study, a phenyl ring was added at the
end of each DPP unit in SF-DPPEH.36 The new acceptor
SF(DPPB)4 (Figure 25, molecule 6.6) had an upshifted LUMO
level but a reduced optical bandgap compared to SF-DPPEH.
Therefore, both the JSC and VOC were enhanced, and an
excellent performance of 5.16% was achieved with P3HT. The
morphological stability was also demonstrated to be better than
the fullerene-based devices by a long-time thermal annealing
test.
Jung et al. synthesized two DPP-based NFAs. DTBT-
(TDPP) 2 had a 4,7-di-2-thienyl-2,1,3-benzothiadiazole
(DTBT) core flanked by two DPP units, and DTDfBT-
(TDPP)2 (Figure 25, molecule 6.7) had a fluorinated core.213
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The two NFAs both displayed a bandgap of ∼1.5 eV, but
fluorination provided DTDfBT(TDPP)2 with downshifted
HOMO and LUMO levels and stronger intermolecular
interaction. In combination with the relatively low-crystallinity
low-bandgap polymer PTB7-Th, DTBDfT(TDPP)2 showed
more crystalline features with reasonably small domains than
DTBT(TDPP)2 in their respective blends. The higher hole and
electron mobilities measured in the PTB7-Th:DTDfBT-
(TDPP)2 blend gave rise to an improved PCE (5.0%) over
the BHJ based on the nonfluorinated molecule (3.0%). It is
worth noting that both efficiencies were obtained through the
aid of 1.0% CN as solvent additive in the dichlorobenzene
(DCB) solution. All of the devices fabricated without CN
showed excessively large domains (PCEs below 1.0%), which
indicated that the strong aggregation tendency of the NFAs
favored a largely separated phase even with the low crystallinity
polymer. This is consistent with the crystalline nature of DPP
and suggests that solvent additive or other methods to
kinetically lock the morphology during film drying are needed
to achieve the small domain sizes.
6.2. Others
Besides the NFAs above, many other structures were also
explored (Figure 26). Here we categorize them into fused-ring
aromatics, linear oligomers, twisted dimers, and 3D structures.
Their properties along with device performance are listed in
Table 3.
6.2.1. Fused-Ring Aromatics. Decacyclene triimides
(DTI, Figure 26, molecule 6.8) were fused-ring aromatics
reported by Pho et al. in 2013, which consisted of a benzene
core and three fused naphthalimide units.214 The best efficiency
was 1.47% with PBDTTPD (Figure 6) as the donor polymer. A
possible factor limiting the efficiency was the large bandgap of
DTI, which constrained light harvesting in the blue region. In a
later report, an naphthalimide unit connecting to a corannulene
(Cor-NI, Figure 26, molecule 6.9) was synthesized by Lu et
al.215 The main absorption of Cor-NI was also in the UV range,
and the overall performance was 1.03% with P3HT. In another
study, Chen et al. reported a rubicence derivative named DIR-
2EH (Figure 26, molecule 6.10), which had a strong absorption
in the range of 400−600 nm.216 Due to a high-lying LUMO
level, the VOC was as high as 1.22 V with P3HT, and the PCE
reached 3.05% at a low D:A ratio of 1:4. Another acceptor with
two naphthalimide units fused onto a diphenylanthrazoline unit
was reported by Li et al. with a name of BNIDPA-BO (Figure
26, molecule 6.11).217 BNIDPA-BO had a planar backbone
with an absorption edge at ∼550 nm, but the main absorption
was in the 300−400 nm region. When PTB7 was used as the
donor polymer, the VOC was as high as 0.98 V but the FF was
only 39%, which resulted in an overall efficiency of 3.08%.
Ebenhoch et al. reported a derivative of SubPc in solution-
processed BHJ OSCs.207 The acceptor named 2 (Figure 26,
molecule 6.12) was obtained by connecting SubPc with a
phenoxy group, which had an absorption edge of ∼620 nm.
Using PTB7 as the donor polymer, a PCE of 3.5% was
achieved.
6.2.2. Linear Oligomers. Linear oligomers can be
developed by connecting different building blocks together.
One example was BT(TTI-n12)2 (Figure 26, molecule 6.13),
where a thienoimide unit was connected to each side of the
benzothiadiazole unit via a thiophene spacer.175 This acceptor
had an almost planar structure with an absorption edge at ∼650
nm. The linear alkyl chain on the imide unit was proved to be
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important for tuning the solubility and crystallinity. Using a
molecular donor DPP-Py (Figure 6) to complement the
absorption, a high VOC of 1.05 V and a PCE of 2.40% were
demonstrated. Another example of linear oligomer was
reported by Kwon et al. The molecule NIDCS (Figure 26,
molecule 6.14) consisted of a phenyl ring as the core unit,
naphthalimides as the flanking units and a thiophene-ethylene
spacer.218 Three acceptors with different side chains on the
phenyl rings were studied. It was shown that the spacers and
the central phenyl ring were nearly coplanar, while a dihedral
angle of ∼45° was observed between the thiophene and the
flanking naphthalimide unit. All three acceptors showed large
bandgaps, and the one without any side chains on the central
unit exhibited the best OPV performance (2.71%) with P3HT
as the donor. The low electron mobility in the blend (5.65 ×
10−8 cm2 V−1 s−1) was the limiting factor for achieving high FF
in these blends. The other two derivatives were further studied
with different donors. Kwon et al., in a later study, utilized a
polymer donor PPDT2FBT (Figure 6) and a NIDCS derivative
with longer alkoxy side chains.219 With more compatible energy
levels between the donor and acceptor, the VOC was improved
to 1.03 V. A thermal annealing step at 90 °C was also found
crucial for achieving the high performance, which was explained
by the increased crystallinity of the acceptor. The best efficiency
was 7.64% benefiting from a high JSC of 11.88 mA cm−2.
Another linear acceptor (Figure 26, molecule 6.15) with
chlorinated isoindigo (IID) as the central unit, thiophene as the
spacer, and naphthalimide as the flanking unit was later
reported by McAfee et al.220 The design strategy was that the
twisted naphthalimide unit could suppress the overcrystalliza-
tion tendency, and chlorination on the IID unit could improve
charge transport. With a molecular donor p-DTS(FBTTh2)2
(Figure 6), the best efficiency was 1.93%. Chatterjee et al.
synthesized a linear acceptor with a naphtho[1,2-c:5,6-c′]bis-
[1,2,5]thiadiazole as the core, thiophene-ethyne as the spacer
and naphthalimide as the end-capping groups (Figure 26,
molecule 6.16).221 With P3HT as the donor polymer, the best
efficiency was 2.81%. Jinnai et al. demonstrated another
example with a simple chemical structure (Figure 26, molecule
6.17).222 The benzothiadiazole-based acceptor had ethyne as
the spacer and phthalimide as the flanking unit. The effect of
alkyl chains on the phthalimide unit was investigated by
comparing five different alkyl chains. The alkyl chains were
found to have a strong influence on the energy levels and the
crystallinity of the materials and in turn the PV device
performance. Noticeably, the overall structural similarity
between the molecules allowed the authors to study the
structure−property relationship, and a good correlation
between JSC and the dispersion component of the surface
energy (γd) of the acceptor molecule was observed. The
authors hypothesized that the branched alkyl chain could
enhance the fraction of the amorphous region and thus expose
more conjugated planes to the D:A interface. The best
performance was achieved using the acceptor with special 2-
methylhexyl alkyl chains. When P3HT was used as the donor
polymer, an efficiency of 2.05% was achieved.
6.2.3. Twisted Dimers. Similar to the strategy used in
constructing PDI dimers, other twisted dimers based on other
electron withdrawing building blocks were also developed.
Spacers were frequently used to connect the building blocks. In
2013, the synthesis of a novel building block named
tetraazabenzodifuoranthene diimides (BFI), which had a large
planar backbone structure, was reported by Li et al.223 Different
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spacers were employed to construct dimers with the BFI
building block. The first example was DBFI-T (Figure 26,
molecule 6.19). With thiophene as the spacer, the two BFI
units showed a twisted structure.224 The acceptor had a large
bandgap and a deep LUMO level, and achieved a PCE of 5.04%
with PSEHTT (Figure 6) as the donor polymer. In a later
study, Li et al. explored four BFI dimers with different
spacers.225 The one with dimethylthiophene as the spacer
(DBFI-DMT, Figure 26, molecule 6.20) showed the largest
dihedral angle between the two BFI units, and the best PCE of
6.4% with the same donor polymer PSEHTT. The improved
PCE for DBFI-DMT over DBFI-T was attributed to the
enhanced electron mobility of DBFI-DMT and its upshifted
LUMO level and high EQEs. A subsequent research by Hwang
et al. demonstrated a dimer named DBFI-EDOT, where EDOT
was used as the spacer to further enlarge the dihedral angle to
76° between the two BFI units.226 With a further enhanced
electron mobility and higher energy levels, the overall
performance for DBFI-EDOT reached 8.1% with PSEHTT.
6.2.4. Three Dimensional Structures. Constructing a 3D
structure is a challenging but promising strategy to develop
high-performance acceptors due to the success of fullerenes. An
azadipyrromethene dimer with an zinc atom as the core
(Zn(WS3)2) was reported by Mao et al. in 2014 (Figure 27),
Figure 27. 3D structure of Zn(WS3)2. Reprinted with permission
from ref 227. Copyright 2014 John Wiley and Sons.
showing a 3D structure.227 In spite of the amorphous nature of
the molecule, the electron mobility in the blend with P3HT
could reach 1.9 × 10−4 cm2 V−1 s−1. With an absorption edge at
∼800 nm, Zn(WS3)2 had a complementary absorption to
P3HT. The BHJ solar cell of P3HT:Zn(WS3)2 showed a PCE
Figure 28. (a) Computed deviation from the molecular plane versus experimental PCE. (b) Computed difference between LUMO+1 and LUMO
energy versus experimental PCE for a device containing a given electron acceptor. The acceptors are classified as described in ref 229. (c) (Lack of)
correlation between molecular size and measured PCE for the considered data set. Reproduced from ref 229 with permission. Copyright 2017 Royal
Society of Chemistry.
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of 4.10%, which was higher than that of P3HT:PCBM. Another
SF-core based 3D acceptor (SF-OR) was recently reported by
Qiu et al., which had a high LUMO level and a high VOC of 0.96
V was achieved with P3HT as the donor polymer.228 Despite a
low mobility, the FF still reached 65%, and a high PCE of
4.66% was thus obtained.
7. COMPARISON AMONG DIFFERENT CORE UNITS
PDI-based NFAs exhibit outstanding thermal and chemical
stabilities, and they could achieve extraordinary electron
mobilities, proved by their successful application in OTFTs.
However, to be solution processable into nanoscale phase
separated grains, approaches such as molecular twisting are
introduced to overcome the overaggregation caused by
excessively strong intermolecular interaction, which dramati-
cally reduced the intrinsic high mobility of PDI. Broadly
speaking, most PDI-based NFAs show an electron mobility in
the range of 10−6 to 10−4 cm2 V−1 s−1, compared to 10−4 to
10−3 cm2 V−1 s−1for the IDT-based counterparts in blend films
with reasonable domain sizes for BHJ solar cell applications.
For DPP-based NFAs, an important limitation of their
application is their relatively high-lying LUMO levels, which
is not compatible with most low-bandgap donor polymers.
Regarding the recent rapid development of the A-D-A type
NFAs, besides their own distinctive advantages, the other
nontrivial reason is the existence of a large library of high-
performance large bandgap polymers as electron donor/hole
acceptor that could be chosen to match with the NFAs, which
generally have strong absorption in the red or even NIR region
of the solar spectra. Moreover, the design strategy of large/
medium bandgap polymers is relatively flexible. In contrast,
there are less high performance narrow bandgap polymers,
especially those with absorption in the NIR region, which limits
the maximum current and increases the difficulty in finding the
best match with novel PDI-based NFAs.
Besides PDIs and A-D-A type NFAs, many other structures
were also explored by different groups. Among them, only the
BFI-based dimers and the two 3D acceptors achieved PCEs
higher than 4%. However, one should not underestimate the
potential of these new structures because PDIs and A-D-A type
NFAs also struggled from limited efficiencies only a few year
ago. Further molecular design of the new acceptors could lead
to continuous improvement of their performance. In addition,
the structure−property relationships obtained in these NFAs
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may also be valuable for the development of any other high-
performance acceptor materials.
