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Organic solar cells (OSCs) have been dominated by donor:acceptor blends based on fullerene acceptors for over two decades.
This situation has changed recently, with non-fullerene (NF) OSCs developing very quickly. The power conversion efficiencies
of NF OSCs have now reached a value of over 13%, which is higher than the best fullerene-based OSCs. NF acceptors show great
tunability in absorption spectra and electron energy levels, providing a wide range of new opportunities. The coexistence of low
voltage losses and high current generation indicates that new regimes of device physics and photophysics are reached in these
systems. This Review highlights these opportunities made possible by NF acceptors, and also discuss the challenges facing the
development of NF OSCs for practical applications.
L
ight absorption in organic semiconductors generates strongly developments of materials and device engineering. A fundamental
bound excitons. Donor (D):acceptor (A) bulk-heterojunction question open to the community is how the excitons split into free
(BHJ) structures, suitable for low-cost solution processing, pro- carriers in these NF OSCs with low driving energies.
vide an efficient approach to split the excitons into free carriers1,2. One of the key challenges for NF acceptors might lie in their
Among different acceptor materials, fullerene derivatives attracted anisotropic structures. It is well acknowledged that D:A π–π inter-
the most attention and gave the highest power conversion efficien- actions, which depend on the molecular orientation between the
cies (PCEs) for almost two decades. Unique to fullerene derivatives donor and acceptor materials, are very important for the charge
is their ball-like fully conjugated structure, which provides strong transfer and transport in the devices17. Compared with the iso-
electron-accepting and isotropic electron-transport capabilities and tropic ball-like conjugated backbones in fullerene derivatives, the
facilitates electron delocalization at the D:A interfaces3. As such, anisotropic conjugated structures of NF acceptors make it more
fullerene derivatives were believed to be a critical component for challenging to ensure efficient π–π interactions18–21. Therefore,
efficient operation of organic solar cells (OSCs). Indeed, acceptor in NF OSCs, it becomes critically important to pair the donors
materials based on molecules other than fullerene derivatives, gen- with acceptors that have the right chemical structure, which
erally categorized as non-fullerene (NF) acceptors, usually resulted must ensure optimal molecular orientation as well as fine-tuned
in low PCEs1,4, which were mainly attributed to the difficulties in the phase separation.
morphological control5. The development of NF acceptors presents opportunities that are
However, this situation has changed recently. The PCEs of NF otherwise not possible in fullerene-based OSCs, and also opens up
OSCs have increased dramatically since 2015, now reaching a challenges that are waiting to be tackled for future applications of
high value of 13.1% (ref. 6). At present, such a high value is better this promising technology. In addition, the operation of NF OSCs
than the efficiency obtained in the best fullerene-based OSCs7,8. also implies new working mechanisms, which could be fundamen-
The quick development of NF OSCs during the past two years tally different from those in fullerene-based OSCs. This Review
has benefited a lot from the synthetic methods, materials design aims to discuss these opportunities, challenges and working mecha-
strategies and device engineering protocols developed during the nisms, hoping to foster further advances in this field. The PCEs of
past two decades for fullerene-based OSCs. The wide range of NF OSCs are likely to be further improced, through both materi-
donor molecules developed for fullerene-based OSCs provides a als chemistry and device engineering. As such, NF OSCs provide a
rich library for immediate use in NF OSCs. In addition, various promising technology for practical applications in the near future,
design strategies originally developed for donor molecules are especially considering that they have also shown excellent thermal
readily available to tune the absorption spectra and energy lev- stability 22,23.
