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Cite this paper: Chin. J. Chem. 2021, 39, 381—390. DOI: 10.1002/cjoc.202000289

On the Understandings of Dielectric Constant and Its Impacts on

the Photovoltaic Efficiency in Organic Solar Cells
Zihao Fu,a Xuning Zhang,a Hong Zhang,b Yanxun Li,b Huiqiong Zhou,b and Yuan Zhang*,a
a
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, No. 37 Xueyuan Road, Beijing
100191, China
b
Key Laboratory of Nanosystem and Hierachical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience
and Technology, Beijing 100190, China

Keywords

Amorphous materials | Donor-acceptor systems | Energy conversion | Nanostructures | Photolysis

Abstract

Dielectric constant (ε) is an important parameter affecting

the power conversion efficiency of organic solar cells (OSC).
Increasing ε of bulk heterojunctions in general can benefit
the performance of OSCs, as an increased ε will reduce the
influence of Coulomb interaction between weakly bound
electron-hole pairs on charge-transfer states or bimolecular
recombination involving mobile carriers to reduce geminate
and nongeminate losses. In this review, we overview the
current understandings on dielectric constant and its im-
pacts on exciton dissociation and voltage losses in OSCs and
summarize recent efforts attempting to modify the dielec-
tric properties of OSC materials through synthetic ap-
proaches. We further discuss the commonly adopted tech-
niques for determining the parameter of ε with stressing the testing conditions that may affect the accuracy of results. At last, we
suggest that novel experimental methods to improve the dielectric constant and resultant physical processes in OSCs will be appreci-
ated, which helps enrich the existing strategy reservoir toward enhancement of photovoltaic efficiencies.

Zihao Fu (left) received his Bachelor degree from Northwestern Polytechnical University
in 2018. He is a master student under the supervision of Prof. Yuan Zhang in the School of
Chemistry at Beihang University, China. His research focuses on the device physics of high
efficiency organic solar cells.
Xuning Zhang (middle) received his Master degree from Xinjiang University in 2017. He is
currently a Ph.D. student under the supervision of Prof. Yuan Zhang in the School of
Chemistry at Beihang University, China. His research focuses on the device physics and
processing of high efficiency solar cells based on organic semiconductors and perovskites.
Yuan Zhang (right) received his Ph.D. in 2010 from the University of Groningen in the
Netherland under the supervision of Prof. Paul. W. M. Blom. His thesis focused on the molecular doping of conjugated polymers, aiming to understand
and improve their charge transport properties. He worked as a postdoctoral researcher (2011—2015) in the Center for Polymers and Organic Solids
(CPOS) at University of California, Santa Barbara, focusing on understanding charge transport and injection properties in molecular semiconduc-
tor-based photovoltaics and field-effect transistors. Currently, he is a professor at the School of Chemistry in Beihang University (China). His research
interests cover the topic of device and materials physics of photovoltaic cells based on organic semiconductors and halide perovskite materials.