As there are increasingly more NFAs emerging each year, it is
essential to systematically investigate the common features
shared by the high-performance molecules and seek the
underlying chemical and physical principle to guide future
molecular design. In early 2017, Kuzmich et al. published an
analysis article by constructing a database of 80 NFAs (with
PCE ≥ 3%) with different core units and molecular geometries
and investigated whether common electronic and geometric
properties of the NFAs such as nonplanarity and molecular size
show any correlation with the overall device performance.229 In
line with our discussion, the authors revealed that, despite that
the highest PCEs for each NFA class were achieved at an
RMSDp between ∼1 and 2, there lacked a direct correlation
(Figure 28a) between the PCE and the nonplanarity of the
NFA (represented by the root-mean-square distance of the sp2
carbon atoms from the best plane passing across them,
RMSDp). Although there were only ∼13 data points with
high nonplanarity (RMSDp ≥ 2), the fact that all of them
showed PCE ≤ ∼6% suggests that excessive molecular twisting
is detrimental to charge transport that limits the overall PCE. In
addition, there appears to be no correlation between molecular
size (represented by the total number of atoms in a molecule)
and device PCE (Figure 28b). However, the authors calculated
the difference between LUMO and LUMO+1 (ΔLUMO) for
the neutral molecule and found that all of the 22 NFAs with
PCE >6% showed <0.5 eV ΔLUMO (Figure 28c). Despite the
fact that the low-lying LUMO+1 level could facilitate charge
separation at the donor/acceptor interface, the discovery of
such an apparent correlation between an isolated property of
the NFA and the overall device efficiency is still intriguing.
More recently, Lopez et al. conducted a statistical analysis of
∼51 000 NFAs. Using DFT calculations, the authors computed
the frontier molecular orbital energies and related them to the
PCEs through the Scharber model.230 Through machine
learning methods, they calibrated theoretical data to exper-
imental results, which allowed them to provide top NFA
candidates and design rules for future studies.
As more and more NFAs are developed, the top-down
analysis, i.e., building correlations from a large set of
experimental data,229,230 could serve as a supplement to the
bottom-up approaches, i.e., using fundamental working
principle to guide molecular design and device fabrication.
8. NONFULLERENE ALL SMALL MOLECULE OPV
Nonfullerene all small molecule solar cells (all SMSCs)
consisting of a p-type molecular donor and an n-type NFA
inherit most of the advantages of polymer:NFA solar cells while
improve batch-to-batch reproducibility. Historically, due to
their vacuum deposition ability and poor solution process-
ability, evaporated planar-heterojunction all-SMSC is the main
architecture to utilize the small molecules.65 Whereas, the
development of solution processed BHJ-type nonfullerene all
SMSCs has been limited by two main restrictions including (i)
overmixing between small molecular donor and acceptors in
the blend and (ii) low electron mobility of the NFA.120,231,232
Since both components of this device platform do not possess
long backbone (like a polymer does) as the charge carrier
transport highway, a lack of phase separation between the
components would likely induce free carriers to be confined
within a limited space by grain boundaries. In spite of these
limitations, thanks to the increasingly numbers of NFAs being
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developed, the PCE of this device platform has increased from
∼5% to >10% within 3 years.199,233−241
In 2013, Sharenko et al. combined the molecular donor p-
DTS(FBTTh2)2 with a monomeric PDI acceptor and obtained
a PCE of 3.0% for the solution processed BHJ solar cell using
0.4 vol % DIO as solvent additive in the chlorobenzene
solution.120 Later, by tuning the solvent additive in the solvent
mixture, Chen et al. achieved a PCE of 3.7% using a
combination of DTS(FBTTh2)2 and bis-PDI-T,241 while the
efficiency was boosted to 5.4% by Kwon et al. using the same
molecular donor and an naphthalimide based NFAs (NIDCS-
MO).240 The same NFA has been employed by Min et al. and a
PCE of 5.3% was demonstrated with a BDTT based p-type
molecular donor (BDTT-S-TR).238 The PCE was obtained by
surveying a series of solvent additive at various concentrations.
With the emergence of NFAs such as IEIC and O-IDTBR,
the PCE of all SMSC has been further enhanced.239 As an
example, Badgujar et al. used O-IDTBR and a rhodanine donor
BDT3TR to obtain device with a PCE >7% and an enhanced
thermal stability.237
Recently, the rapid PCE growth in IDT/IDTT-based
polymer:NFA solar cell field has also promoted the develop-
ment of relevant all SMSCs. Yang et al. synthesized an A-D-A
molecular donor (DRTB-T) using an alkylthienyl-substitued
BDT trimer as the core unit capped with 3-ethylrhodanines.235
The wide bandgap donor was combined with IC-C6IDT-IC,188
a narrow bandgap NFA, to obtain an efficient BHJ device with
efficiency up to 9.08%. The high PCE was enabled by a solvent
vapor annealing (SVA) process: a 30 s dichloromethane SVA
increased the PCE from 5.03% (as-cast) to 7.47% and a 60 s
dichloromethane SVA further enhanced the PCE to 9.08%.
This indicated a dramatic morphology evolution during SVA
and was confirmed by morphological characterization, which
revealed a clear increase in crystallinity of the blend film, mainly
caused by the enhanced intermolecular order of the acceptor.
In a more recent work by Bin et al., the authors designed a
pair of small molecular donors inspired by the success of the
BDTT-alt-FBTA D−A copolymers. The two small molecular
donors have different conjugation lengths enabled by the
difference in their side chains. Donor H11 had thienyl
conjugated side chains while the other donor H12 had alkoxy
side chains on the BDT unit. In combination with a highly
crystalline low bandgap NFA IDIC, the blend of H11:IDIC and
H12:IDIC yielded the best PCEs of 9.73% and 5.51%,
respectively, with a thermal annealing at 120 °C for 10 min
performed prior to electrode deposition. Compared to the
PCEs of the as-cast samples (5.37% for H11:IDIC and 1.83%
for H12:IDIC), thermal annealing caused a remarkable
enhancement to the device. Through a series of morphological
characterizations (Figure 29), thermal annealing has been
shown to induce prominent self-aggregation of the small
molecules and cause enhanced and more balanced hole and
electron mobilities for both material sets. Overall, the extended
conjugation of H11 and the extra crystallinity introduced by
thermal annealing provided a huge enhancement to the
performance of the device, which suggested a lack of phase
separation between the components in these two systems
originally. Furthermore, on the basis of this work, Qiu et al.
designed another molecular donor using cyano end-capping
groups and improved the donor:IDIC photovoltaic device
performance to 10.11%.234
Most of these reports utilize solvent additives or post-
treatments such as SVA or thermal annealing to tune the film
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Chemical Reviews
Figure 29. (a) Line cuts of the 2D-GIWAXS patterns of (b) H11, (c)
IDIC, (d) H11:IDIC (as-cast), and (e) H11:IDIC (thermal annealed).
Adapted with permission from ref 233. Copyright (2017) American
Chemical Society.
morphology. For most of them, the result of these
morphological tuning techniques is the enhanced crystallinity
for at least one of the components and enhanced phase
separation between the donor and acceptor. The general trend
for all SMSC is the propensity of forming an overmixed phase
due to the absence of polymerization that reduces the entropy
gain during mixing. Therefore, designing a BHJ of this type
should start with a NFA with a high crystallization tendency. In
fact, Figure 29 shows that even IDIC, whose pure film showed a
high crystallinity, lost most of the crystalline behavior in a blend
film with H11, which further demonstrated the high propensity
for two small molecules to mix. With a careful optimization of
solvent additives, SVA, or thermal annealing, the morphology
of the film can be modified to a state where charge transport is
enhanced while the initial intermixing is not totally destroyed.
These recent advances demonstrate the great potential of the
all SMSC. The flexible synthesis and readily tuned
spectroscopical and electrochemical properties of both
components in this device platform has provide numerous
potential combinations to further improve the device perform-
ance. As both branches (small molecule donor and small
molecule acceptor) are developing in a fast pace, it would not
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be surprising to observe further breakthroughs upcoming in the
near future.
9. TERNARY BLEND NONFULLERENE OPV
9.1. Motivations to Use Ternary Blend
To maintain the simplicity of the single-junction structure and
in the meantime broaden the absorption range of the OSCs,
ternary blend bulk heterojunction (BHJ) OSCs have been
developed where two donors and one acceptor or one donor
and two acceptors are blended together during device
fabrication. The original motivation for introducing a third
component into the active medium is to broaden the
absorption spectrum. Despite this beneficial effect on JSC, the
VOC of ternary blend solar cells has originally been predicted to
be pinned to the smaller VOC of the corresponding binary
blends of the constituent components,242 thus increasing the
overall energy loss of the device. However, ternary OSCs have
gone beyond expectations since the demonstration of devices
whose VOC change continuously with the film composition
(Figure 30a,b).243−245
The origin of the tunable VOC is complicated.247−251
Mainstream models such as organic alloy formation246,252 and
parallel-like BHJ,245,253 were used to explain such composi-
tional dependence of VOC. Street and co-workers revealed that
the charge transfer state energy also showed a dependence on
film composition (Figure 30c, d), which indicated the
formation of an organic alloy between the two acceptors (or
two donors).246 By comparing two donor:donor:acceptor
ternary systems where two different pairs of donor polymers
have either large or small interfacial tension, Gobalasingham et
al. proposed that the minimized interfacial tension between the
two donors, which allows the donors to better intermix, is the
prerequisite for the alloy formation and tunable VOC.254
Morphological studies and ionization potential measurements
on these ternary systems by Khlyabich et al. further confirmed
the effectiveness of using surface tension as a proxy to predict
organic alloy formation (Figure 31).249 The same correlation
has been observed by Jiang et al. on a series of nonfullerene
ternary blends with one polymer donor and two small
molecular acceptors.255 When the two acceptors (with different
LUMO levels) had a small interfacial tension (γ), the VOC of
the ternary devices demonstrated a tuned VOC with respect to
the weight percentage of the acceptor, whereas the devices
showed a pinned VOC when a NFA (ITIC-Th) was combined
with PC71BM due to the large interfacial tension between these
acceptors. In spite of these explanations, the result is that,
through the introduction of the third component, the ternary
device’s VOC could be tuned between the VOC of corresponding
binary blend devices, which is a considerable bonus effect in
addition to the absorption spectrum broadening. This
significantly increases the perceived impact of this device
platform.
9.2. Benefits of NFAs in Ternary Blend OPVs
Similar to the binary blend BHJ, a large fraction of previously
reported ternary blends contain a significant amount of
fullerenes,256−263 whose absorption cannot be easily tuned
and is relatively weak. Hence, in order to broaden the
absorption, the majority of the effort was focused on exploring
the option of two polymer donors and one fullerene
acceptor.254,261,264−271 However, polymers are large molecules.
From Flory−Huggins theory, the entropy gain for mixing
monomers is S = −R(ϕ1 ln ϕ1 + ϕ2 ln ϕ2), where ϕ1 and ϕ2 are
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Chemical Reviews Review

Figure 30. (a) Structures and corresponding HOMO and LUMO energy levels of P3HT, ICBA, and PC61BM. (b) VOC for the ternary blend BHJ
solar cells as a function of the amount of ICBA in the blend. (a, b) Adapted with permission from ref 244. Copyright (2011) American Chemical
Society. (c) Photocurrent spectra response data for the P3HT:PCBM:ICBA (D:A1x:A2(1−x)) ternary blend solar cells plotted as a function of ICBA
fraction in PCBM:ICBA pair. The inset indicates the CT transition or interface band gap that is being measured, and the pair of dashed lines
indicates the range over which the interface band gap energy is extracted. (d) Expanded plot of the peaks near 1.7 eV with the background
subtracted. The peak centered above 1.7 eV corresponds to PCBM absorption, and the peak centered below 1.7 eV corresponds to ICBA. (c, d)
Adapted with permission from ref 246. Copyright (2013) American Chemical Society.

the volume fractions of monomer 1 and 2. In contrast, when
mixing two polymers, the entropy gain becomes
ϕ1 ϕ2
S = −R ( N1
ln ϕ1 + N2 )
ln ϕ2 , where N1 and N2 are the degree
of polymerization of polymer 1 and polymer 2, respectively.
This suggests that the entropy gain for mixing two polymers is
much less than mixing two monomers/small molecules, which
is also the main reason for the enhanced difficulty to reduce
phase separation in all-polymer BHJ solar cells. Therefore, to
reduce ΔGmixing, the enthalpy of mixing, RTχϕ1ϕ2, must be
minimized, which creates a criterion that the Flory−Huggins
interaction parameter χ cannot be too large for achieving
adequate mixing. This explains why the tunable VOC in the
ternary blend with two polymers and one acceptor only occurs
when the two polymers have excellent molecular miscibility.
