ISSN 18112382, Polymer Science, Ser. C, 2014, Vol. 56, No. 1, pp. 72–83. © Pleiades Publishing, Ltd., 2014.

Original Russian Text © V.A. Trukhanov, D.Yu. Paraschuk, 2014, published in Vysokomolekulyarnye Soedineniya, Ser. C, 2014, Vol. 56, No. 1, pp. 76–88.

NonFullerene Acceptors for Organic Solar Cells

V. A. Trukhanov and D. Yu. Paraschuk
International Laser Center and Faculty of Physics, Moscow State University, Moscow, 119991 Russia
email: vtrukhanov@mail.ru
Received February 6, 2013

Abstract—Solar cells based on organic semiconductor molecules are a promising alternative to conventional
silicon photocells owing to their low cost, simple production, and good mechanical properties. Effective
organic photocells are based on a heterojunction using an active layer consisting of two different organic semi
conductors, one of which is an electron donor, while the other is an acceptor. Progress in organic photovol
taics is related to the development of new donor materials, while fullerene derivatives are commonly used as
acceptors. The advantages and disadvantages of fullerene compounds for organic solar cells are discussed in
this review, the principles of their operation are briefly considered, and the most successful new nonfullerene
acceptors are described. The application of latter acceptors has made it possible to fabricate organic solar cells
with an efficiency of about 2–4%.
DOI: 10.1134/S181123821401010X

INTRODUCTION energy levels of the frontier orbitals were elaborated as

Currently, the portion of solar energy in global
energy production is substantially increasing. The
demand for solar cells (SCs) that are newer, cheaper,
and more technologically advanced for mass produc
tion is an urgent issue because traditional silicon SCs
are too expensive. SCs based on organic semiconduc
tors (organic SCs) can possess, in addition to poten
tially lower cost production, a number of new features,
such as mechanical flexibility, low mass, and translu
cency. The highest efficiency for an organic SC today
is 12% [1], which is comparable to the efficiency of an
inorganic SC based on amorphous silicon [2]. The
principles of organic SCs differ somewhat from those
of traditional inorganic SCs [3]. For example, an effi
cient organic SC requires a heterojunction [4], which
arises from the contact of two different organic semi
conductors, one of which is an electron donor, while
the other is an electron acceptor. Historically, the first
proposed heterojunction was a planar heterojunction
whose active layer was composed of two layers: a donor
layer (phthalocyanine) and an acceptor layer (perylene
derivative). This layout made it possible to achieve 1%
efficiency. In the 1990s, a bulk heterojunction featur
ing an active layer composed of a mixture of a donor
and an acceptor was proposed. In this case, the area of
the heterojunction was increased and effective charge
separation was achieved throughout the volume of the
active layer, thereby increasing efficiency to 3% [5]. A
further increase in efficiency of an organic SC became
possible owing to the development of new donor
organic semiconductors (polymers, oligomers, etc.)
with improved properties, such as a broader band of
spectral sensitivity and a high chargecarrier mobility.
Materials with specially selected locations of the
well [6, 7]. In addition, fullerenes C60 and C70 and their
soluble derivatives are always used as acceptors in the
best examples of organic SCs. The advantage in the
application of fullerenes and their derivatives as accep
tors for organic SCs is related to the following factors.
First, they are able to form a nanoscale morphology of
the bulk heterojunction during mixing with donor sub
stances required for the effective separation and trans
port of charges. Second, fullerenes have a high elec
tron affinity, which is required for the capture of elec
trons from a donor material. Third, fullerenes exhibit
high electron mobility [8, 9]. Figure 1 shows the struc
tural formulas of some fullerene acceptors. During the
development of organic SCs, the most widely used
fullerenes are methanofullerenes, such as phenyl
C61butyric acid methyl ester (PCBM, 1a), and simi
lar compounds based on C70, such as phenylC71
butyric acid methyl ester (PC70BM, 2). PC70BM pos
sesses a slightly higher optical absorption than PCBM.
Nevertheless, a search for optimal fullerene derivatives
for organic SCs was conducted in recent years. For
example, PCBM analogs that contained a thiophene
(1b) [10], fluorene (1c), or triphenylamine substituent
(1d) [11], instead of a phenyl group, were synthesized.
Several dozen methanofullerenes with different
structural variations of substituents in the cyclopro
pane ring (in which two carbon atoms belong to
fullerene, while the third carbon atom belong to an
addend) were investigated [12, 13]. However, the
investigated organic SCs, i.e., methanofullerenes
based on the most studied donor polymer, poly3hex
ylthiophene (P3HT, 3) were not able to produce a
higher efficiency than that of PCBM and PC70BM,
which was 4–5% [14]. Many researchers believe that