els of NF acceptors, allowing better flexibility in realizing donor-
acceptor systems with complementary absorption and optimized State-of-the-art non-fullerene acceptors
energy band diagram. The development of a few high-performing Based on chemical structures, state-of-the-art NF acceptors can
molecules, discussed in the next section, has also contributed to be categorized into two types: acceptors based on fused aromatic
attracting the interest of the research community on NF OSCs. diimides, and acceptors based on strong intramolecular electron
From the device point of view, the fact that excitons can separate push–pulling effects. These high-performance NF acceptors share
efficiently upon negligible driving energies9–14 contributes to high two features in common (Fig. 1a). First, their conjugated back-
PCEs in NF OSCs. As a result, NF OSCs often show high photo- bones are modified with π-conjugated functional groups involv-
current and low voltage losses at the same time. In contrast, charge ing highly electronegative elements—for example, oxygen (in the
separation in fullerene-based OSCs usually becomes problematic form of a carbonyl group) and/or nitrogen (in the forms of a cyano
under low driving energies, presenting a trade-off between high group or nitrogen-containing hetero-aromatic segments). Second,
photocurrent and high photovoltage15,16. Currently, the device phys- π-electrons in these functional groups can be well delocalized into
ics and photophysics investigations are lagging behind the rapid the backbones. The first feature provides strong electron-accepting
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy
1
of Sciences, Beijing 100190, China. 2Biomolecular and organic electronics, Department of Physics, Chemistry and Biology (IFM), Linköping University,
Linköping SE-58183, Sweden. 3Cavendish Laboratory, J J Thomson Avenue, Cambridge CB3 0HE, UK. *e-mail: hjhzlz@iccas.ac.cn; fenga@ifm.liu.se
a
Functional groups
O N C
O
N O CN * High electron Low electron Link to Conjugated
negative atom negative atom
N N C * backbone
N O CN (O & N) (C)
O n
O N
O C Conjugated linkage
PV (A PDI derivative acceptor) CN-PPV *
b c R O O R d C8H17 C10H21
R R R N O
O N O
O N O O N O O N O N
O
Ar * *
O S S
N
O n
* * N O O N
S C8H17
O N O O N O O N O OR R O C10H21 N2200 (acceptor)
* * PCE = 9.5%
R R R SF-PDI2 (acceptor)
S Voc = 1.11 V C6H13 PCE = 9.16%
PDI Dimeric PDI Ar = * C2H 5
C10H21 Jsc = 13.3 mA cm–2 Voc = 0.85 V
S C10H21
O R O R Jsc = 15.2 mA cm–2
N N * * C10H21 O
O O C10H21 SN O N S S
N N S C8H17
S S N N
Ar O
O n * * S S S N
N N S
S O F F S
R O R O S F C6H13 F S S O S
And so on S C7H15
n N n
NDI Polymeric NDI C8H17 O
C6H13 C2H 5
P3TEA (donor) C6H13 PTzBI (donor)
C7H15
e f
C6H13 C6H13 F C6H13
F C6H13
CN CN CN CN CN CN CN CN CN CN NC
S CH3 O S
S S F
EG1 EG1 = * * * S S CN
EG1 * CH3 * NC
O
S S CH3 F CN S
O O O O O
IT-4F (acceptor) C6H13 F
C6H13 C6H13 ITCC IT-DM IT-M ITIC IT-4F C6H13 F
Figure 1 | State-of-the-art NF acceptors. a, Key features of successful NF acceptors (PV and CN-PPV are the first NF acceptor materials used in the
heterojunction and bulk heterojunction OSCs, respectively): the functional groups, which are linked by high electron negative atoms (for example, oxygen
or nitrogen) and low electron negative atoms (usually carbon) through a conjugated linkage, offer strong electron accepting capabilities. These functional
groups are then linked to conjugated backbones. b, Two typical types of acceptor materials based on aromatic diimide derivatives: dimeric PDIs and
polymeric NDIs, where Ar represents the linkers between the units. c, Performance and molecular structures of NF OSCs using small-molecule aromatic
diimides (SF-PDI2) as the acceptor and P3TEA as the donor. d, Performance and molecular structures of NF OSCs using polymeric aromatic diimides
(N2200) as the acceptor and PTzBI as the donor. e,f, Molecular structures of eight ITIC-like acceptors with different intramolecular charge transfer (ICT)
effects, with the structures and photovoltaic performance of the combination PBDBT-T-SF: IT-4F shown in f.
abilities, and the second feature ensures a relatively low reorganiza- OSCs—it was used as the electron acceptor in the pioneering bilayer
tion energy so that the accepted electrons can be transported easily devices in 1986 (Fig. 1a)26. Since then, this type of material has been
without being trapped. In addition, for solution-processed OSCs, considered as a promising candidate for NF OSCs. Among various
appropriate functional groups also need to be carefully designed derivatives of fused aromatic diimides, perylene diimides (PDIs)
to satisfy the solubility requirement—this is different to vacuum- and naphthalene diimides (NDIs) (Fig. 1b), widely used in the tra-
deposited OSCs. We note that in vacuum-deposited solar cells, ditional dye industry, are two of the most intensively studied accep-
NF acceptors also demonstrate great potential in enhancing light tor molecules because of their advantages in strong light absorption,
absorption and hence attract considerable attention24,25, consistent low synthesis cost and excellent stability.
with recent development in solution-processed OSCs. PDIs have been frequently used in small molecular acceptors27.