Compared to polymer blends, without the reduced entropy
gain during mixing, two small molecules are more likely to form
an intermixed phase. For example, when PC61BM and ICBA are
used in a ternary blend of P3HT, the device VOCs display an
almost linear compositional dependence,244 whereas fullerenes
3479
still possess the aforementioned limitations such as weak and
less tunable absorption, which reduces the potential for their
application in ternary blend OPVs.
NFAs, in contrast, do not have such a strong phase
separation tendency as two polymers or the common problems
possessed by fullerenes. Their feasible synthesis and easily
tunable optical properties make them ideal candidates for
enhancing JSC and VOC simultaneously in ternary blends.
Therefore, designing a pair of complementarily absorbing
miscible NFAs as acceptors in ternary blends is a promising
route to improve the performance of single-junction OPVs. We
note that, despite being beyond the scope of the review, this
idea has already been proved effective in multiple all small
molecule solar cells where two small molecule donors with
decent miscibility and complementary absorption were blended
with a fullerene acceptor and provide improved PCE over the
binary devices.259,272,273 In addition to device efficiency
improvement, it has also been suggested by multiple reports
that introducing the third component into the binary blend can
enhance the device stability. This may have huge impacts on
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Chemical Reviews Review

Figure 32. Visual illustration of the binary P3HT:IDTBR blend with

Figure 31. (a) Relationship between interfacial tension and VOC of the IDFBR presence, wherein the crystallinity of both P3HT and IDTBR
ternary blend device. Adapted with permission from ref 254. Copyright is preserved. Adapted with permission from ref 26. Copyright 2017
(2016) American Chemical Society. (b) VOC as a function of ITIC-Th Nature Publishing Group.
weight percentage for devices with a polymer:ITIC-Th:acceptor
ternary blend active layer. γ is the interfacial tension between the
two acceptors: a small γ corresponds to a quasi-linear relationship ance compared to the binary counterparts, owing mainly to the
while a large γ provides a pinned VOC. It is noted that PC71BM has a increased JSC and VOC. Besides efficiency, the NFA ternary
lower LUMO level than ITIC-Th while the other three NFAs have device demonstrated outstanding dark and photostability in air.
higher LUMO levels than ITIC-Th, which is accounted for the reverse Another work related to this design rule is reported by Liu et
trend in their VOCs. Reprinted with permission from ref 255. al., who also utilized two complementarily absorbing NFAs in a
Copyright 2016 John Wiley and Sons. ternary blend, one of which (SdiPBI-Se) absorbs strongly in
∼400−600 nm while the other (ITIC-Th) in ∼600−800 nm
reducing the energy payback time and the effective cost of (Figure 33).275 In combination with a polymer (PDBT-T1)
OPVs, which will be discussed in more details in the stability- that absorbs strongly at ∼500−700 nm, the ternary blend solar
focusing section 10. In section 9.3, we focus exclusively on the cells, at an optimal composition, were able to achieve
materials and photovoltaic device efficiency of ternary blend
OPVs with at least one NFA employed. For more details
regarding fundamentals of ternary OPV and discussions on
other types of ternary blend OPVs, review articles are
available.263−265,274
9.3. Utilizing NFAs in Ternary Blend OPVs
9.3.1. Pair of Miscible NFAs in Ternary Blend. A typical
example of employing two compatible NFAs with comple-
mentary absorption was given by Baran et al.26 The authors
employed IDTBR, a NFA working extremely well with the
prototypical polymer P3HT, and an indenofluorene analogue,
IDFBR, as acceptors in ternary blends with either P3HT or
PTB7-Th as the donor polymer. The absorption maxima for
IDTBR and IDFBR were at ∼690 nm and ∼530 nm,
respectively, which provided the ternary blend films with a
wider spectral range than the binary counterparts did. Despite
their similar chemical structures, differential scanning calorim-
etry (DSC) and morphological studies revealed different
behaviors between IDTBR and IDFBR in the ternary blend: Figure 33. (a) Chemical structures of PDBT-T1, SdiPBI-Se, and
the more diffusive and less crystalline IDFBR dispersed in both ITIC-Th. (b) Normalized UV−vis absorption spectra of neat PDBT-
crystalline polymer phase and crystalline IDTBR phase (Figure T1, SdiPBI-Se, and ITIC-Th films. (c) Schematic diagram of ternary
32), allowing the formation of a three-component redox organic solar cell device structure. (d) Energy level diagrams for
cascade. As a result, both P3HT based and PTB7-Th based PDBT-T1, SdiPBI-Se, and ITIC-Th. Reprinted with permission from
ternary blend devices showed enhanced photovoltaic perform- ref 275. Copyright 2016 John Wiley and Sons.

3480 DOI: 10.1021/acs.chemrev.7b00535

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Chemical Reviews
significantly enhanced JSC compared to either binary device
based on the constituent components. In addition, despite the
structural dissimilarity between the two NFAs, i.e., one based
on perylene bisimide while the other containing an IDT core,
the two NFAs demonstrate decent miscibility confirmed by the
morphological characterizations, which led to a linear relation-
ship between VOC and film composition. As a result of both
improved JSC and tunable VOC, the best ternary device
demonstrated a PCE ∼10.3%, much higher than the binary
counterparts (∼8.2% and ∼6.4%).
In line with these work, Yu et al. employed two NFAs with
IDT cores, IT-M and IEIC-O,194 whose bandgaps were 1.58
and 1.37 eV, respectively, in a ternary blend in combination
with a large bandgap polymer, J52.276 The similar LUMO levels
between IDT and IT-M offered their binary BHJ devices, when
each was blended with J52, almost identical VOCs, but the
elevated HOMO level of IEIC-O caused a red-shifted
absorption, which provided more complementary solar
spectrum coverage and was the main source of the improve-
ment in JSC (from binary 17.1 to ternary 19.7 mA/cm2) and
thus PCE (from 9.4% binary to 11.1% ternary) at a IT-M:IEIC-
O weight ratio of 4:1. Besides, the structural similarity provides
the NFAs with compatible morphology, i.e., the blend
morphology of IT-M and IEIC-O can be viewed as the
compositional average of morphology formed by the individual
material. This is another factor for maintaining the high FF in
the ternary blend device.
Furthermore, Jiang et al. systematically studied the device
performance of a series of polymer:NFA1:NFA2-based ternary
blends, where NFA1 and NFA2 are two different nonfullerene
acceptors.255 By comparing four different combinations of
NFA1 and NFA2 including the structurally similar ITIC-Th
and IEIC-Th, the structurally dissimilar ITIC-Th and SF-PDI4
or TPE-PDI4, the authors not only confirmed the role of
surface tension in influencing device behavior (tuned vs pinned
VOC) but also provided a morphology control method for
constructing nonfullerene ternary blends. It was found that the
morphology of the ternary blend could be effectively controlled
through the use of two NFAs with a small interfacial tension
and a polymer with a temperature dependent aggregation
property. An enhanced PCE (11.2%) was achieved despite the
similar absorption ranges of the two NFAs, which was
attributed to the enhanced electron transport through (higher
FF) and elevated LUMO level of the third component (higher
VOC). Su et al. reported a ternary blend consisting ITIC and
IDIC as acceptors and a large bandgap polymer PSTZ as
donor.277 However, ITIC and IDIC have almost identical
absorption range. The authors attribute the device performance
enhancement to the improved morphology and charge
transport by tuning the ratio of the two NFAs. These results
imply that in addition to broadening absorption range and
increase VOC, blending two NFAs also has a potential to fine-
tune the blend morphology. This clearly is another advantage
for this device platform as tuning the morphology278 in a
controllable fashion has significant implication for charge
generation and transport of OPVs.
9.3.2. Blending NFA with a Pair of Polymer Donors.
The idea of broadening spectral range using NFA has been
extended to all-polymer solar cells. Ding et al. added 6 wt %
ITIC into a polymer donor:polymer acceptor blend (PTP8:P-
(NDI2HD-T)).279 Compared to both polymers, ITIC has a
red-shifted absorption. Besides, the addition of ITIC played
another critical role of balancing hole and electron mobility
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through tuning the blend film morphology. As a result, a PCE
improvement from ∼6% binary to ∼7% ternary was achieved.
The same NFA, ITIC, has been utilized by Zhong et al. in a
ternary blend with two conjugated polymer donors, J51 and
PTB7-Th, and an improved ternary device PCE of ∼9.7% was
observed by carefully tuning the film composition.280
In ref 194, to further utilize the photons in shorter
wavelength region, ternary solar cells with a small amount of
a medium bandgap donor polymer J52 was added to the blend
of PBDTTT-EFT:IEICO-4F, and the efficiency was improved
from 10.0% to 10.9%, benefiting from the exceptionally high JSC
of 25.3 mA cm−2.
9.3.3. Combining NFA and Fullerene in a Ternary
Blend. NFAs have also found their application in ternary blend
OPVs in conjunction with fullerene to enhance photovoltaic
performance.
Chen et al. used a tiny amount of fullerene to sensitize the
binary blend formed by a red-to-NIR absorbing NFA, IEIC-O
and a medium bandgap polymer PBDTTT-E-T.281 With a
minute amount of only 5% (w/w) in the blend, the ternary
devices were able to achieve increased JSC and FF. Due to the
low fraction of fullerene, the enhanced current cannot be
simply explained by the broadened absorption. Instead, through
morphological investigation and charge transfer mechanism
studies (Figure 34), the authors concluded that the fullerenes
that have higher LUMO levels than IEIC-O, serving the dual
roles of facilitating electron transfer by forming an energetic
cascade and adjusting the blend morphology toward the
direction of reducing geminate recombination. Another work
reported by the same group also employed bis-PC71BM as the
third component and added it into the polymer:NFA blend.282
At a weight ratio of 1:1:0.2 (PBDB-T:IT-M:bis-PC71BM), the
ternary device showed an optimized PCE of 12.20% with
simultaneously enhanced JSC, VOC, and FF. It was concluded
that more effective dissociation of excitons at the polymer:-
acceptor interface was the main factor contributing to the
device performance enhancement.
In another report by Fan et al.,283 the authors also took
advantage of the electronic property of the NFA, IFBR, and
used it to design a charge transfer cascade. Both IFBR’s HOMO
and LUMO lie between the polymer and fullerene, which
dramatically suppressed trap-assisted recombination in the
ternary blend device. As a result, together with the broadened
spectral coverage by IFBR, the best ternary blend exhibited an
>40% increase in PCE compared to the polymer:fullerene
binary device.
Difference in molecular interaction between NFA and
fullerene in a ternary blend could cause variations in phase
separation. One report by Chen et al.284 employed the organic
alloy formation between the NFA (TPE-4PDI) and PC71BM to
explain the tunable VOC in the ternary blend PTB7-Th:TPE-
4PDI:PC71BM, despite the drastically different chemical nature
between the two acceptors. The authors used DFT calculations
to simulate the composition dependence of VOC. At a mass
electron DOS ratio of 2:1 between PC71BM and TPC-4PDI,
the calculated VOC curve fit well with the experimental data,
which provides support to their model. In another ternary
system reported by Liu et al.,253 where ITIC-Th and PC71BM
were blended together with a wide bandgap polymer (PDBT-
T1), the quasi-linear relationship between VOC and ITIC-Th
weight ratio was interpreted by a parallel-like BHJ model. The
authors carried out grazing-incidence X-ray diffraction
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Chemical Reviews
Figure 34. (a) Electron spin resonance (ESR) response of the
PBDTTT-E-T:Bis-PC71BM:IEICO ternary blends. (b) Schematic of
charge transfer in ternary blend films. (c) EQE spectra of PBDDTTT-
E-T:IEICO binary and PBDTTT-E-T:Bis-PC71BM:IEICO ternary
blend devices. Reprinted with permission from ref 281. Copyright
2017 John Wiley and Sons.
(GIXRD) and R-SoXS studies and concluded that ITIC-Th and
PC71BM form their own transport network.
In general, NFA and fullerenes have rather different chemical
structures and electronic and material properties. Different
miscibility between NFA and fullerene may cause a
fundamentally different working principle of ternary blend
solar cells. For example, both organic alloy and parallel linkage
models have been used to explain device behavior in different
systems, indicating dramatically different interaction between
fullerene and NFA in the blends. Meanwhile, miscibility and
morphology characterization are highly demanded in con-
junction with the energy diagram and recombination analysis
when the model of charge transfer cascade is used to explain
device performance since the energetically favorable transition
may be spatially forbidden (or vice versa). Broadly speaking,
different mechanisms may coexist in determining the overall
device performance. Therefore, interpreting device result in
NFA/fullerene blends requires a better understanding on the
molecular interaction among polymer, fullerene, and NFA.