72
 NONFULLERENE ACCEPTORS FOR ORGANIC SOLAR CELLS 73

Ar OCH3 S
O OCH3 n

1 2 3

OCH3 OC6H13
Si Si
O O
Lu3N

O
H3CO

4 5 6 7

S
Ar = (1а), (1b), (1c) and N (1d)

Fig. 1. Structural formulas of fullerene derivatives 1, 2, and 47 and poly3hexylthiophene 3.

this efficiency value for the pair P3HT–PCBM
(PC70BM) is close to the theoretical limit. Conse
quently, the motivation for development of new meth
anofullerenes for organic SCs may be more process
able synthesis and better purification than those of
PCBM [15].
One of the disadvantages of methanofullerenes is
overly high electron affinity (a low energy of the lowest
unoccupied molecular orbital (LUMO)), which limits
the operating voltage of organic SCs [3]. To reduce the
electron affinity of fullerenes, two approaches were
demonstrated: opening of fullerene double bonds and
creating fullerene compounds with metals. Opening of
fullerene double bonds increases the energy gap
between the frontier molecular orbitals by ~0.1 eV.
This is why methanofullerenes have an approximately
0.1 eV lower affinity than parent fullerene; for bis and
trismethanofullerene, the affinity values are already
lower by ~0.2 and ~0.3 eV, respectively [16]. As a
result, the opencircuit voltage of SCs based on P3HT
and bisPCBM 4 was 0.73 V (0.58 V for PCBM); thus,
the efficiency improved to 4.5%, which is higher than
that of PCBM, 3.8% [17]. Note that the connection of
additional ligands to fullerene reduces the mobility of
charge carriers [16, 18], and moreover, bisPCBM and
trisPCBM contain a number of isomers that may
lower the efficiency of a solar cell.
In addition to methanofullerenes, silylmethyl
fullerene 5 [19], which possesses an electron affinity
~0.1 eV lower than that of PCBM, was proposed. The
use of such a silicone fullerene derivative as an accep
tor made it possible to reach an opencircuit voltage of
0.75 V and an efficiency of 5.2%. Y. Li et al. developed
indeneC60bisadduct 6, which had a 6.48% effi
ciency in a mixture with P3HT [20]. Fullerene accep
tor 6 was easier to synthesize, and its solubility was
higher than that of PCBM [21].
In the case of fullerene compounds with metal, the
metal distributes a part of the electron density on the
fullerene, thereby significantly reducing its electron
affinity. The most successful studies were [22, 23],
where endohedral metallofullerene Lu3NС80PCBH 7
was synthesized and an even higher opencircuit volt
age value (0.81–0.89 V) was attained in a mixture with
P3HT; in this case, the maximum efficiency was 4.2%.
However, the synthesis of endohedral metallof
ullerenes is very expensive and it is hardly possible to
rely on their largescale production. In addition, a