The key considerations for the molecular design of PDI-based accep-
Acceptors based on fused aromatic diimides. Fused aromatic diim- tors are to restrain their aggregation effects and improve their misci-
ide derivative was the first acceptor material used in heterojunction bility with polymer donors. PDIs have rigid and planar conjugated
a b
ITCC
1.0 IT-DM
IT-M –4.0
ITIC
Normalized absorption
IT-4F
IEICO-4F
IT-DM
IEICO
IEICO-4F
IT-4F
ITCC
IT-M
IEIC
ITIC
0.5
–5.0
–5.5
0.0
Optimal geometry
c C6H13 C6H13 d
O S CN
S CN
CN S
CN S O Bulky non-conjugated
Electron pushing
ITIC C6H13 C6H13
Electron pulling
Top view Side view
e
1 2 3
Figure 2 | Unique features of ITIC and its derivatives. a,b, The absorption spectra (a) and molecular energy levels (b) of the ITIC-like molecules in Fig. 1e
can be easily tuned by modulating ICT effects. The molecular energy levels were estimated from the electrochemical cyclic voltammetry measurements.
c, The ITIC molecule includes electron-pushing and electron-pulling units, where the electron-pushing units are shield by bulky non-conjugated side
chains. d, Top and side views of the optimal geometry of the ITIC molecule. e, Bimolecular packing mode indicates that the electron-deficient end-capping
units form π–π interactions with the adjacent acceptor molecule for efficient intermolecular charge transport and with the donor materials for efficient
charge transfer. The electron-rich central unit is not involved in π–π interactions due to the steric hindrance of the non-conjugated side groups, and is only
involved in intramolecular charge transport. Adapted from ref. 39, Wiley (d,e).
(CT) state when the electron–hole pair is still confined to the het- The CT energies can be determined by measuring the absorp-
erojunction, prior to long-range separation3,15. Although it is an tion and/or emission from the CT states by using highly sensitive
important parameter, the Egap in literature was usually arbitrarily photothermal deflection spectroscopy, Fourier-transform photo-
determined from the absorption onset. An appropriate approach current spectroscopy-EQE (FTPS-EQE) or electroluminescence
might be to use the crossing point between the normalized absorp- (EL) measurements48–50. For systems with large driving energies, a
tion and luminescence spectra to determine the Egap (refs 9,46). redshift in the absorption and emission spectra of CT states will
This crossing point corresponds to the energy of the transition be observed compared with those of the singlet excitons from the
from the zeroth vibrational ground state to the zeroth vibrational pristine donor or acceptor materials15. In contrast, for systems
first excited state. An alternative approach suggests the use of the with negligible driving energies, the absorption and emission of
inflection point of the external quantum efficiency (EQE) spec- the devices will be dominated by those from the pristine donor or
trum at long wavelengths to determine the Egap (ref. 47). Given that acceptor materials (Fig. 3a)9,46.
EQE measurements are routinely reported in photovoltaic research Note that a small driving energy approaching zero does not nec-
articles, this method can be conveniently used to extract Egap from essarily guarantee a small voltage loss, as the voltage losses in OSCs
this literature; moreover, it might be particularly advantageous for include the contributions from both the loss due to charge trans-
analysing materials whose absorption onset shifts upon mixing. fer (that is, the driving energy) and the loss due to non-radiative
Normalized FTPS-EQE
injected into the device in dark53. Low non-radiative VOC losses are 10–1
made possible when the EQEEL is enhanced. In other words, a great
solar cell also needs to be a great light-emitting diode54. Generally, Pristine P3TEA
OSCs have much stronger non-radiative VOC losses (in the range of 0.5 P3TEA:SF-PDI2 blend
0.30–0.48 V) compared with highly efficient inorganic or perovskite 10–3
Absorption
S PBDB-T
parameters at the same time. 0.3
Devices. Tandem solar cells, where two or more sub-cells with com-
plementary absorption bands are internally integrated, provide an
effective approach to enhance the light absorption and reduce the
thermal losses in single-junction solar cells80–83. The advantages of 120
tandem structures have not been fully explored in fullerene-based
OSCs, as they usually demonstrate large voltage losses. In contrast, 0.0 30 °C 90 °C 30 °C
NF OSCs can significantly enhance the PCE of tandem OSCs,
thanks to their highly tunable absorption as well as the coexistence 400 600 800
of low voltage losses and efficient charge separation. By carefully Wavelength (nm)
tuning the absorption of both front and rear sub-cells, NF-based b
tandem cells have demonstrated high PCEs of 13.8% (ref. 84) and Neat PBDB-T PBDB-T:ITIC PBDB-T:PC71BM
more recently over 14% (ref. 85). A main reason for such a high 3.0 6.0 6.0
efficiency is the reduced voltage loss. A critical challenge for current
Height (nm)
tandem NF OSCs is the photocurrent mismatch between the front
and rear sub-cells. This can in principle be solved by increasing the
–3.0 –6.0 –6.0
thickness of both sub-cells with optimized bandgaps, so that differ-
ent parts of the light spectrum can be effectivey absorbed by each 0.0 2.0 µm 0.0 2.0 µm 0.0 2.0 µm
sub-cell. However, as discussed previously, the efficiencies of thick
NF OSCs are currently limited by poor charge transport.