Furthermore, systematic investigation of the voltage loss
mechanism is also needed to clarify the role of NFA in such
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blends. Additionally, studies on ternary device stability are
needed to figure out whether the introduction of fullerenes in
NFA OPVs decrease the lifetime of the devices.
10. ENHANCED DEVICE STABILITY OF
NONFULLERENE OPV
As the maximum reported PCE reached above 13%, OPV
device’s operational stability becomes increasingly vital for the
objective of commercialization. Possible degradation routes of
OPVs are manifold.17,285−287 For example, the morphology
optimized for device efficiency might not be in thermodynam-
ical equilibrium, which causes the nanoscale morphology to
change during operation, particularly for the fullerene involved
systems due to their high diffusivity.288−291 In addition,
dimerization of fullerenes caused by photochemical reaction
further increases device instability.288−291 Besides, molecular
oxygen has been shown to cause both reversible and irreversible
effects on performance of the devices based of π-conjugated
systems.17,286 As fullerenes play a role in most of these
degradation pathways, the replacement of fullerenes with NFAs
could be beneficial for device longevity.
10.1. Enhanced Stability of BHJ Solar Cells with IDT Based
A-D-A Type NFAs
On the basis of the improved device longevity for P3HT:O-
IDTBR demonstrated by Holliday et al.25 (section 5.2.1), Baran
et al. further revealed that an 800 h exposure to air made the
P3HT:PC71BM BHJ solar cell nonfunctional, whereas the
device retained 70% of the efficiency under the same condition
once the fullerene was replaced with IDTBR (Figure 35).26 The
same trend had been observed in these devices under 1.5 AM
illumination, unencapsulated in air.
Later, Gasparini et al. compared the “burn-in” effect (a rapid
decay in the early stage followed by a flattened slower decay at
longer times) between P3HT:PC71BM and P3HT:IDTBR
devices.27 It was concluded that fullerene dimerization was the
primary cause of the photoinduced burn-in. Replacing PC71BM
eliminated not only dimerization but also the disorder induced
voltage loss.
In a later work by Wadsworth et al., the stability of
nonfullerene solar cells fabricated using a low bandgap polymer
(PffBT4T-2DT) and an A-D-A type acceptor (EH-IDTBR)
was systematically compared among various processing solvents
for the active layer.28 The authors showed that the devices
whose active layers were processed from hydrocarbon solvents
such as o-xylene, mesitylene, and trimethylbenzene showed
more reproducible device performance. In addition, the
mesitylene processed nonfullerene device maintained ∼92%
of its initial PCE after 4000 h storage in a N2 atmosphere and
∼80% initial PCE after 250 h under illumination, which
outperformed the devices processed from chlorobenzene.
The workhorse A-D-A type NFA, ITIC, showed excellent
thermal stability in the BHJ solar cells with PBDB-T as the
polymer donor.29 In comparison to PBDB-T:PC71BM, PBDB-
T:ITIC based device exhibited little PCE decline after being
thermally annealed at 100 °C for 250 h, while the former
dropped by >40% of its initial value (Figure 36). In line with
these reports, decent thermal stabilities were also presented in
other A-D-A type NFA based solar cells.30,31
Choi et al. synthesized a novel conjugated polymer, 3MT-Th,
and evaluated its performance in BHJ solar cells with ITIC as
the electron acceptor.32 The active layer was fabricated using
nonhalogenated solvent. Compared to PTB7-Th:ITIC, 3MT-
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Figure 35. (a) Shelf storage lifetime (dark, in air) comparison of
P3HT:IDTBR:IDFBR device efficiencies with other polymer:fullerene
systems. Devices were exposed to ambient conditions over a 1200 h
duration or until devices no longer showed any diode behavior. (b)
Photostability of P3HT:IDTBR:IDFBR device and polymer:fullerene
solar cells (in air, unencapsulated, under AM1.5 illumination at 1 sun)
for 90 h. Adapted with permission from ref 26. Copyright 2017 Nature
Publishing Group.
Figure 36. PCEs of the PBDB-T:PC71BM and PBDB-T:ITIC devices
against time of thermal annealing at 100 °C. Reprinted with
permission from ref 29. Copyright 2016 John Wiley and Sons.
Th:ITIC based devices exhibited superior shelf lifetime with no
obvious PCE decay after 1000 h (Figure 37), which was
attributed to the robust morphology formed between 3MT-Th
and ITIC. By measuring the UV−vis spectra of both pure and
blend films under illumination, the authors observed a fast
decay of the 0−0 vibronic peak in the neat PTB7-Th film,
which was not observed for 3MT-Th. In addition, from the
variation of the 649 and 703 nm peaks of the UV−vis spectra
upon illumination time (in air), the authors attributed
enhanced stability of 3MT-Th:ITIC to mainly the better
photostability of the polymer in the blend.
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Figure 37. Evaluation of device performance stability under ambient
conditions up to 1100 h storage. (a) 3MT-Th:ITIC processed from
toluene with 0.25% diphenyl ether (DPE) and (b) PTB7-Th:ITIC
processed from toluene with 0.25% DPE. The average photovoltaic
parameters were obtained from four devices. Reprinted with
permission from ref 32. Copyright 2017 John Wiley and Sons.
In the most recent highly efficient nonfullerene solar cells by
Zhao et al.33 and Zhao et al.,19 the ITIC derivatives ITIC-Th1
and IT-4F outperform PC71BM in terms of not only device
efficiency but also device longevity. The same observation has
also been made by Choi et al. on PTB7-Th:IDT(DCV)2
nonfullerene solar cells compared with the fullerene counter-
parts.34
In a later report by Guo et al., the authors presented a 10.5%
PCE for nonfullerene solar cells based on PTZ1:IDIC.
Preliminary evaluation revealed decent thermal stability for
the unencapsulated devices with a device area of 0.81 cm2. After
a 10 h thermal annealing at 100 °C, the PCE of device still
retains 81% of the original value.
10.2. Enhanced Stability of BHJ Solar Cells with PDI or DPP
Based NFAs
Since most of the top-of-the-line PCEs of nonfullerene solar
cells were achieved using ITIC or other IDT core based NFAs,
there are relatively fewer studies on device longevity with
acceptors based on PDI or other core units. However, rylene
diimides and DPP based molecules are well-known for their
pronounced thermal and chemical stabilities. 103,143 As
improved PCEs are being progressively published for PDI-
based NFAs, systematic studies on PDI based nonfullerene
devices are expected to emerge. The work shown below
manifest the huge potential of using PDIs to improve device
longevity.
Lin et al. have evaluated the ambient stability of nonfullerene
solar cells based on a series of three-dimensional PDI based
acceptors.35 It was shown that the intramolecular twisting of
these acceptors not only produced a dramatic difference in
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Figure 38. (a) Normalized UV−vis−NIR absorption spectra of PTB7-Th and ATT-2 in thin films. (b) The standard human eye sensitivity spectra.
(c) Shelf stability of ATT-2:PTB7-Th in ambient conditions. The inset shows photographs of the institute abbreviation without (top) and with
(bottom) the semitransparent device. (a−c) Reprinted with permission from ref 292. Copyright 2017 John Wiley and Sons. (d) Absorption spectra
of PTB7-Th and IHIC pure films and PTB7-Th: IHIC blended films. (e) Visible transmission spectrum of the optimized semitransparent device
with the architecture of indium tin oxide (ITO)/zinc oxide (ZnO)/PTB7-Th:IHIC(100 nm)/MoO3/Au(1 nm)/Ag(15 nm). Inset shows the
structure of the acceptor molecule. (f) Photographs of Bo Ya Pogoda in Peking University taken with exactly the same camera settings on a sunny
day: (left) without any filter; (right) with semitransparent device based on the architecture of ITO/ZnO/PTB7-Th:IHIC(100 nm)/MoO3/Au(1
nm)/Ag(15 nm). (d−f) Reprinted with permission from ref 293. Copyright 2017 John Wiley and Sons.

device performance but also resulted in a significant variation in
device shelf stability in air. The efficiency of the device based on
TPC-PDI4, which was the NFA with the most intramolecular
twisting, decreased to a level of 76.8% of the original PCE after
2 weeks. In contrast, the less twisted core offered TPPz-PDI4
and TPE-PDI4-based devices with excellent shelf stability by
maintaining over 90% of the original PCE, which outperformed
that of the fullerene-based one. This result might be caused by
the excessive twisting of the TPC core that could facilitate
molecular diffusion in the blend, which is detrimental for
morphological stability.
Li et al. investigated thermal stability for nonfullerene solar
cell devices consisting of P3HT and a DPP based NFA,
SF(DPPB) 4.36 After 3 h of thermal annealing at 150 °C, while
the nonfullerene device showed no evidence of PCE decay, the
fullerene based counterpart displayed an efficiency below 1%.
10.3. Enhanced Stability of Ternary Blend Nonfullerene
Solar Cells
In the work mentioned in section 10.1,26 in addition to the
enhanced stability obtained by replacing fullerene with IDTBR,
interestingly, the authors found that the ternary device based on
a blend of P3HT:IDTBR:IDFBR (1:0.7:0.3 weight ratio)
demonstrated further enhanced dark and photostability
compared to the binary devices. 80% initial performance was
retained after 800 h exposure to air and 85% was retained after
90 h in air under illumination for the ternary device.
Wang et al. reported that using m-ITIC as the third
component could significantly enhance the thermal stability
compared to the PTB7-Th:PC71BM binary blend, which is not
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surprising considering the more thermally stable and less
diffusive nature of the A-D-A NFA.262
Shastry et al. demonstrated another avenue to improve
device stability.37 By adding high mobility single-walled carbon
nanotubes as the third component in a nonfullerene blend
formed by PTB7 and a helical PDI dimer(hPDI2), the ternary
device showed reduced bimolecular recombination and
enhanced stability at both 1 sun and concentrated illumination.
10.4. Semitransparent Nonfullerene Solar Cell with
Enhanced Stability
In addition to stability, the readily tunable optical property of
NFAs made them ideal candidates for fabricating semi-
transparent photovoltaic devices. In ref 292, the authors
demonstrated a semitransparent OPV device fabricated using
PTB7-Th:ATT-2, whose main absorption located in the range
of 600−850 nm, which allowed high transmittance of the blue
photons (Figure 38a−c). The normal device with thick
electrode showed a high PCE of 9.58% with decent ambient
stability, i.e., >8.5% PCE after 14 days in air without
encapsulation. By reducing the Ag electrode thickness to
below 20 nm, the semitransparent device showed a high PCE of
7.74%.
A more recent publication by Wang et al. demonstrated the
synthesis of a novel NFA, IHIC, which exhibited strong
absorption in the NIR region (∼600−900 nm) with a superior
electron mobility.293 The authors exploited the narrow bandgap
of IHIC (1.38 eV) and blended it with the archetypal narrow
bandgap polymer, PTB7-Th (bandgap ∼1.58 eV). The
resultant BHJ solar cell manifested not only a high PCE of
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9.77% but also a high average visible transmittance of 36% due
to the minimal absorption of the blend film in the green-blue
wavelength region (Figure 38d−f). Furthermore, an initial
stability test revealed that the unencapsulated semitransparent
device retained ∼97% of its initial PCE after a continuous
illumination for 130 min (AM 1.5G, 1 sun).
10.5. Summary
Despite the limited number of publications on device stability
so far, substitution of fullerenes with NFAs appears to fulfill the
expectation of stability improvement. However, other degrada-
tion routes still affect device longevity strongly, such as the
oxidative degradation of the donor as well as the interfacial
layer degradation. Intriguingly, the strategy of designing ternary
blend nonfullerene OPVs may not be necessarily detrimental to
device longevity. Future research on NFAs should not only
focus on their photovoltaic PCE but also on the device
longevity and other factors that affect eventual commercializa-
tion. Introducing industrial figure of merit is necessary in the
near future to evaluate the full potential of a new material.294
Considering that most OPVs in the literature were not
optimized for device longevity, there is a huge potential for
chemists and device engineers to design more stable NFAs and
further improve device stability to essentially reduce the
efficiency-stability-cost gap.
11. REDUCING VOLTAGE LOSS
One of the most important factors that limit the efficiency of
OPVs is the relatively large voltage loss from the bandgap (Eg)
of the light absorber to the device open-circuit voltage (VOC).
For example, one of the best performing OPVs reported to
date, PffBT4T-2OD:PC71BM,295 has a VOC of 0.77 V for an Eg
of 1.65 eV, corresponding to a voltage loss of 0.88 V. In
contrast, state-of-the-art c-Si or perovskite cells have much
lower voltage losses, typically in the range of 0.40−0.55
V.86,87,296 In order to understand the reason behind the large
voltage loss suffered by OPV, we have to review the origins of
voltage losses in a solar cell.