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74 TRUKHANOV, PARASCHUK
number of metals can form stable exohedral com
plexes with fullerenes [24, 25], thus reducing the elec
tron affinity of the complex by 0.4 eV with respect to
that of the initial fullerene [26]. These complexes are
easy to synthesize, and they may provide a higher volt
age of organic SCs [27].
Although fullerene acceptors have made it possible
to create the most effective organic SCs yet, they have
a number of disadvantages. First, fullerenes weakly
absorb solar radiation [28, 29]. Second, fullerenes
possess overly high electron affinity, which limits the
voltage of an organic SC. Third, they can be relatively
easily photooxidized, a circumstance that has a cru
cial effect on the lifetime of a solar cell. Furthermore,
synthesis and purification of fullerene derivatives
require significant energy consumption and solvent
costs [30, 31]. The aforementioned disadvantages of
fullerene have stimulated elaboration of nonfullerene
acceptors: acceptor organic semiconducting materials
based on other molecular structures. It is expected that
a greater variety of acceptor materials might provide a
larger number of successful combinations with donor
materials, including those existing and those to be cre
ated in the future. This circumstance will make it pos
sible to create SCs with higher efficiency and
improved properties, such as high opencircuit volt
ages, long lifetimes, and ease of mass production.
This review deals with the most effective organic
SCs fabricated on the basis of different classes of
organic nonfullerene acceptors. The synthesis and
study of new acceptors for organic nonfullerene SCs
were described in detail in reviews [32, 33]; in the cur
rent review, fullerenefree organic SCs with the high
est efficiency (2–4%) will be considered along with
the most recent investigations on the elaboration of
nonfullerene acceptors.
COMPOSITION OF ORGANIC SOLAR CELLS
Organic SCs are based on organic semiconducting
organic macromolecules that have a carbon skeleton
with alternating single and multiple bonds that form a
πconjugated system. Organic semiconductors
include conjugated polymers (the simplest example is
polyacetylene) and lowmolecularmass compounds
(oligomers, fullerenes, etc.). In the traditional models
of solidstate physics, the analogue of the upper edge
of the valence band in organic semiconductor mole
cules is considered to be the highest occupied molec
ular orbital (HOMO), while the analogue of the lower
edge of the conduction band is considered to be the
LUMO. The analogue of the bandgap energy is usu
ally considered to be the energy difference between the
HOMO and the LUMO. The position of the LUMO
level relative to the vacuum level is electron affinity χ
of an organic semiconductor in the first approxima
POLYMER SCIENCE
tion, and the position of the HOMO level relative to
the vacuum level is ionization potential Φ.
A typical organic SC consists of an active layer
located between two electrodes, one of which is trans
parent (Fig. 2a, 2b). Indium tin oxide (ITO) with a
conductive polymer complex of poly(ethylenediox
ythiophene)–polystyrenesulfonate (PEDOT:PSS,
P:P) is generally used as the transparent electrode.
Electrode materials have different work functions; the
electrode with a lower work function is called the cath
ode, and the electrode with the higher work function is
called the anode. The organic active layer of an SC
consists of two organic semiconductors with different
values of electron affinity χ and ionization potential Φ:
an electron donor (with smaller values of χ and Φ) and
an acceptor (with larger χ and Φ values). At the con
tact between the donor and the acceptor, a heterojunc
tion of the second kind is formed. A donor and an
acceptor in the active layer can be either two separate
layers (a planar heterojunction, Fig. 2a) or a mixture of
the donor and the acceptor on the nanometer scale
with a large contact area (a socalled bulk heterojunc
tion, Fig. 2b).
The process of converting optical radiation into
electricity in organic an SC is shown schematically in
Fig. 2c and involves the following multistage process.
When a photon is absorbed in the active layer (by
either the donor or the acceptor), exciton 1 (a bound
electron–hole pair) is formed. An exciton of an
organic semiconductor possesses a large binding
energy, so that the probability of its dissociation into a
free electron and hole influenced by thermal motion is
extremely small. Exciton dissociation can be achieved
with a heterojunction because the contact of donor
and acceptor materials has a gap in the energy levels
that provides for a high electric field. Excitons have a
finite lifetime (about 1 ns or less) after which they relax
(2) to the ground state (the electron and hole recom
bine); the specific diffusion length of an exciton is on
the order of 10 nm for disordered organic semicon
ductors [34]. The contact of a donor with an acceptor
in the active layer with a bulk heterojunction is distrib
uted throughout the volume, so that the efficiency of
an SC with a bulk heterojunction is generally higher
than that for an SC with a planar heterojunction. If a
diffusing exciton (3) reaches the heterojunction, fast
charge transfer (4) occurs, thereby resulting in elec
tron localization in the acceptor and hole localization
in the donor. However, an electron and a hole are still
bound via the Coulomb force [35, 36]; separation into
free charges occurs owing to the electric field that
forms inside the active layer because of different work
functions of the cathode and the anode. Further, an
electron moves to the cathode via the acceptor phase,
while a hole moves to the anode (5) via the donor
phase; thus, a photocurrent (6) appears. For an SC
based on a bulk heterojunction, the phase morphology
of the donor and the acceptor is important: On the one
hand, the heterojunction interface should be located
Series C Vol. 56 No. 1 2014
 NONFULLERENE ACCEPTORS FOR ORGANIC SOLAR CELLS 75

(a) (b)
Cathode Cathode
Donor
Acceptor
Donor Acceptor
Anode Anode
Transparent support Transparent support

(c) (d)
I
Ec Ldif
4
2
1 5
Anode 3 6 VM V
6 Cathode PM
5 Voc
IM
Donor Acceptor Ev
Isc

Fig. 2. Schemes of organic solar cells with (a) a planar heterojunction and (b) a bulk heterojunction; (c) energy diagram of an
organic solar cell and the process of converting light into electricity; (d) a typical current–voltage characteristic of a solar cell
(solid line) under illumination and (dashed line) in the dark.