*E-mail: yuanzhang@buaa.edu.cn View HTML Article

Chin. J. Chem. 2021, 39, 381－390 © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH 381
Recent Advances
Contents
1. Introduction
2. Discussion
2.1. Definition of dielectric constant
2.2. Benefits of high dielectric constants in OSCs
2.2.1. Charge generation and exciton binding energy
2.2.2. Reduced bimolecular recombination and
dielectric effect to increase VOC
2.2.3. Reduced energy loss in OSCs
2.3. Methods of increasing dielectric constants
2.3.1. Measurement of dielectric constant
2.3.2. Materials core modification
2.3.3. Side chain modification
2.4. Factors affecting the preciseness of dielectric
constant determination
2.4.1. Alternating current frequency
2.4.2. Direct current biasing
2.4.3. The effect of illumination
2.5. Future development of high dielectric constant OSC
materials
3. Conclusions and Perspectives
1. Introduction
Organic solar cells (OSCs), as one of the third-generation pho-
tovoltaic technologies, have the advantages of low cost, flexible
assembly, light weight, being foldable, and large-area processing
through R2R (roll-to-roll). Photovoltaic effect is defined as the
potential difference between different parts of the junction
caused by light. The first silicon solar device with a power conver-
sion efficiency (PCE) of 6% came out of Bell Scientific Research
[1]
Center In 1986. Tang et al. reported planar heterojunction solar
[2]
cells based on organic photo-absorbing materials. In 1994,
Heeger and Yu et al. proposed the smart concept of bulk hetero-
junction (BHJ) structure with which the photocurrents were ap-
preciably enhanced due to the enlargement of donor-acceptor
[3]
interfacial areas, leading to a PCE of 2.9%. The BHJ in solid state
is featured with three-dimensional interpenetrating networks,
where the electron and hole transport within the donor and ac-
ceptor domains, respectively. Since its invention, the BHJ has be-
come the dominant structure for OSC researches. Due to the de-
velopment of non-fullerene acceptors (NFA), the PCEs of OSCs
[4]
have exceeded 10% in the last couple of years, and recently PCE
[5]
over 17% was reported based on well-engineered NFAs. Despite
these accomplishments in OSCs, there are two main factors limit-
ing the commercial production of OSCs, namely the photoelectric
conversion efficiency and stability. There are tremendous efforts
on improving the PCEs of OSCs in the perspective of new materi-
[6] [7]
als synthesis, energy level alignment, morphology optimiza-
[8] [9]
tion, device architecture engineering, and interface modifica-
[10]
tion. In addition to these approaches, the attempts on modify-
ing the dielectric constant of donors or acceptors to realize en-
[11]
hanced photovoltaic efficiencies have been made.
Due to the presence of the dominant carbon atoms (with light
heteroatoms), weak intermolecular coupling (or dipoles) with
disorder nature, most organic semiconductor materials have a low
relative dielectric constant (εr < 6), which is a critical limiting fac-
tor for exciton dissociation and charge separation in OSCs. Gener-
ally speaking, increasing the εr of the semiconductor can lower
the exciton binding energy (Eb) and reduce geminate recombina-
[12]
tion losses, thereby it is beneficial to the overall device per-
formance in OSCs. In addition, the increase in the dielectric con-
stant reduces the encounter probability between separated holes
[13]
and electrons, due to the decrease of coulombic radius, which
is favorable for the mitigation on bimolecular recombination, a
382 www.cjc.wiley-vch.de © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Fu et al.
[14]
dominant loss pathway in OSCs. Given the relevance of εr to
some of the essential physical processes in operating OSCs, there
382 have been a handful of documented studies focusing on increas-
382 ing the dielectric constant in the polymer donors or small molec-
382 [15]
ular acceptors, aiming to obtain modified photovoltaic charac-
383 teristics and improvement on PCEs.
[16]
383 This review is organized as follows: we will first provide the
general concept of dielectric constant and elaborate its impacts
383 on the properties of charge generation and voltage loss in OSCs.
384 We will turn to discuss representative synthetic approaches used
384 to increase the dielectric constant of OSC materials and correlate
384 these modifications to device efficiencies. Then, we will discuss
385 the commonly adopted experimental techniques for determina-
386 tion of εr with focus on the factors affecting the measurement
accuracy. At last, outlook on the potentials with increased dielec-
386 tric constant for OSCs with non-fullerene acceptors will be pro-