Figure 39 illustrates the voltage loss pathways found in an
inorganic (a) and an organic (b) solar cell. Based on detailed
balance theory,87,297−299 the overall energy loss for any solar
cell (both inorganic and organic) can be attributed to the three
terms shown in eq 2.
Figure 39. Energy loss in inorganic and organic solar cells. Adapted
with permission from ref 87. Copyright 2016 Nature Publishing
Group.
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qΔV = Eg − qVOC
SQ SQ rad rad
= (Eg − qV OC ) + (qV OC − qVOC ) + (qVOC − qVOC)
SQ rad,belowgap non − rad
= (Eg − qV OC ) + qΔVOC + qΔVOC
= ΔE1 + ΔE2 + ΔE3
(2)
where q is the elementary charge, ΔV is the voltage loss, VSQOC is
the maximum voltage attainable according to the Shockley−
Queisser limit (which assumes no absorption below the optical
gap of the cell),300 Vrad
OC is the open-circuit voltage when only
radiative recombination is present, ΔVrad,belowgap is the voltage
OC
loss of radiative recombination from sub-bandgap absorption,
and ΔVnon−rad is voltage loss due to nonradiative recombina-
OC
tion.
The first term of the energy losses in eq 2 (Eg − qVSQ OC)
corresponds to radiative recombination originating from
absorption above the bandgap. This loss is unavoidable for
any type of solar cell and is typically between 0.25 and 0.30 eV.
The second term (qΔVrad,belowgap
OC ) corresponds to additional
radiative recombination from absorption below the bandgap.
For inorganic and perovskite cells, this term is negligible due to
steep absorption edges and thus can be neglected from the
energy diagram shown in Figure 39.297 In contrast, this loss is
typically much higher for OPVs due to the presence of CTS at
the donor−acceptor heterojunction as evident from the red-
shifted absorption spectrum.301 As discussed in section 2, OPVs
typically rely on an energy offset between the electron affinity
of the donor and acceptor materials to provide a driving force
for overcoming the binding energy of the excitons to form
charge carriers. The requirement of this energy offset (typically
>0.2 eV) to enable efficient charge generation leads to
significant voltage loss. For examples, this loss is as large as
0.67 V for P3HT:PCBM blend and 0.2 V for the state-of-the-art
PTB7:PCBM blend.
In order to minimize this loss in OPVs, it is necessary to
reduce the energy difference between the singlet exciton on the
donor and/or acceptor and the interfacial CTS without
reducing charge generation efficiency. Previous attempts to
achieving this goal using blends of donor polymer and fullerene
acceptors have generally been unsuccessful, with the gain in
PCE due to increased VOC compromised by a large reduction in
photocurrent.71 However, recent studies have reported OPV
blends of novel donor polymers and nonfullerene acceptors
that exhibit highly efficient charge generation efficiencies
despite having small donor−acceptor energy offset. Examples
of these novel systems include P3TEA:SF-PDI2,87 PTB7-
Th:IEICO-4F,19 and PvBDTTAZ:O-IDTBR.88 These blends
have steep absorption edges as typically found in inorganic
cells, and, as a result, the voltage loss corresponding to CTS
absorption in these blends is much smaller than that observed
in typical high-performance OPVs.
The third term (qΔVnon−rad
OC = −kT ln (ηEL)) is due to
nonradiative recombination, where k is the Boltzmann constant,
T is the temperature and ηEL is the electroluminescence (EL)
quantum efficiency of the diode when charge carriers are
injected into the device in the dark.298,302 Inorganic solar cells
typically have ΔVnon−rad
OC in the range of 0.25 V, while this value
is typically larger for OPVs (0.38−0.44 V).303 The large
difference is due to the very low ηEL of bulk-heterojunction
blends (typically ∼10−6−10−8) compared to that typically
found in silicon or perovskite cells (typically ∼10−2−10−3). It is
thus clear that increasing the ηEL of OPVs can lead to lower
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voltage losses, with 1 order of magnitude increase in ηEL
corresponding to 60 mV reduction in ΔVnon−radOC . This is indeed
the case in the model high-efficiency, low-voltage loss OPV
blend, P3TEA:SF-PDI2,87 where a high ηEL of ∼10−4 is
achieved. Unlike typical OPV blends based on fullerene
acceptors, where the electroluminescence that arises from
CTS emission is clearly red-shifted relative to the donor/
acceptor singlet emission, the EL spectrum of the P3TEA:SF-
PDI2 blend resembles that of the pure polymer (P3TEA)
device. This indicates that the EL emission of P3TEA:SF-PDI2
is mainly from the singlet excitons in the polymer, which are
most likely populated following electron transfer from the CTS
enabled by the small donor−acceptor energy offset.304 This
finding indicates that reducing the energetic offset at the
interface can in principle improve VOC by reducing both
ΔVrad,belowgap
OC and ΔVnon−rad
OC and is a promising way to improve
OPV efficiency provided that efficient charge generation can be
maintained.
Such systems inspire the OPV community to reconsider
whether the widely quoted exciton binding energy (∼0.3 eV)
was based on a sound theoretical foundation. In general, this
value was estimated by calculating the Columbic attraction of
an electron and a hole assuming a close contact (e.g., 1 nm)
between the two charges.305 However, recent studies have
shown that the positive charge (i.e., a hole) on the chain of a
polymer might have a large initial excitation volume
approaching 20 nm3.306 Consider a polymer as a cylinder,
assuming a 0.8 nm radius for the cylinder, the delocalization
distance of the exciton on the polymer chain could be as large
as 9 nm. Another study measured the electro-absorption signal
in a fullerene system using transient absorption spectroscopy
and estimated the electron−hole distance to be ∼4 nm, which
would significantly reduce the exciton binding energy to <0.1
eV.83 Thereafter, the exciton binding energy might be smaller
than 0.3 eV considering that the effective electron−hole pair
distance is significantly larger than that assumed previously.
This analysis should apply to both fullerene and nonfullerene
solar cells, and it does not explain why NFA seems to be more
successful in achieving highly efficient systems with a negligible
driving force. Nevertheless, the fundamental mechanism of
efficient charge generation in an organic blend without
requiring a driving force remains unclear, and the origin of
nonradiative recombination in OPVs on a molecular level at the
interface is far from understood.
It is thus necessary to identify the microscopic details of OPV
blends that govern voltage loss. The analysis above based on
detailed balance does not account for the microscopic
parameters associated with OPV blends. Examples of these
parameters include the degree of donor−acceptor mixing and
the interfacial energetic disorder, which is expected to be more
significant in organic materials compared to inorganics. Several
studies have applied more complex and realistic models for the
density of interfacial CTS and free carriers in OPV
blends.85,86,307,308 In particular, the recent work by Burke et
al. relates the low VOC of OPVs to a combination of their high
degree of mixing, short CTS lifetimes, large amounts of
interfacial energetic disorder, and low dielectric constants
leading to high CTS binding energies.86 By optimizing these
microscopic parameters of the interface between donor and
acceptor materials through molecular design, the performance
of OPVs can be systematically improved through increases in
VOC. Furthermore, the impact of molecular orientation at the
interface on charge generation efficiency and nonradiative
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recombination has been studied theoretically based on
calculations309−311 and experimentally with the use of
controlled donor and/or acceptor orientations in planar
heterojunction devices.312−315 In particular, the recent study
by Ran et al.314 shows that a face-on molecular geometry of the
donor at the interface reduces nonradiative recombination
(increase VOC), while an edge-on orientation favors charge
generation (increase current).
In summary, the large voltage loss in OPVs is due to two
main factors. One is the existence of a significant offset between
the bandgap of the donor/acceptor materials and the energy of
the CT state. The other is the relatively large nonradiative
recombination loss in OSCs, evidenced by low electro-
luminescence quantum efficiency (ηEL) of OPV blends.
Identifying and optimizing the microscopic details that governs
these loss pathways would facilitate the development of highly
efficient OPVs with small voltage losses comparable to those
typically found in inorganic devices.
12. CHALLENGES AND PERSPECTIVES
12.1. Perspectives on Molecular Design Strategy and
Synthetic Complexity
Thanks to the diversified material design strategy, over 100
NFAs have been reported for efficient OPV devices and the
PCE of single-junction nonfullerene OPVs has boosted from
∼3% to >13% within ∼5 years. In addition to concerning the
energetics and optical properties, due to the requirement for an
interpenetrating bicontinuous network, the chemists need to
make balanced assessment on the solubility, aggregation
tendency, and molecular miscibility with the donor as well as
the potential carrier mobility when designing new NFAs.
Developing molecules to satisfy these demands would be the
essential goal. Whereas, at the current stage, each material class
demonstrates merits fulfilling some of these criterions but
shows limitations in the others. Future molecular design should
have balanced attentions paid on energetics (influencing charge
separation and VOC, see section 11), light absorption, free
carrier generation (morphology), charge transport, and
synthetic flexibility.
12.1.1. Molecular Design to Enhance Light Absorp-
tion. A highly complementary absorption between the donor
and acceptor is the prerequisite of a broad and strong EQE
spectrum and is one of the most crucial reasons for the success
of NFAs. PDI-based NFAs, in general, exhibit absorption
coefficients of ∼105 M−1 cm−1 in solution and ∼104 cm−1 in a
thin film while typical high performance IDT-based NFAs show
absorption coefficients of ∼105 cm−1 in a thin film. Compared
to the A-D-A type NFAs whose absorption profiles are more
readily to tune, PDI molecules show relatively fixed absorption
in the range 500−650 nm. Consequently, design strategies to
enhance extinction coefficients and alternating the spectral
range are strongly desired for PDI acceptors. As demonstrated
in section 4.1.5, multiple cases have shown that the ring-fusion
strategy can be used to significantly increase the absorption
coefficients and therefore serves as the top candidate for solving
this issue. Modifying the molecular geometry through
connecting multiple PDI units together can also lead to
changes in both absorptivity as well as absorption range.
Furthermore, the higher homologue of PDI such as TDIs can
be considered as they exhibit higher absorption coefficients and
more red-shifted absorption spectra than PDIs.
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In contrast, the absorption profile of A-D-A type NFAs is
easier to tailor due to the facile synthesis. The electron
donating and accepting building blocks as well as the spacer
units can be modified separately, which creates a large number
of combinations and makes it feasible to realize strong
absorptions even in the NIR region. This also opens up
numerous opportunities for the design of semitransparent
OPVs with a wide range of color options. To make further
improvement of the optical property, future molecular design
could take advantage of the established methods such as tuning
the intramolecular push−pull character, elongating/expanding
the conjugation, introducing halogenation to the “A” moiety,
etc.
Besides their tunable absorption in the long-wavelength
region, the presence of a wide range of efficient large bandgap
polymers is an important reason for the rapid progress of the A-
D-A type NFAs. In contrast, there are less narrow-bandgap
polymer donors with competitive performances. Therefore, to
further utilize NFAs such as PDIs, effort should also be made
on developing compatible donors, particularly those with
absorption in the NIR region.
Regarding light absorption, building blocks such as quinoidal
thiophene derivatives and DPP deserve further exploration as
they can be used to construct chromophores with strong
absorptions that have direct improvement over the fullerenes.
Further structural modification should focus on reducing the
high-lying LUMO levels of DPP-based NFAs, which could
make them compatible with more donor materials.
12.1.2. Molecular Design to Balance Morphology and
Charge Transport. The requirement for both a reasonably
small domain size for efficient exciton dissociation and a
bicontinuous network for long-range charge transport increases
the complexity of the material design. In the NFA-based active
layers, the small domain size is typically achieved through a
decent miscibility between the donor and the NFA while the
bicontinuous charge-transport network is facilitated by an
enhanced intermolecular order (or sometimes referred to as the
crystallinity in most literature). As discussed in section 4.1.4,
finding the optimal balance between miscibility and crystallinity
is not straightforward. Using a highly crystalline material with a
high OTFT or pure-film SCLC mobility may result in a largely
phase-separated morphology in the BHJ blend. As a result,
crystallinity is sometimes exchanged for miscibility to harvest
more excitons during material design. For instance, introducing
molecular twisting to enhance solution processability and
reduce the domain size is widely employed to construct PDI
acceptors. However, controlling the extent of twisting is
challenging. An excessive amount of molecular twisting may
result in molecules that are too amorphous to form pure
domains with sufficient intermolecular stacking for efficient
long-range charge transport. In these cases, molecular design
approaches to exchange miscibility for crystallinity is needed.
Despite the facts that techniques such as thermal annealing and
the solvent additive approach can be employed to tune the
morphology during or after film formation, a proper pair of
donor and acceptor materials with appropriate molecular
miscibility and crystallinity are strongly desired.