5.0 3.0 5.0
In addition to tandem cells, ternary devices, where the active
Phase (*)
layer consists of three components, offer another feasible approach
to extend the light absorption of the conventional binary OSCs86,87.
The emergence of NF OSCs provides a wide range of possibili- –5.0 –3.0 –5.0
ties for ternary devices: the third component can be a polymer 0.0 2.0 µm 0.0 2.0 µm 0.0 2.0 µm
or small molecule donor 88, a fullerene-based acceptor 89,90, or an
NF acceptor (either polymer or small molecule)91. In addition to Figure 4 | The aggregation effects of the donor materials (PBDB-T as
absorption and energy-level considerations, obtaining optimized an example) in high-efficiency NF OSCs. a, Temperature-dependent
morphology when a third component is added is critical to ter- absorption spectra of PBDB-T, which shows strong aggregation effects and
nary devices. In cases where the third component is a fullerene good dispersibility in dilute solution. The inset shows that the solution is
derivative, the ratio of fullerene derivatives is usually kept low clear and that the temperature-dependent colour change is well reversible.
for good morphology. In order to significantly extend the light b, The topography (top) and phase (bottom) images of the neat PBDB-T,
absorption, one of the effective approaches might be to use a third PBDB-T:ITIC and PBDB-T:PC71BM films spin-coated from chlorobenzene
component that is similar to an existing component in chemical solution under ambient temperature. The nanometre-sized aggregations
structure but different in absorption region. For example, a very can be clearly observed in the neat film, and the two blend films show very
recent work employed two ITIC-like acceptors (IT-M and IEICO) similar phase separation morphologies, indicating that the morphology of
and demonstrated that these two acceptors are well miscible with the blend films are mainly determined by the aggregation of the polymer.
each other 91. With weight ratios changing from 1:0 to 0:1, the light
absorbed by these two acceptors can always effectively contrib- absorption nor the small voltages loss requirements. Instead, NF
ute to the photocurrent generation. In addition, ternary devices OSCs provide the possibilities to meet both requirements. For
have shown improved stability compared with binary devices23. example, a low-bandgap NF-acceptor (namely IEICO-4F) demon-
Rich device physics might also be involved in these new ternary strates great potential for this application88. Absorption of IEICO-4F
devices. For example, it was previously believed that the two mainly locates in the deep-red and near-infrared region, ranging
donors or two acceptors in ternary devices form alloys, so that the from ~700 nm to ~1,000 nm. At the same time, it delivers a high VOC
VOC lies between the VOC values of two binary devices89,92. However, (larger than 0.7 V), demonstrating a small voltage loss. In addition
recently a ternary device demonstrated a VOC value higher than to the explorations of more NF acceptors for this application, efforts
the VOC values of both binary devices93. This finding not only pro- should also be devoted to achieving an optimized trade-off between
vides a unique approach to enhance the photovoltage of ternary transparency and conductivity of transparent electrodes.
devices, but also implies new device physics for ternary devices.