387 vided.
387
387
2. Discussion
387
388 2.1. Definition of dielectric constant
Dielectric constant is a dimensionless factor, usually expressed
as ε, which is always relative to the vacuum dielectric constant (ε0
‒12 [17]
= 8.854×10 F/m ). The response of a material medium to the
electric field can be described by the dielectric constant, which is
derived from the molecular polarization of different types and
different time scales. If the time required to apply the electric
field is shorter than the polarization response time required for
the material, it will not affect the capacitive response of the entire
material. Therefore, materials with high dielectric constants are
more resistant to electric fields than materials with low dielectric
constants. The term “dielectric constant” for organic semicon-
ductors generally refers to the static dielectric constant that is
based on an assumption that ε can remain approximately a con-
stant for a given frequency range until the frequency is very high,
which then corresponds to the optical dielectric constant equaling
the square of refractive index. In reality, due to the different po-
larization mechanisms, the dielectric constant of a material can
exhibit a frequency-dependence (see detailed discussion in Sec-
tion 2.4). In this review, we mainly focus on discussing the static
dielectric constant that is relevant to the electronic behaviors in
OSCs. As known, the dielectric constant in organic semiconductors
6 [18]
is low. For comparison, the εr of silicon 12.1 at 10 Hz, while
low values of 2—5 are generally found in organic semiconduc-
tors.
[19-20]
The low dielectric constant of organic semiconductors
can lead to the formation of polarons and Frenkel excitons, re-
sulting in high exciton binding energies from several hundred of
[21]
meV to 1.4 eV. Compared with materials with high dielectric
[22]
constants (e.g., Si or halide perovskites ), the low dielectric con-
stants in organic semiconductors can enhance the Coulomb inter-
action between holes and electrons, thereby increasing the at-
traction and repulsion effects. The dielectric constant plays an
important role in the performance of OSCs. In a photovoltaic de-
vice, the absorbed photons create excitons that are dissociated at
the donor-acceptor interface. The resultant electron-hole pairs
that are coulombically bound (on charge transfer-states or
CT-states) need to be further separated into mobile carriers. With
the assistance of internal electric field, the mobile carriers are
transported toward the electrodes, yielding the photocurrent.
Meanwhile, the generation of charges can lead to the splitting of
quasi-Fermi levels in the donor and acceptor, resulting in a pho-
tovoltage. In these processes, the coulomb interactions deter-
mined by the dielectric constant negatively affect charge separa-
tion and prompt charge recombination. Therefore, increase of the
dielectric constant of BHJs is generally preferred for OSCs with the
[23]
key merits summarized by Koster et al., such as (1) it reduces
Chin. J. Chem. 2021, 39, 381－390
Dielectric Constant and Its Impacts on the Photovoltaic Efficiency
bimolecular recombination; (2) it reduces the reorganization en-
ergy, thereby allowing fast interfacial charge transfer under small-
er energy offsets, according to Marcus theory; (3) it reduces the
exciton binding energy, which is favorable for exciton dissociation
at the donor and acceptor interface; (4) it reduces the Coulomb
attraction between CT excitons, facilitating the dissociation of
weakly bound electron-hole pairs into mobile carriers; (5) it re-
duces the Coulomb attraction between mobile carriers due to the
increase of screening effect, which helps reduce non-geminate
recombination. Although the general merits of a higher dielectric
constant are acknowledged, at least with a theoretical perspective,
how it affects functional OSC devices is yet incompletely under-
stood. In fact, there are some inconsistencies in previous studies
[24]
on the role of dielectric constant, from which unhelpful infor-
mation is provided. In this review, we hope that the discussed
fundamentals of dielectric properties could provide useful infor-
mation relevant to the current understandings on the role of εr in
OSCs and experimental approaches for mediation of this im-
portant parameter.
2.2. Benefits of high dielectric constants in OSCs
The benefits of increasing dielectric constants of BHJs have
[11]
been theoretically evidenced. A meaningful prediction on the
merits of using high εr BHJ absorbers can be seen from the simu-
lations of experimentally obtained current-voltage characteristics
of fullerene solar cells based on a drift-diffusion model. Through