The electron mobilities of the PDI acceptors are typically in
the range of 10−5 to ∼10−4 cm2 V−1 s−1, which are able to
enable a relatively high FF (mostly in the range of 50−65%).
However, further enhancement is essential to match the high
hole mobility of the state-of-the-art donor materials. To this
end, juditious molecular design methods that can enhance
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intermolecular charge transfer while maintaining adequate
solubility and miscibility are strongly needed. Historically,
sacrificing aggregation for solubility/miscibility results in many
amorphous PDI molecules, which can be employed as
structural templates for modifications to occur. Approaches
such as ring-fusion and ortho-position functionalization have
been proved effective in enhancing the overly reduced planarity
and should be further explored on more structures. Novel
molecular shapes such as 3D geometries, “double-decker”
configurations,165 or “slip-stacked” structures127 can also be
further investigated.
On the other hand, high performance A-D-A type NFAs
typically exhibit an electron mobility in the range of 10−4 to
10−3 cm2 V−1 s−1. In addition, a large fraction of IDT-based
NFAs show a preferentially face-on orientation in the blend
film, which is a desirable property for charge transport in OPV
applications. Since the “D”, “A”, and spacer units can be
functionalized independently, the currently established method-
ologies can still be employed to realize more combination of
these moieties. Extending the central conjugation length/area
seems to be a useful approach to improve the optical and
electronic property. Side chain engineering is another effective
method to tune intermolecular interaction. Replacing the
alkylphenyl side chain with an alkylthienyl one or changing the
grafting site of the side chain have shown positive effects on
device performance. Furthermore, in addition to the well-
known fluorination method, using a fused thiophene ring to
substitute the phenyl ring can also be applied to tune the
electron withdrawing ability and electron mobility when
designing the “A” unit.
Finally, considering that the PDI-based and IDT-based NFAs
showed <3% PCE only a few years ago, new NFAs with other
core units should not be ignored. When properly designed,
fused-ring aromatics, linear oligomers, and twisted dimers
comprising other building blocks may reveal a great potential to
compete with the current generation NFAs.
12.1.3. Synthetic Complexity. As the potential alternative
to fullerenes, NFAs may be able to overcome the high synthetic
complexity of fullerenes, which is important for the future large-
scale production and commercialization. The high-performance
PDI molecule SdiPBI-Se (see Table 1, molecule 4.9) was
synthesized through a simple one-pot procedure with a high
yield from a simple precursor 1-nitroperylene bisimide.135
Moreover, the PDI acceptor TPH-Se (molecule 4.37) that
exhibited a 9.3% PCE was also prepared through a one-pot
synthesis using a readily available precursor with an excellent
yield (87%).162 Regarding the production of fullerenes, Anctil
et al. have systematically investigated the energy and environ-
mental impacts through quantifying the life cycle embodied
energy of both C60 and C70 fullerenes and their derivatives.316 It
was shown that each step in the purification and modification of
fullerenes increases both energy inputs and material losses. It
was concluded that the embodied energy of all fullerenes are
notably higher than most common chemicals, which will have a
strong impact on the embodied energy of the final product.
This is one of the most fundamental motivations to replace
fullerenes with NFAs. While the synthetic complexity for
polymer and molecular donors has been analyzed,317,318 similar
studies on NFAs have not been reported.
Despite the fact that a comprehensive analysis of all of the
NFAs is outside the scope of this review, here we briefly discuss
the synthesis of one of the best-performing PDI derivatives
(TPH-Se) and the benchmark A-D-A type NFA, ITIC. Starting
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from perylene-3,4,9,10-tetracarboxylic dianhydride, 6-undeca-
none, and 1,3,5-tribromobenzene, TPH-Se can be synthesized
in eight steps with a total yield of ∼48%.162,319−321 In contrast,
the synthesis of ITIC from 3-bromothiophene, 1,4-dibromo-
2,5-dimethylbenzene, and 1,3-indandione requires 11 steps with
a total yield of <7%.322−327 For the best-performing A-D-A type
NFA, IT-4F, the fluorination of the IC group further increases
the synthetic complexity.194 It is clear that currently rylene
derivatives are better than A-D-A type NFAs in terms of
synthetic complexity. However, previous reports of A-D-A type
NFAs may have paid more attention to assessing the target
molecule instead of optimizing the synthetic steps and
improving the yields of each step. Therefore, further study on
chemistry will be helpful for not only reducing the synthetic
complexity of existing NFAs but also developing novel NFAs
with improved synthetic schemes.
A good example is the recent report of the synthesis of a
PDI-based NFA without column chromatography.136 Other
preliminary work showing simplified material synthesis for
individual NFAs is also available.200,328,329 These results
indicate that there is a tremendous room to improve in terms
of the synthesis of NFA materials. In addition, as some NFAs
can only achieve their best performance with specific donor
polymers, the synthetic complexity of the corresponding donor
polymer should also be considered. For example, the donor
polymer PDBT-T1, which was used together with TPH-Se,
contains a monomer dithienobenzodithiophene with a high
synthetic complexity based on a previous analysis.317 Therefore,
analysis of the active layer as a synergistic whole instead of each
material will be more accurate and instructive.
12.2. Studying Charge Transport
Electron mobility is one of the most important parameters to
evaluate the overall potential of an acceptor material. Unlike
PCBM, whose electron mobility is typically comparable to or
higher than the hole mobility of polymers in the blend, many
NFAs show lower mobility than polymers, which is one of the
key reasons limiting the FF of the OPV device. A subtle
modification of the chemical structure can result in a drastic
change in the stacking behavior and thus the electron mobility
of the NFA. The nanoscale network of NFAs in thin film is
dramatically different among different backbones, let alone
between NFAs and fullerenes.
To date, most reported mobilities for NFAs are obtained
from fitting space-charge-limited current (SCLC) models to
single-carrier diodes. SCLC model is useful for evaluating
macroscopic, device length scale mobilities for injected carriers.
To experimentally probe the mobility of photogenerated
carriers, others techniques such as time-of-flight and photo-
induced charge extraction by linearly increasing voltage (photo-
CELIV) could be employed.25,27,90,177,267,330,331 Besides photo-
generated carriers, photo-CELIV is also the only technique that
can be performed on actual OPV devices.332
Nevertheless, these methods measure the motion of carriers
at the device length scale, e.g., tens to hundreds of nanometers.
Previous work has shown that the local mobility in a shorter-
ranged molecular length scale could be largely different from
the mobilities in the macroscopic length scale, which can be
limited by grain boundaries.333 Since the local mobility is more
sensitive to the probability for an electron to hop from one
NFA molecule to another, it could be used to correlate with the
nanoscale order of the NFAs revealed by morphological
characterizations, which could serve as a great supplement to
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the macroscopic mobility mentioned above. Time-resolved
microwave conductivity (TRMC) is a technique for this
purpose with a nanosecond time resolution.334 TRMC has
been carried out to compare the local carrier mobility and
charge photogeneration between fullerene and nonfullerene
systems.43,101 For instance, TRMC studies have been
performed on PSEHTT:DBFI-T and PSEHTT:BFI-P2 non-
fullerene systems, in comparison to a PCBM-based control
sample.224 The authors showed that the dependence of
transient photoconductivity maxima for the PSEHTT:DBFI-T
blend is significantly higher than that for the fullerene or BFI-
P2 based blend, consistent with their photovoltaic performance.
In addition, by varying the excitation wavelength, the position
of the peaks could be used to reveal the interplay of charge
generation pathways from excitons in the donor and acceptor
phase.
12.3. Understanding Morphology of Nonfullerene Active
Layers
The active layer morphology of BHJ type solar cells requires a
bicontinuous interpenetrating network for balancing exciton
harvest and charge transport. Morphology formation is a
complex process influenced by numerous factors including the
intrinsic material properties such as molecular weight,335−338
regioregularity,335,339−344 purity, miscibility between donor and
acceptors,345−352 the effect of solvents and additives,353−356 film
processing conditions, and post film formation treat-
ments.281,335,357−362 Both thermodynamics and kinetics play
critical roles in determining the final morphology under which
the device is established. Accumulated understanding of
morphology is accompanied by the emergence of novel
materials and device fabrication techniques. The morphology
of polymer:fullerene BHJs has been investigated for decades
and is still one of the most debatable topics. The current state
of understanding of polymer:fullerene BHJ morphology
involves a multiphase model where ordered crystallites,
relatively pure donor and acceptor aggregates, and molecularly
mixed amorphous domains coexist in the blend film.363 The
delegated roles of these phases on light absorption, charge
generation, and charge transport are still under debate.364
12.3.1. Quantitative Morphology-Performance Corre-
lations. The aggregation properties of NFAs and the
miscibility between NFAs and donor materials can be largely
different from fullerenes. For instance, DPP-based polymers
show inferior miscibility with ITIC and the microsized phase
separation make the BHJ device perform much worse than their
fullerene-based counterpart does.365 At this point in time, most
morphological studies on nonfullerene OPVs are specific to the
presented case. Quantitative and systematic investigation of film
morphology with a focus on correlating them with measured
device parameters are strongly needed. In addition, polymer:-
NFA blend films are different from polymer:fullerene films in
terms of material contrasts, which increases the complexity to
extract meaningful information from some widely used imaging
techniques. This further elevated the difficulty to evaluate
nonfullerene-based active layer morphology at length scales
relevant for BHJ. In spite of this, insightful results have been
shown in some recent articles by utilizing soft and/or hard X-
ray scattering techniques to characterize the nanoscale
morphology of some highly efficient nonfullerene solar cells.
For example, through the use of resonant soft X-ray scattering
(R-SoXS), Ye et al. were able to establish a strong correlation
between the average compositional variation, or sometime
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referred to as domain purity, at a length scale of ∼10 nm, and
the FF and JSC of solar cell devices based on high-efficiency
polymer:NFA blends, namely PBDB-T:IT-M and PBDB-T:IT-
DM with different fabrication processes (Figure 40).366
Figure 40. (a) Plot of FF of the PBDB-T:IT-DM nonfullerene devices
versus the respective composition variation of the high-q peak (Δρ)
obtained from R-SoXS. Reprinted with permission from ref 366.
Copyright 2017 John Wiley and Sons. (b) Plot of (010) coherence
length of SMA versus the FF for a series of polymer:IDT-based NFA
blends. Reprinted with permission from ref 367. Copyright 2017 John
Wiley and Sons.
Hu et al. combined GIWAXS and R-SoXS to characterize a
series of polymer:NFA blends.367 To better unravel the role of
NFA in the high-performance polymer:NFA blends, the
archetypal NFA, ITIC-Th, was chosen as the single NFA and
a series of polymers were compared. It was found that, when
combined with different polymers, ITIC-Th demonstrated
different propensity to aggregate/crystallize. Further analysis
revealed that the photovoltaic devices’ FF and JSC increased
monotonically with increasing coherence length of the (010)
peak of the NFA (Figure 40), calculated from GIWAXS
experiments. Intriguingly, such correlation could not be built
with the (010) peak coherence lengths of the polymer.
These results have two main indications. First, different
polymers interact with these IDT-based NFAs differently, the
results of which were clearly reflected by the different
aggregation of NFAs in the film. The aggregation of the
NFAs may or may not affect the aggregation/crystallization of
the polymer, judging from the data alone, although the average
compositional variation seemed to correlate better with the
NFAs’ (010) coherence lengths. Second, the fact that the device
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performance is more strongly influenced by the π−π stacking of
the NFA rather than that of the polymer suggests the charge
transport of these state-of-the-art IDT-based NFAs is rather
different from both polymers and fullerenes. It was established
that the most efficient charge transport is along the backbone,
followed by the π−π stacking direction and then the lamellar
stacking direction. Due to the fact that polymers in general have
much longer conjugated backbones than the small molecular
NFAs, although still important, the impact of the (010)
coherence length for polymers on the overall hole conduction is
less than the impact of (010) coherence length for the small
molecules. These conclusions should not be limited to IDT-
based A-D-A type NFAs. As the molecular twisting and
coplanarity paradigm for the rylene-based NFAs is more
significant, it would be expected that similar studies been
carried out onto more polymer:NFA combinations.
Since IDT-based A-D-A type small molecules represent the
state-of-the-art NFAs, in a broader context, these results
indicate that at the moment, in a high-performance polymer:-
NFA blend, the nanoscale morphology and local conductivity
of NFAs are the limiting factors that govern the overall device
performance. Nevertheless, the high FFs achieved in some of
the NFA-based BHJ blends prove that these issues can be
overcome through judicious molecular design and morphology
optimization.