In some applications, absorbing only part of the light spec- Outlook
trum—rather than maximizing the light absorbed—could be use- Previous efficiency predictions of OSCs are based on the assump-
ful. A typical example is semitransparent OSCs94–96, which provide tion that significant driving energies are needed for efficient charge
unique opportunities for niche applications—for instance, for smart separation. Since NF OSCs have successfully demonstrated high
windows. Ideal semitransparent OSCs are supposed to have weak quantum efficiency on negligible driving energies, we feel it neces-
absorption in the visible region and strong absorption in the near- sary to re-estimate the efficiency (Fig. 5a). All the parameters can
infrared region97. In addition, a low voltage loss is also required be empirically estimated other than non-radiative recombination
for high efficiency. Fullerene-based OSCs can meet neither the losses, which the community has yet to understand, as discussed
16 0.8 CIGS 15
0.27 15 0.6 14
FF
14 13
12
13 11
12 0.7 10
11
10
Figure 5 | New efficiency prediction for OSCs based on NF acceptors. a, Efficiency prediction (plotted in colour scale, with numbers on the contour lines
representing PCE in %) for NF OSCs based on the assumption that they can work efficiently upon negligible driving energies. This figure highlights the
importance of reducing the non-radiative recombination losses to further enhance the PCEs. b, Empirical relationship between the VOC and the FF, together
with the reported high-FF devices, including both inorganic and perovskite solar cells (in red), fullerene OSCs (in black), and NF OSCs (in green). The data
are collected from refs 6,38,99–101. c, An alternative way to predict the efficiency of NF OSCs, showing the efficiency versus the energy losses.
previously. The EQE is assumed to be 85% above the bandgap; the the lab-scale devices to large-scale modules using low-cost print-
VOC is determined by equation (1), where ΔE1 is calculated based on ing techniques, there are several additional issues to be taken care
the bandgap, ΔE2 is assumed to be 0.05 due to non-ideal band edge9, of. First, green solvents are required for processing. Currently,
and ΔE3 (non-radiative recombination losses) is used as the y axis; the lab-scale high-efficiency NF OSCs are mainly processed from
the FF is based on the well-established empirical relationship98: toxic chlorinated solvents (for instance, chloroform or chloroben-
zene). Fortunately, compared to fullerene derivatives, NF accep-
γ – ln(γOC + 0.72) tors show excellent solubility in a larger range of solvents, offering
FF = OC (2)
γOC + 1 more possibilities to select green solvents. For example, a NF OSC
with over 11% PCE was recently reported by using a mixture of
where γOC = qVOC/nkT, q is the elementary charge, n is the diode tetrahydrofuran and isopropanol as processing solvents, which
ideality factor, k is the Bolztmann constant and T is the tempera- are low toxic and also biodegradable58. Second, thickness toler-
ture. Figure 5b shows the maximum FF (FFmax) as a function of the ance is preferable for large-scale applications. Currently, the effi-
VOC, indicating that smaller voltage losses (hence larger VOC) also ciency of NF OSCs drops significantly with increasing thickness
mean larger possible FF for a given material. In reality, the FF can- from 100 to 250 nm, mainly due to decreasing FF6. As discussed
not reach the maximum value even for crystalline GaAs and Si solar previously, future efforts to increase the carrier mobilities might
cells99. We summarize high-FF OSCs (based on both fullerene and help to solve this problem. Third, detailed investigations on sta-
NF acceptors) available in literature in the figure6,38,100,101. We find bilities are needed23. It is well acknowledged that anisotropic NF
that the values lie within a range of FFmax – (0.1 ± 0.04), and an FF of acceptors with rigid backbones are less mobile than fullerenes in
FFmax – 0.1 is used in the efficiency estimation. the blend, leading to better morphological stability than fullerene-
As expected, non-radiative recombination VOC losses play a key based OSCs, which have been proved in a few highly efficient NF
role in determining the efficiency of the OSCs. A high efficiency OSCs22. However, stability of NF OSCs under different environ-
of 19% is within reach at wavelengths around 860 ± 60 nm, if the mental factors (for instance, oxygen, moisture and elevated tem-
non-radiative recombination VOC loss could be decreased to ~0.21 V. peratures) needs to be systematically studied. Fourth, new donor
Therefore, understanding and decreasing the non-radiative recom- and acceptor materials need to be developed. State-of-the-art NF
bination is key to further enhancing the PCEs of NF OSCs. The OSC donor and acceptor materials are based on complicated syn-
non-radiative recombination losses can potentially originate from thesis routes, making the cost of NF OSCs high. It will be desirable
the materials and energetic levels9,55. In addition to decreasing non- for future applications to design new materials, which combine
radiative recombination, optimizing the EQE is also important to low cost and high performance.
reach high efficiency. Although a high EQE of 83% was reported
in the literature for NF OSCs, such a high value only covers a small Received 27 September 2017; accepted 6 December 2017;
wavelength range6. Especially, most of the high-efficiency NF OSCs published online 23 January 2018
show low EQE values at short wavelengths due to limited absorp-
tion in this region. The light absorption at short wavelengths can be References
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