at each point within the active layer within a radius less
than the excitondiffusion length; on the other hand,
effective collection of charges on electrodes should be
provided via a continuous pathway from each point to
the anode via donor phase and to the cathode via the
acceptor phase.
The main work characteristic of any SC is the cur
rent–voltage characteristic (CVC); a typical CVC is
shown schematically in Fig. 2d. The main operating
parameters of an SC are shortcircuit current Isc,
opencircuit voltage Voc, fill factor FF, and the effi
ciency. The latter is defined as the ratio between max
imum SC power Pmax (i.e., the point of the CVC where
the product of voltage and current is maximum) and
incidentradiation power Pir:
Pmax
η= × 100%
Pir
The fill factor characterizes the closeness of the
CVC form in the fourth quadrant to a rectangular and
is defined as the ratio between the product of current
IM and voltage VM at the point of maximum power to
the product of current Isc and voltage Voc:
I MVM
FF = × 100%
I scVoc
Another important characteristics of an organic SC
is the spectrum of the external quantum efficiency
(EQE): the ratio of shortcircuit current density Isc to
incidentphoton flux density Iph at wavelength λ:
I (λ)
EQE(λ) = sc × 100%,
eJ ph(λ)
where the electron charge is e = 1.6 × 10–19 C.
The parameters of materials used in the fabrication
of organic SCs, in particular those of the new accep
tors (electron mobility, absorption spectrum, miscibil
ity with donors, etc.), have a strong influence on the
processes of energy conversion. This circumstance in
turn affects the basic electrical characteristics of SCs,
such as the shortcircuit current, opencircuit voltage,
fill factor, and efficiency. Therefore many factors
should be taken into account during development of
new acceptors; that is the focus of discussion in the
next section of this review.
ORGANIC SOLAR CELLS BASED
ON NONFULLERENE ACCEPTORS
This section covers research into the creation of
organic SCs with heterojunctions based on non
fullerene acceptors with the highest efficiency. The
main requirements for such acceptors are relatively
high electron mobility μe, comparable to the hole
mobility in a donor material; a wide and intense
absorption spectrum with maximum correspondence
to the solar spectrum; and the optimum value of elec
tron affinity χ. The latter should be ~0.2–0.5 eV lower
than that in fullerene acceptors in order to provide a

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

76 TRUKHANOV, PARASCHUK
high Voc value, but on the other hand, it should be
~0.3–0.4 eV higher than the electron affinity of the
donor to provide for efficient exciton dissociation. The
other main requirements for the nonfullerene accep
tors are the ability to form a bulk heterojunction with
a specific scale of donor–acceptor phase separation of
about 10 nm, high solubility, and photostability. Below,
the influence of the molecular structuring of accep
tors, their absorption spectra, chargecarrier mobility,
and the position of energy levels (HOMO and LUMO)
on the main characteristics of SCs, such as efficiency,
shortcircuit current density, opencircuit voltage, fill
factor, and the EQE.
Figure 3 shows the structural formulas of a typical
polymer and lowmolecularmass donors used in the
creation of SCs with nonfullerene acceptors. Figure 4
shows the structural formulas of nonfullerene accep
tors applied for fabrication of the most effective
organic fullerenefree SCs, discussed below. Figure 5
shows the absorption spectra of a series of non
fullerene acceptors.
The table presents the parameters of SC samples
formed on the basis of nonfullerene acceptors A1–
A11: the acceptor and donor materials, their weight
ratio in an active layer, activelayer thickness Lac, the
anode and cathode materials, and area S of the SC
workspace. The following characteristics of acceptors
are additionally given: electron mobility μe and elec
tron affinity χ, which is equal in the first approxima
tion to the position of the LUMO energy level. Mobil
ity measurements for acceptors A1–A5, A10, and A11
were determined with the method of current limited
by the space charge, while mobility measurements for
A7 were determined through the fieldeffecttransistor
method. The table additionally lists the main parame
ters of organic SCs fabricated from nonfullerene
acceptors: the shortcircuit current density, opencir
cuit voltage, filling factor, efficiency, and maximum
EQE value.
Figure 6 shows the I–V characteristics of samples
of organic fullerenefree SCs. It is evident that the
perylenediimide derivatives have values of the short
circuit current density in the range 4–9 mA/cm2 and
values of the opencircuit voltage in the range 0.7–
1.0 V. For other nonfullerene acceptors (A5, A8–
A11), the values of shortcircuit current density lie in
the range 2.6–6.4 mA/cm2 and the values of opencir
cuit voltage lie in the range 0.8–1.2 V.
The spectra of the external quantum efficiency of
organic SCs with nonfullerene acceptors A1– A11
are shown in Fig. 7. From a comparison of EQEspec
tra shapes and the absorption spectra for components
of the active layer, the contribution of donor and
acceptor phases to a photocurrent can be estimated, as
will be done below.
POLYMER SCIENCE
PerylenediimideBased Acceptors
The most efficient organic fullerenefree SCs, up
to 4%, were fabricated with the use of perylenediimide
derivatives as acceptors (A1–A4, A7). Perylenediim
ides possess high electron affinity χ (Table) because of
electronwithdrawing imide groups that are conju
gated with perylene aromatic cores. These compounds
are popular for fabrication of organic electronic
devices owing to superior chemical, thermal, and pho
tochemical stability and high electron mobility [37].
Furthermore, perylenediimides are currently pro
duced on the multiton scale and are used as commer
cial dyes [38]. Note that the first organicheterojunc
tionbased SC, proposed by C.W. Tang [4], was pro
duced with the use of perylenediimide derivatives as
the acceptor and copper phthalocyanine as the donor.
Some of the most efficient organic fullerenefree
SCs (with efficiency up to 4%) were developed by
Sharma et al. [39–41]. In these studies, the authors
attached two tertbutylphenoxy groups to perylenedi
imide; then, by the varying imide substituents, they
developed a series of highly efficient acceptors A1–A3
(Fig. 4). On the basis of acceptor A1 with anthracenyl
substituents paired with donor oligomer D3, an
organic SC was furnished with an efficiency of 2.85%
(Voc = 0.92 V, a fill factor of 47%, see Fig. 6a) [39].
Analogously, on the basis of a mixture of acceptor A2
and donor D4, a sample with an efficiency of 1.87%
was obtained [40]. The efficiency of this device could
be increased up to 3.17% via introduction of a thin
layer of zinc oxide between the active layer and an alu
minum electrode [40]. Presumably, an additional thin
layer of ZnO not only improved the transport of elec
trons from the active layer to a cathode but also
increased the light absorption in the active layer owing
to optical interference between the incident light and
the reflected light from the aluminum electrode. The
most outstanding fullerenefree organic solar cell was
fabricated from a mixture of cyanogroupcontaining
acceptor A3 with seleniumbased donor oligomer D5.
This SC has shown 3.88% efficiency, which is a record
for an organic fullerenefree SC with bulk heterojunc
tion [41]. This high efficiency of photovoltaic devices
based on acceptor A3 is related to its wide absorption
spectrum (Fig. 5a).
In a recent paper, A. Sharenko et al. developed an
organic SC with 3% efficiency on the basis of
perylenediimide acceptor A4 and narrowband low
molecularmass organosilicon donor D6 [42]. Such an
efficiency has been achieved via the selection of the
optimum ratio of the donor and the acceptor, small
special additives to the solvent, and thermalannealing
conditions for organic an SC: The optimized sample
had a donor–acceptor mass ratio of 1 : 1, and diio
dooctane (0.4%) was used as an additive to the solvent
(chlorobenzene). The absorption spectrum of accep
tor A4 (Fig. 5a) is well overlapped by the solar spec
trum, and its contribution to photocurrent is compa
Series C Vol. 56 No. 1 2014
 NONFULLERENE ACCEPTORS FOR ORGANIC SOLAR CELLS 77