In addition to understanding the solid state morphology after
the solid film is formed, grasping the morphology formation
process from an in situ point of view is also critical because the
formation of the solid state BHJ usually involves the use of
solvent mixtures, solvent additive, postfilm-formation-treat-
ments (thermal annealing, solvent vapor annealing, etc.), or
temperature dependent film drying.364 Building a thorough
understanding of morphology forming processes arising from
either liquid−liquid demixing or crystallization is necessary to
develop structure−property-processing-performance relation-
ships.
12.3.2. Molecular Miscibility. Despite the fact that kinetic
controls during film formation can make the active layer dry at
a thermodynamically instable state, understanding the mixing
capabilities of semiconducting polymer blends is essential for
predicting the thermodynamically stable state of the film which
is related to the morphological stability. To this end, Flory−
Huggins368 or Flory−Rehner369 theory have been utilized by
various groups to evaluate the miscibility between different
components in polymer-based blends.347,351,352,366,370−378 Most
of these studies focused on the polymer and fullerene
miscibility, but the preliminary result indicates the potential
to use the Flory−Huggins interaction parameter and the
calculated spinodal demixing curve to explain certain
morphology result such as average compositional variation
(Figure 41). Nevertheless, robust theoretical models and
experimental techniques to evaluate the miscibility and assess
phase separation from the thermodynamic viewpoint is needed.
12.3.3. Solvent Additive Effect. The use of solvent
additives has been considered one of the most effective
methods to tune the morphology of the active layer of BHJ
OPVs.379−381 Most of the high PCEs for polymer:fullerene
devices were realized through the implantation of solvent
additive(s).355 High boiling point solvents such as DIO, 1,8-
octanedithiol (ODT), and CN are the most widely used
additives, which have been employed in both fullerene355,379,382
and nonfullerene-based blends (Tables 1−3).171,241
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Figure 41. (a) Calculated χ parameters at room temperature from
Hansen solubility parameters and inferred χ at the annealing
temperature (160 °C) in relation to spinodal and binodal curves of
the polymer:SMA systems for a given weight ratio of 1:1 (the dashed
lines indicate the composition in the amorphous mixed domain in the
limit of complete phase separation at the respective χ and the gray
horizontal line represents the critical χc ≈ 0.8). (b) Plot of
composition variation of the high-q peak (Δρ) under various
processing conditions in relation to the room temperature and
Hansen solubility parameters derived χ parameter of the nonfullerene
OSCs. Reprinted with permission from ref 366. Copyright 2017 John
Wiley and Sons.
The role of a solvent additive in tuning the morphology is
complicated, and the explanation varies from case to case.
Generally, the main functions of solvent additives are tuning
the degree of phase separation and/or changing the crystallinity
of one or both components. In most fullerene-based systems,
solvent additives have been considered a selective solvent that
exhibits differential solubility to the acceptor and donor in the
blend solution.8,10,383,384 Particularly, it is widely acknowledged
that DIO, the solvent additive that is less volatile than common
organic solvents such as CB and CF, exhibits selective solubility
to PC71BM, which promotes the aggregation of fullerenes and
allows the fullerene to achieve an overall higher crystallinity
(more crystalline domains with comparable crystal size) when
combined with the workhorse material PTB7.355 Akin to the
role of DIO, in the NREL certified 11.5% polymer:fullerene
OPV system,10 the high-boiling point solvent additive 1-
phenylnaphthalene (PN) has been reported to play multiple
synergistic effects including (i) enhancing the electron mobility,
(ii) enhancing domain purity while reducing domain size, and
(iii) promoting a face-on orientation of the polymer.
Alternatively, solvents such as CN can be a cosoluble
additive, which has been found to be able to suppress the
aggregation of polymer(s) and prevent the formation of
undesirably large domains.385,386 In addition, solvent additives
can modify the vertical phase segregation.371,387 Nevertheless,
the goal of a solvent additive is to alternate the morphology
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toward a more ideal BHJ nanostructure than that the original
solvent can provide.
Compared to fullerene-based OPVs, nonfullerene donor:-
acceptor blends, in general, demonstrate less demand for
solvent additives. A possible explanation could be that the
solubility selectivity between the donor polymer and the NFA
is reduced in comparison to that between the polymer and
fullerene. For instance, Song et al. compared the effect of DIO
on film morphology and device performance in both PC71BM
and ITIC based blends with the same polymer donor, PTB7-
Th.388 It was concluded that, unlike the fullerene-based blend
where DIO increased the absorption and aggregation of
PC71BM (and thus the FF and JSC), the PTB7-Th:ITIC
blend showed slightly inferior morphological, optical, and
electrical properties after adding DIO into the main solvent
(CB).
Nevertheless, the requirement for solvent additive including
the choice of the additive and/or its volume fraction in the
solvent mixture varies among different material systems. For
example, the nonfullerene blends based on PDI molecules
demonstrate, on average, a stronger requirement for solvent
additive (Table 1) than the nonfullerene blend based on A-D-A
type NFAs (Table 2). The main reason could be that, although
different functionalities and/or molecular geometries have been
introduced, most PDI acceptors are still not able to enable a
favorable morphology with highly crystalline, reasonable small
yet pure domains, which, consequently, requires additional
efforts such as the assist of a solvent additive to address. In
contrast, several high-performance A-D-A type NFAs are
capable of forming a near optimal morphology with the
donor due to a balanced molecular miscibility and crystallinity,
which therefore releases the requirement for solvent additives.
It is noteworthy that this is only a general discussion, and there
are certainly cases where an A-D-A type NFA requires a solvent
additive or a donor:PDI blend does not rely on any additive to
achieve a high device performance.
Despite the fact that solvent additives are beneficial for the
realization of a high PCE, they should better be precluded for
eventual industry-scale production of the OPV devices as they
may induce device instability and irreproducibility.389 There-
fore, future material design for the active layer should focus not
only on the optical property and energetics but also on
optimizing miscibility as well as crystallinity of the materials to
achieve additive-free processing.
12.3.4. Vertical Phase Segregation. Besides morphology
in the bulk, the distribution of organic materials in the direction
perpendicular to the substrate, also known as the vertical phase
segregation, is of equal importance because the transport of
charges in the vertical direction results in charge extrac-
tion.348,362,390−408 It is accepted by the field that relative surface
tension can be used to predict the wetting propensity of a
component in the blend at a certain interface, e.g., the
component with higher surface tension tends to segregate
toward the interface with a high surface tension.390,394,409
PCBM, in general, has a higher surface tension than lots of
polymers reported and is therefore more likely to segregate to
the bottom (substrate). However, surface tension of novel
NFAs may differ strongly from fullerenes or polymers.
Therefore, depending on the relative surface tension between
the NFA and the polymer, appropriate device architectures, e.g.,
normal vs inverted, needs be selected to avoid intense surface
recombination. Alternatively, solvent additives and post-treat-
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Figure 42. (a, c) Molecular structures of electron donor and electron acceptor materials in the (a) front and (c) rear cells. (b) Device architecture of
the tandem OSCs. (d) Molecular structure of the interconnection layer, PCP-Na, in the tandem cells. (e) Transmittance spectra of ZnO/PCP-Na
ICLs with different PCP-Na thicknesses. (f) Schematic energy level diagram of each material used in this study. Adapted with permission from ref 20.
Copyright (2017) American Chemical Society.
ments such as solvent vapor annealing are needed to tune the
vertical phase segregation for a given device architecture.
12.4. Multijunction NFA OPVs
Multijunction OPVs have been previously explored in the
polymer:fullerene BHJ solar cells with the majority effort
focused on the series connected tandem structure,410−416 where
the bottom and top subcells are separated by a recombination
medium. Apparently, the total VOC of the series connection
tandem device should theoretically equal the sum of the VOCs
of the two subcells. The main motivation for this device
platform is to increase the absorption breadth by using two
subcells with complementary absorption profiles.
In general, nonfullerene tandem OPVs should inherit all
advantages of the tandem structure and avoid the aforemen-
tioned drawbacks inherent to fullerenes. In a recent publication
by Cui et al., the authors employed nonfullerene blends
consisting of materials with both large and narrow bandgaps to
broaden the absorption spectrum (Figure 42). Through the use
of a recombination layer with extremely high transmittance that
minimizes parasitic absorption, the authors demonstrated a
PCE of above 13.0% for the tandem device, which showed
dramatic improvement over the individually optimized top and
bottom subcells (9.0% and 10.1%). Another work by Liu et
al.417 also took advantage of the complementary absorption of
the subcells. In combination with the high VOC of each cell, the
resultant tandem device achieved a PCE of 8.48% with a high
VOC of 1.97 V.
Besides these known benefits, some intrinsic properties of
the NFA based single-junction OPVs may further stimulate the
construction of the tandem device. For example, a large fraction
of high-performance nonfullerene solar cells have relatively thin
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optimal active layer thicknesses, i.e., about or less than 100 nm,
as a result of the limited electron mobility of the NFAs. The
thin active layer may not have sufficient absorption for
achieving high JSC. Therefore, fabricating homotandem device,
where the top and bottom subcells consist of the same
materials sets, can enhance light trapping and make further use
of the photons penetrated through the front cell. On the other
hand, reduced energy loss provides multiple nonfullerene single
junction devices with high VOC while maintaining decent JSC
and FF. Hence, stacking two such subcells in a series
connection fashion can afford the tandem device an exception-
ally high VOC, which may allow the realization of certain
application requiring high-voltage operation, such as water
splitting.418,419
Driven by the high VOC and the low active layer thickness in
the 9.5% single-junction PTFB-O:SF-PDI2 device,87 Chen et al.
fabricated homotandem devices and achieved a homotandem
nonfullerene solar cell with a PCE of 10.8% and an
extraordinarily high VOC of >2.1 V.420 This result was obtained
through constructing a novel all-solution processed recombi-
nation layer that did not require harsh post-treatment and
carefully designing the two active layers’ thicknesses under the
guidance of optical modeling. The high VOC has enabled
successful demonstration of photovoltaic-driven water splitting
(Figure 43).
Zuo et al. fabricated highly efficient homotandem devices
based on PTB7-Th and ITIC or 4TIC.421 The tandem device
was connected in parallel, which does not require strict
photocurrent matching to maximize the overall JSC. The use of
homotandem also guarantees voltage matching across the
parallel-connected subcells. As a result, high JSCs of ∼17.92 and
20.81 mA cm−2 were demonstrated for the ITIC and 4TIC
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Figure 43. Photo of photovoltaic-driven water splitting using the high-
voltage homotandem nonfullerene organic solar cell in ref 420. An
electrochemical cell was connected to the tandem solar cell illuminated
under AM 1.5G (100 mW cm−2), with the platinum wire and nickel
foam electrodes immersed in a 1 M NaOH electrolyte solution.
Reprinted with permission from ref 420. Copyright 2017 John Wiley
and Sons.
based tandem device, respectively. The improved JSCs enabled
high PCEs of 10.03% and 11.08%, respectively.
In summary, the easily tunable optical properties of NFAs
make them suitable candidates for application in a multi-
junction device. Considering the low energy loss offered by
certain donor:NFA combinations, the tandem device could
achieve extraordinarily high VOC while maintaining decent
current and FF. One of the reasons limiting the development of
this device platform is the lack of effective recombination layers
with high photon transmittance and efficient charge recombi-
Figure 44. (a) Typical J−V characteristics of PBDB-T:ITIC devices with a structure of ITO/PEDOT:PSS/PBDB-T:ITIC/WSCP/Al under
simulated AM 1.5G irradiation (100 mW cm−2). The WSCP interlayer thickness is ∼5 nm. (b) Schematic illustration of the exciton separation and
transport in BHJ and the charge transfer states at the donor/WSCP interface. (c−f) Energy level diagrams of PTB7-Th:N2200 BHJ with a (c) thin
or (d and e) thick interface layer and (f) PTB7-Th:IDT-2BR BHJ with a thick PFN-2TNDI interface layer. Reproduced from ref 423 with
permission. Copyright 2017 Royal Society of Chemistry.
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nation. The requirement of harsh treatment of most
recombination layers also limits the choices of active layers.
With the increasingly emerged recombination layers with
desired properties, the tandem strategy could be considered as
another promising option to further optimize device efficiency.
12.5. Device Structure Engineering and New Interfacial
Layers
In addition to the majority effort spent on active layer
optimization such as donor/acceptor designing and morphol-
ogy tuning, another critical aspect in improving the overall
device efficiency and stability is interfacial engineering. The
importance of choosing the proper interlayer cannot be
overstated as an inferior interface between active layer and
electrodes have manifold negative impacts on charge extraction
including (i) forming a nonohmic contact with the active layer,
(ii) causing an unfavorable vertical phase segregation of the
active layer, (iii) undesired doping of the active medium, (iv)
diffusion into the active layer (v) increasing series resistance,
(vi) causing parasitic absorption, and (vii) reducing device
stability, etc.
Multiple interlayers and/or electrodes have been shown to
interact with fullerenes.422 The influence of such interaction can
be either positive or negative. Many interlayers were inten-
tionally optimized for fullerene based OPV devices. Con-
sequently, after the fullerenes are replaced with novel NFAs, the
known benefits from previous interlayers may not exist and new
interfacial interaction may be introduced. Exploiting a
compatible interlayer is essential for further boost of PCE
and stability of the NFA-based devices.
As a typical example, the recent publication by Sun et al.423
introduced a NDI based water-soluble conjugated polymer
(WSCP), namely PDI-2TNDI, as the electron transport layer
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Figure 45. (a) PCE of P3HT:IDT-2BR based BHJ solar cells as a function of active layer thickness. Reproduced from ref 184 with permission.
Copyright 2015 Royal Society of Chemistry. (b) PCE versus active layer thickness of the solar cells based on PTZ1:IDIC. (c) J−V characteristics of
the optimized solar cells based on PTZ1:IDIC with different active area. (b, c) Reprinted with permission from ref 426. Copyright 2017 John Wiley
and Sons. (d) Device parameters (PCE, JSC, VOC, and FF) versus the active layer (PBDB-T-SF:IT-4F) thickness. Adapted with permission from ref
19. Copyright (2017) American Chemical Society.
between the active layer and the cathode. By comparing the
PFN-2TNDI with another interlayer (PFN), the authors
delineated the difference of interfacial doping between a
fullerene-based BHJ and a nonfullerene based BHJ (Figure 44).
A clear interfacial n-doping was observed at the fullerene/
WSCP while the doping at the NFA/WSCP interface was not
prominent. Therefore, in terms of reducing contact resistance
and forming an ohmic contact with the NFA based active layer,
the self-doped PFN-2TNDI outperformed PFN. Furthermore,
the authors revealed that PFN-2TNDI could serve the role of
dissociating the exciton of the polymer donor at the interface. A
pronounced PCE value of 11.1% was achieved in nonfullerene
solar cells.
This research clearly demonstrates the importance of
tailoring interfacial properties among different material systems.
To better harvest the potential of the novel nonfullerene active
medium, further understanding of the role of different
interlayers is strongly demanded.
12.6. Thick Active Layer, Large-Area Devices,
Environmentally Friendly Processing, and Roll-to-Roll
Printing
The thickness of the active layer of an organic solar cell has a
strong impact on its potential for industrial-scale production. In
general, the thickness of the active layer of an polymer:fullerene
based organic solar cell is from tens to hundreds of
nanometers.295,424,425 In comparison, most of the nonfullerene
BHJ organic solar cells reported contain an active layer with
thickness around or below 100 nm due to the relatively low
electron mobility of the NFA, which limits photon harvesting
and could affect the overall robustness of the device, particularly
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for large-scale production. Nevertheless, the emergence of
recent high mobility NFAs have alleviated this problem. For
example, in ref 184, the device performance of P3HT:IDT-2BR
was shown to be relatively insensitive to the active layer
thickness in the range of 60−220 nm (Figure 45a), which
further confirmed the efficient charge transport enabled by the
high electron mobility of the acceptor. This was the first report
that nonfullerene OSCs could perform well in a relatively thick
(over 200 nm) active layer.
The PCE of the PTZ1:IDIC nonfullerene solar cell in ref 426
retains a high value (>9%) at an active layer thickness of 210
nm with a decent FF (66.8%; Figure 45b). It is worth noting
that a 10.5% efficient solar cell at an active device area of 81
mm2 was demonstrated for PTZ1:IDIC (Figure 45c). The PCE
of the PBDB-T-SF:IT-4F based device in ref 19 also
demonstrated a weak dependence on the active layer thickness:
a PCE >12% was obtained for active layers with thickness up to
200 nm and a PCE >10% was achieved using an 300 nm-thick
active layer (Figure 45d). The authors also obtained an 11.1%
efficient device at a device area of 1.00 cm2 in this work.
Similarly, a thick active layer and efficient nonfullerene solar
cells were achieved using NFAs including IDT-2BR,184 m-
ITIC,191 IT-OM-2,427 di-PBI,133 ITIC,428 etc.
The active layers of most efficient OPV devices are processed
using chlorinated solvents such as chlorobenzene, o-dichlor-
obenzene, or chloroform, which are not environmentally
friendly solvents. However, previous work have already
shown that eco-friendlier solvents can be employed to process
the organic layer based on polymer:fullerene blends.10
Similarly, nonchlorinated, environmentally friendlier solvents
have also been utilized to process nonfullerene solar cells. A few
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typical examples include the use of anisole to make a 5.43% all-
polymer solar cell,429 the use of a toluene/diphenylether
mixture to fabricate a 9.73% polymer:NFA solar cell,32 the use
of a mixture of THF and IPA to fabricate a highly efficient
(11.34%) polymer:NFA solar cell,430 and the use of mesitylene
as the active layer solvents to achieve a 11.1% (higher than that
processed from chlorobenzene) polymer:NFA solar cell with
long-term device stability.28
One of the unique features of organic solar cells is the
capability of being roll-to-roll (R2R) printed into large area,
flexible devices. Although most R2R based mass production of
OPVs were based on fullerene acceptors,431−436 nonfullerene
roll-coated devices have also been realized.382,437,438 For
instance, Cheng et al. demonstrated roll-coated all polymer
solar cells in 2014437 and Liu et. fabricated polymer:NFA based
nonfullerene solar cells using a slot-die coating and flexographic
printing methods.438 Recently, Liu et al. showed polymer:NFA
(PTB7-Th:IEIC) solar cells fabricated via a roll-coating process
under ambient conditions.382 The authors compared both
flexible ITO and ITO-free substrates (Figure 46), which
Figure 46. (a) PEDOT:PSS PH1000 and ZnO coated PET flexible
substrate with an Ag grid (ITO-free substrate), (b) slot-die coating of
the active layer of PTB7-TH:IEIC and top PEDOT:PSS layer on the
mini roll-coater in sequence, (c) flexographic printing of the top Ag
electrode, and (d) long stripes of roll-coated nonfullerene OSCs based
on the ITO-free substrate. Reproduced from ref 437 with permission.
Copyright 2015 Royal Society of Chemistry.
exhibited PCEs up to 2.26% and 1.79%, respectively,
comparable to the reference devices with fullerene acceptors
under the same conditions. Noticeably, the nonfullerene
devices displayed better dark shelf stability than the fullerene-
based devices.
13. CONCLUDING REMARKS
The examples presented in this review clearly demonstrate that
the nonfullerene acceptor is a promising class of materials to
replace fullerenes in organic solar cells. Diversified building
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Review
blocks and molecular design strategies, along with convergent
and low-cost synthetic routes have been employed in practice
to build over 100 NFAs with tunable spectroscopical and
electrochemical properties. NFAs have been employed to
combine with either polymer or molecular donors in a variety
OPV device platforms including binary/ternary single-junction
and multijunction solar cells, which demonstrated not only
record power conversion efficiencies but also improved
chemical, thermal, and photostability. At the current PCE-
advancing pace, efficiencies over 15% can be forecasted for
single-junction nonfullerene OPVs in the near future. More
excitingly, environmentally friendly solvents, room-temperature
processing, large area, and thick-active layer have been exercised
by various groups to fabricate NFA-based organic solar cells.
These accomplishments manifest the potential for industrial
production and eventual commercialization of OPVs based on
this material class.
On the other hand, morphology and device physics studies
have shown that, at the current stage, improving the nanoscale
organization and charge carrier conduction of the acceptors by
designing new or optimizing known NFAs to match with the
high-performance polymers, whose emergence were based on
the knowledge gained from the past decades, is still essential to
further enhance device performance. Empirical design rules can
be gained from analysis of the known material properties and
device parameters, which can stimulate the development of new
materials and/or discover better material combinations. Never-
theless, a better understanding of the physical processes
governing device operation, such as the morphology forming
process and charge generation and recombination mechanism,
is required to guide future research.
AUTHOR INFORMATION
Corresponding Author
*E-mail: hyan@ust.hk.
ORCID
Zonglong Zhu: 0000-0002-8285-9665
Jie Zhang: 0000-0001-8536-5436
Fei Huang: 0000-0001-9665-6642
He Yan: 0000-0003-1780-8308
Author Contributions
∥
G.Z., J.Z., P.C.Y.C., and K.J. contributed equally to this work.
Notes
The authors declare no competing financial interest.
Biographies
Guangye Zhang received his Ph.D. degree in 2015 from University of
California, Los Angeles for his study in the field of organic
photovoltaics under the direction of Professor Benjamin Schwartz.
He is currently a research assistant professor at HKUST. Besides
organic and hybrid solar cells, his research interests include
optoelectronic techniques such as transient photovoltage, charge
extraction, and photocurrent spectral response.
Jingbo Zhao received his B.Sc. degree in Peking University in 2012,
after which he joined Professor He Yan’s group in HKUST and
obtained his Ph.D. degree in 2015. He worked as a Postdoctoral
Fellow in the same group and then moved to City University of Hong
Kong as a Research Fellow in Professor Alex K.-Y. Jen’s group. His
research interests include development of functional materials for
organic and perovskite solar cells, understanding the structure-
DOI: 10.1021/acs.chemrev.7b00535
Chem. Rev. 2018, 118, 3447−3507
Chemical Reviews
performance relationship of organic semiconductors and fabrication of
flexible electronic devices.
Philip C. Y. Chow obtained his Ph.D. degree from the University of
Cambridge in 2016 for his studies of charge dynamics in organic solar
cells. He is currently a Research Assistant Professor at HKUST with
research interests in organic optoelectronic devices.
Kui Jiang obtained his B.S. degree in Chemistry from Wuhan
University with Professor Jingui Qin in 2011. After that, he moved to
the Hong Kong University of Science and Technology. He is currently
a Ph.D. candidate under the direction of Professor He (Henry) Yan.
His current research focuses on the devices fabrication for photovoltaic
solar cells.
Jianquan Zhang received his B.S. degree in Polymer Science and
Engineering from Zhejiang University, People’s Republic of China, in
2015. He is currently a Ph.D. student under the supervision of
Professor He Yan. His interests lie in the synthesis of novel donor
polymers and small molecular acceptors for nonfullerene organic solar
cells.
Zonglong Zhu received his Ph.D. degree in Hong Kong University of
Science and Technology in 2015 and worked as a postdoc fellow in
Materials Science & Engineering Department at the University of
Washington until 2017. Currently, he works in Prof. Henry Yan’s
group as a visiting scholar. His current research is in electronic devices
based on inorganic/organic perovskites, especially for their applica-
tions in photovoltaics and light-emitting diodes.
Jie Zhang received his B.S. degree in Chemistry from Northeast
Normal University in 2007 and gained his Ph.D. degree in Materials
Science from the South China University of Technology in 2012 under
the supervision of Prof. Yong Cao and Prof. Fei Huang. His research
interests are conjugated functional materials for organic/polymer
optoelectronics.
Fei Huang received his B.S. degree in Chemistry from Peking
University in 2000 and gained his Ph.D. degree in Materials Science
from the South China University of Technology in 2005 under the
supervision of Prof. Yong Cao. After postdoctoral work at University
of Washington with Prof. Alex K.-Y. Jen, he began his academic career
in 2009 as a professor of South China University of Technology. His
main interests are in the fields of organic functional materials and
devices for optoelectronics.
He (Henry) Yan received his B.Sc. degree from Peking University in
2000 and obtained his Ph.D. degree from Northwestern University in
2004. He spent most his research career at Polyera Corporation before
joining HKUST in 2012. He is currently an associate professor in the
department of chemistry at HKUST, an associate director of HKUST
Energy Institute, and an adjunct professor at South China University
of Technology. His main research interests focus on organic
semiconducting materials for organic and perovskite solar cells.
ACKNOWLEDGMENTS
The work described in this paper was partially supported by the
National Basic Research Program of China (973 Program
Project Numbers 2013CB834701 and 2014CB643501), the
ShenZhen Technology and Innovation Commission (Project
Number JCYJ20170413173814007), the Hong Kong Research
Grants Council (Project Nos. T23-407/13 N, N_HKUST623/
13, 16305915, 16322416, 606012, 16306117, and 16303917),
HK JEBN Limited, HKUST president’s office (Project FP201),
and the National Science Foundation of China (No.
21374090). We especially thank Hong Kong Innovation and
3495
Review
Technology Commission for the support through projects ITC-
CNERC14SC01 and ITS/083/15.
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