C4H9 C2H5
C4H9
O
S C2H5
S
n S CN
S NO2

S NO2 S S
S CN N N
S
S n

C2H5 C4H9
D1 D2 D3
CN
OC6H13 NO2
S CN
NO2
NO2 S OC6H13 NO2 S S
CN CN N N
D4 Se
D5
S N Si N S
N N
S S
S F F S
S S
D6

Fig. 3. Donor organic semiconductors used in organic solar cells with nonfullerene acceptors: D1 and D2 are polymeric donor;
D3–D6 are lowmolecularmass donors.

rable with that of a donor. However, organic SCs based
on the same donor D6 mixed with fullerene acceptors
have much greater efficiency: in particular, the tandem
with PC70BM (Figs. 1, 2) possesses an efficiency of 7%
[43]. This circumstance is related above all to the fact
that acceptor A4 has an electron mobility, μn = 1.7 ×
10–4 cm2/(V s) (table), that is one order lower than that
of fullerene derivatives, μn ~ 10 ⎯3 cm2/(V s) [44]. Sec
ond, the efficiency is lower because electron transport
in acceptor A4 is hampered by traps, as reported in
[45]. Further investigation should be aimed at
improvement of the electron transport in acceptor
materials.
Nevertheless, the efficiency of organic SCs based
on mixtures of perylenediimides with lowmolecular
mass donors is significantly higher than that of SCs
that use conjugated polymers as donors [46]. This cir
cumstance is largely related to the fact that perylene
diimides tend to crystallize in blends with polymers,
thereby causing largescale phase separation (about
several micrometers) [47]; i.e., the morphology of the
active layer with the bulk heterojunction becomes sub
optimal for charge separation, and as a result, SC cur
rent decreases. To solve the problem of acceptor crys
tallization, it was proposed to synthesize nonplanar
perylenediimidebased molecules (Fig. 4, A7), which
have a lower tendency to crystallize [48]. In an accep
tor A7 molecule, two perylenediimide units are con
nected with hydrazine, and the repulsion of electron
clouds on oxygen atoms causes the plane perylenedi
imide fragments to be located perpendicularly to each
other. It is assumed that a decrease in planarity of a
molecule leads to a decrease in phase separation in a
mixture with a donor polymer, a situation that pro
motes more efficient charge separation at the hetero
junction. Furthermore, typical nonplanar acceptor A7
is characterized by an increased coefficient of absorp
tion in the wavelength range 500–600 nm relative to
that of PC70BM; this circumstance makes it promising
to apply acceptor A7 in combination with narrowband

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

78 TRUKHANOV, PARASCHUK

O O O
O O O O O O

N N N N CN N N N N CN

O O O O CN N O O N CN
O O O

A1 A2 A3
C4H9
O N O C4H9 C4H9
C2H5
C2H5 C2H5 C6H13 O N O
N N S S
O O
S S S
S S S
O N N O
S S
C2H5 Si C2H5 O N O C6H13
C2H5 C2H5
C4H9 C4H9 C2H5
O N O C4H9 C4H9
C4H9

A4 A5 A6
O O
C7H15 O O C7H15
N N N N
C7H15 O O C7H15
O O
S
C4H9
A7 N
O C2H5 C4H9
S C2H5 O
N C2H5
O N N O
C4H9 S N O
N N
S S
O O
A8 N O N
C8H17 C8H17 C2H5
N N C4H9
O O O O
S C2H5 S
C4H9 O
S N
N
C4H9
S O
C2H5
CN CN
A9 A10 A11

Fig. 4. Nonfullerene acceptors used as activelayer components of organic solar cells.

conjugated polymers as donors that have a bimodal rents differed by one order. This outcome supports the
absorption spectrum with a dip in a mentioned wave hypothesis that a nonplanar acceptormolecule struc
length region. Acceptor A7, despite its nonplanarity, has ture causes an increase in the shortcircuit current.
a fairly high electron mobility, μn = 8 × 10–3 cm2/(V s), The external quantum efficiency of an organic SC
comparable with the mobility in PC70BM. Organic based on A7:D2 in the range 400–800 nm has a value
SCs with efficiency 2.77% were designed on the basis of 30–40% without deep dips (Fig. 7a), a result that
of a mixture of nonplanar perylenediimide acceptor indicates the good combination of the absorption
A7 and lowbandgap conjugated polymer D2 (table). spectra of polymer D2 and acceptor A7 [48]. Micro
Note that the shortcircuit current of 7.9 mA/cm2 scopic investigation the A2:A7 active layer has not
(Fig. 6a) is one of the highest for SCs with nonful revealed the presence of micrometersized acceptor
lerene acceptors. For comparison, similar samples crystals, which, in contrast, were observed in an SC
were prepared on the basis of a planar acceptor con based on a planar acceptor [48]. Further research may
sisting of a single fragment of an A7 molecule under be directed to the selection of better suitable donor
the same conditions. These samples exhibited an materials that can successfully work together with
opencircuit voltage of 0.65 V, a shortcircuit current nonplanar perylenediimide acceptors.
of only 0.85 mA/cm2, a filling factor of 30%, and an
efficiency of 0.13%. The sample based on nonplanar EQE spectra for SCs with perylenediimide accep
acceptor A7 surpassed in all respects a similar sample tors A1–A4 and A7 (Fig. 7a) have two peaks: one in
based on a planar acceptor, and the shortcircuit cur the wavelength range 400–500 nm, corresponding to

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 NONFULLERENE ACCEPTORS FOR ORGANIC SOLAR CELLS 79

Absorbance, rel. units Absorbance, rel. units

1.2 (a) 1.2 (b)
A1 A5
A2 A8
A3 A9
0.8 A4 0.8 A11

0.4 0.4

0 0
300 400 500 600 700 800 300 400 500 600 700 800
λ, nm λ, nm

Fig. 5. Absorption spectra of nonfullerene acceptors: (a) perylenediimine derivatives A1–A4 and (b) other acceptors A5, A8, A9,
and A11.

Current density, mA/cm2 Current density, mA/cm2

4 0
(a) (b)

0 −2

−4 −4 A5
A1 A6
A2 A8
−8 A3 −6 A9
A4 A10
A7 A11
−12 −8
–0.2 0 0.4 0.8 0 0.4 0.8 1.2
Voltage, V Voltage, V

Fig. 6. Current–voltage characteristics of organic SCs with nonfullerene acceptors: (a) perylenediimine derivatives A1–A4 and
A7 and (b) other acceptors A5, A6, and A8–A11.

acceptor absorption (A1–A4 or A7); the other at 600–
700 nm, corresponding to donor absorption (D2–
D5). This circumstance indicates that the contribu
tion to the total photocurrent is made by excitons gen
erated both in the donor and in the acceptor.
DiketopyrrolopyrroleBased Acceptors
The possibility of diketopyrrolopyrrole (DPP) to
be an acceptor for an organic SC was indicated in [49].
Although some DPP derivatives showed high electron
mobility, the synthesized DPPbased acceptors made
it possible to obtain an organic SC with a low effi
ciency of <1.2% [32]. However, in a recent paper,
Y. Lin et al. synthesized siliconecontaining acceptor
A5 (Fig. 4) on the basis of DPP and dibenzosilole,
where dibenzosilole was applied to reduce the LUMO
and thus increase the electron affinity [50]. An organic
SC containing these acceptors mixed with P3HT (D1)
showed a maximum efficiency of 2.5% at a donor–
acceptor ratio of 1.2 : 1.0 after annealing at 120°C for
15 min. Furthermore, the sample possessed a rela
tively high opencircuit voltage of 0.97 V (see table,
Fig. 6b).
In another paper, starlike acceptor A11, based on
DPP and triphenylamine [51], was proposed. An
organic SC based on a mixture of starshaped acceptor
A11 and P3HT as a donor had a small efficiency of
1.2%, but quite a high opencircuit voltage for an
organic SC, 1.18 V (Fig. 6b).
EQE spectra of SCs with organic acceptors based
on DPP (A5 and A11) show a fairly broad plateau in
the range 300–700 nm with peaks at 470 nm and
shoulders at 400 and 600 nm; the shape of latter is sim

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

80 TRUKHANOV, PARASCHUK
EQE, %
(a)
60
40
A1
20 A2
A3
A4
0 A7
400 500 600 700
λ, nm
Fig. 7. Spectra of the external quantum efficiency of organic fullerenefree SCs: (a) perylenediimine derivatives A1–A4 and A7
and (b) other acceptors A5 and A8–A11.
ilar to the absorption peaks of acceptors A5 and A11.
This result suggests that excitons generated by the
absorption of light in the acceptor make a significant
contribution to the photocurrent.
In general, the acceptors based on DPP, despite
their low efficiency values, are interesting in terms of
achieving a high opencircuit voltage because they
have a fairly high energy level of the LUMO (χ ~
3.3 eV), while the opencircuit voltage is mainly deter
mined by the energy difference between the HOMO of
donor and the LUMO of acceptor.
Other NonFullerene Acceptors
One of the ways to improve the efficiency of organic
SCs is the use of highboiling additives (e.g., 1,8diio
dootane) to solutions applied for activelayer coating.
This method proved to be effective for SCs based on
P3HTPCBM and mixtures of polymers with narrow
band PCBM [52]. For organic SCs based on non
fullerene acceptors, the successful application of addi
tives to the component solution of an active layer was
demonstrated for naphthalenediimide acceptor A6
(Fig. 4) with P3HT [53]. With this approach, it was
possible to increase the efficiency of a P3HT–A6
based organic SC from 0.14 to 1.5% with the use of
1,8diiodootane as an additive. Between the electrodes
and the active layer of these photocells, there were
additional layers (P3HT and TBPI) that prevented the
transport of minority carriers. The mechanism of the
increase in efficiency is based on the fact that the solu
tion of the additive controls the size and provides con
tinuity to the acceptorphase domains in the active
layer. The optimal l,8diiodootane concentration in
the solution of activelayer components turned out to
be ~0.2 vol %, which is much lower than that for the
polymer–fullerene organic SCs (2–3%). The electron
and atomic force microscopy results showed that the
domain size of acceptor A6 increased sharply from the
EQE, %
(b)
50
40
A5
30 A8
A9
A10
20 A11
10
0
800 400 500 600 700 800
λ, nm
nanometer level at the optimum diiodooctane con
centration (0.2%) to the micrometer level at high con
centrations (higher than 0.5 vol %). The results show
the possibility of the application of additives to solu
tions of activelayer components to optimize mor
phology and improve the efficiency of organic SCs
with bulk heterojunctions based on nonfullerene
acceptors.
J.T. Bloking et al. proposed nonfullerene acceptor
A8 (Fig. 4) that contained electrondeficient vinylim
ide moieties attached to the benzothiadiazolyl frag
ment and that was applied for fabrication of a solar cell
with an efficiency of 2.54% [54]. Because the LUMO
level (χ ~ 3.3 eV) of acceptor A8 is higher than that of
PCBM, an extremely high opencircuit voltage was
obtained, 0.96 V (table, Fig. 6b). Moreover, this
acceptor has a high absorption rate: more than
105 M ⎯1 cm–1 [54]. The EQE spectrum (Fig. 7b)
showed that the contribution of the acceptor A8 phase
to the photocurrent was significant. The absorption
spectrum of the acceptor is shown in Fig. 5b.
One variety of promising nonfullerene acceptors is
fluorantenimide derivatives (Fig. 4, A9 and A10) [55,
56]. On the basis of a mixture of acceptor A9 and
P3HT, an organic SC with an efficiency of 1.86% was
fabricated via adjustment of the optimum donor–
acceptor ratio (1 : 2) and the annealing conditions of
the photocell (at 100°C for 10 min) [55]. Microscopy
studies revealed that the optimal domain size for donor
and acceptor phases was 10.7 nm, which was achieved
via slow evaporation of the solvent for preparation of
the active layer and subsequent thermal annealing.
The samples have fairly good stability: 3 months of
storage in darkness did not affect the efficiency, and
when they were illuminated for 10 h with a solarradi
ation simulator, the drop in efficiency was less than
10%. In addition, it was shown that the samples have
high thermal and chemical stability.
POLYMER SCIENCE Series C Vol. 56 No. 1 2014
 Characteristics of the best samples of organic solar cells based on nonfullerene acceptors

Donorto µe, Isc, Efficien Maximum Refe

Acceptor Donor L , nm Anode Cathode S, mm2 χ, eV V , V FF, %
acceptor ratio ас cm2/(V s) mA/cm2 oc cy, % EQE % rences

А1 D3 1:1 80 ITO Al 25 10–4 3.85 6.60 0.92 47 2.85 50 [39]

POLYMER SCIENCE
А2 D4 1 : 3.5 80–90 P:P ZnO/Al – 5.6 × 10–3 3.80 6.30 0.95 53 3.17 65 [40]

Series C
А3 D5 1:1 100 P:P Al 25 5.1 × 10–4 3.95 8.30 0.90 52 3.88 45 [41]

Vol. 56
А4 D6 1:1 110 P:P Ca/Al 13.5 1.7 × 10–4 – 7.40 0.78 52 3.0 40 [42]

No. 1
А5 D1 1.2 : 1 180–190 P:P Ca/Al 4 2.8 × 10–5 3.28 4.91 0.97 43 2.05 30 [50]

2014
А6 D1 1:1 70 P : P/P3HT TPBI/Al 4 – 4.10 3.51 0.82 52 1.5 – [53]

А7 D2 1:1 100 MoOx ZnO 14 8.0 × 10–3 4.06 7.90 0.76 46 2.77 40 [48]

А8 D1 1:1 – P:P LiF/Al – – 3.30 4.70 0.96 56 2.54 42 [54]

А9 D1 1:2 90–95 P:P LiF/Al 15 0.3 × 10–5 3.50 4.40 0.76 56 1.86 29 [55]
NONFULLERENE ACCEPTORS FOR ORGANIC SOLAR CELLS

А10 D1 1:1 – MoO3 ZnO – 0.9 × 10–5 3.44 6.35 0.95 48 2.90 48 [56]

А11 D1 1:1 – P:P Ca/Al – 6.8 × 10–6 3.26 2.68 1.18 38 1.20 16 [51]
81
82 TRUKHANOV, PARASCHUK
Further, the efficiency of organic SCs based on flu
orantheneimide acceptors was enhanced through
application of new substituents: phenyl (A10) instead
of thiophene (A9). The efficiency of SC samples with
bulk heterojunctions based on a mixture of P3HT with
the A10 was 2.90%. The authors suggested that this
result is related to the fact that acceptor A10 has a
higher electron mobility, μn = 0.9 × 10–5 cm2/(V s),
than that of acceptor A9, μn = 0.3 × 10–5 cm2/(V s)
[5B]. It is also possible that the increase in efficiency is
caused by the nonplanarity (similarly to the SC based
on nonplanar acceptor A7 [48]) of molecule A10: phe
nyl substituents are lying in the plane perpendicular to
the plane of most of the molecule. Nonplanarity of
acceptor molecules prevents crystallization; therefore,
a size reduction of the characteristic acceptor domain
can be achieved in a mixture at a level of ~10 nm.
After comparison of the absorption spectra of
acceptors A9 and A10 (Fig. 5b) with P3HT and the
EQE spectra of the organic SCs based on them
(Fig. 7b), it may be concluded that these acceptors sig
nificantly contribute to the photocurrent.
CONCLUSIONS
Significant progress has been seen in organic pho
tovoltaics over the last decade. The development of
new materials, mainly donor organic semiconductors,
has played a very important role in this field. A large
number of fullerene derivatives have been applied as
acceptors. However, studies into the development of
new nonfullerene acceptors are gaining momentum.
It ultimately has been assumed that these acceptors,
on the one hand, will possess all desirable properties of
fullerene acceptors, and on the other hand, will be free
from their drawbacks. This review has covered the
most successful nonfullerene acceptors that form the
basis for the fabrication of highefficiency organic
solar cells. The most efficient solar cells were those
based on perylenediimide derivatives (up to 4%).
However, the efficiency of the best organic solar cells
not containing fullerene is quite low in comparison to
that of fullereneacceptorbased photocells (more
than 10%). Various approaches to improve the effi
ciency of fullerenefree organic solar cells were pro
posed in the observed studies. The aim of most of them
was to achieve the optimum morphology of the
donor–acceptor mixture, e.g., via application of non
planar acceptor molecules, or supplying additives to
the solution of activelayer components, or thermal
annealing. Other approaches to improve operation
may be to increase the efficiency and expand the light
absorption spectrum, to improve electron mobility
and the LUMO level for a higher opencircuit voltage,
and to increase the length of exciton diffusion in
acceptor phase. A critical role will be played by a deep
understanding of the interaction between the donor
and acceptor forming the active layer and the ways to
create an optimum morphology of the active layer.
POLYMER SCIENCE
During the preparation of this review a report on the
creation of organic solar cell based on phtalocyanine
nonfullerene acceptor with PCE 8.4% was published
[57].
ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion of Basic Research (project no. 130312472OFI
m2).
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