increasing the εr, the simulation results indicated that enlarge-
ment of εr could beneficially reduce the reorganization energy of
CT-states, thus allowing for efficient interfacial charge transfer
[25]
under a small ΔEoff, according to Marcus theory. Moreover, the
biomolecular recombination rate could be favorably reduced with
enlarged εr, due to the reduced coulomb interaction between
mobile carriers. With these theoretical insights, some implications
can be obtained: 1) Charge generation can be further promoted in
low-offset BHJ-OSCs if εr increases; 2) the tradeoff of voltage loss
with regard to charge generation can be further mitigated, as
reducing ΔEoff favors the reduction of radiative and non-radiative
[26]
recombination losses for VOC; 3) the reduced bimolecular re-
combination rate due to the increased εr will reduce the depend-
[64]
ence of photocurrent on bias when the electric field is low, thus
facilitating charge extraction and the increase of fill factor (FF) in
OSCs.
2.2.1. Charge generation and exciton binding energy. OSCs
typically use the bulk heterojunction (BHJ) structure in which an
electron donor D (e.g., conjugated polymers or small molecule
semiconductors) and an electron acceptor A (e.g., fullerenes,
non-fullerene small molecule acceptors, or polymeric acceptors)
[27]
are mixed with nanoscale phase separation. The key reason to
adopt BHJ structure instead of single-components (e.g., perov-
skite solar cells) is the required exciton dissociation that cannot
efficiently occur in a single layer of neat donor or acceptor, due to
the small dielectric constant of organic BHJs (typically of 3—4) and
[28]
resultant high exciton binding energy. In a BHJ, the energy off-
sets ΔEoff (between the HOMO and LUMO of D/A) provide the
driving force for excitons to be dissociated at the D/A interface. In
principle, this driving force (energetic offset) needs to be compa-
rable to the exciton binding energy, otherwise severe exciton re-
combination will be encountered, causing increased geminate
[29]
losses. The required ΔEoff for charge generation inevitably in-
duces a tradeoff between charge generation and VOC, a major
[30]
barrier for the improvement of PCE. Due to the interaction
between D and A, charge transfer states are formed, namely the
[31]
weakly bound electron-hole pairs (or CT excitons). CT states can
either dissociate into mobile carriers or decay to the ground states
via radiative or nonradiative pathways. In these competitions, the
dissociation of CT-states, that are critically affected by the attrac-
tion between weakly bound electron-hole pairs, plays a vital role
Chin. J. Chem. 2021, 39, 381－390 © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem.
in charge generation and ultimate PCE of OSCs. Generally speak-
ing, the exciton binding energy Eb is sensitive to the dielectric
[32]
constant. Taking the case of exciton binding energy of CT-states,
[33]
which follows the relation,
𝑞2
𝐸bCT = (1)
4π𝜀0 𝜀𝑟 𝑟
(here q is the elementary charge, r is the separation distance be-
tween the electron-hole pair), increasing εr will reduce the bind-
[34]
ing energy of CT excitons, provided that r is unchanged. Given
the low values of εr in organic semiconductors, one expects for-
mation of Frenkel excitons with a large exciton binding energies
(hundreds of meV) upon photoexcitation. By taking a modified
Onsager theory where the electron-hole pair dissociation takes
place when random energetic disorder (here taking an estimate of
100 meV) equals the Coulomb energy, the Coulomb capture radi-
us is 4.8 nm with an εr of 3. Favorably, the capture radius can re-
duce down to 1.4 nm when εr increases to 10, meaning that at-
traction between the electron-hole pair weakens. In this context,
the dissociation probability P(E) is predicted to increase over two
[35]
orders of magnitude when εr increases from 3 to 10, suggesting
more efficient charge separation.
As discussed above, due to the energy offset, an efficiency up
[23]
to 10% is expected with ΔEoff of 0.4 eV for fullerene solar cells.
It is interesting that in some recently reported NFA-BHJ systems,
efficient interfacial charge transfer has been observed under a low
[64]
or even zero ΔEoff. This seems to indicate that there are addi-
tional energy sources for the dissociation of excitons, the mecha-
[37]
nisms of which are currently under active discussion. We advise
the readers to bear in mind that despite the relatively fast intrinsic
charge transfer (sub-picoseconds) observed in some low offset
[38]
NFA-OSCs, whether the dielectric constant plays a role in the
whole processes of charge generation and resultant high efficien-
cies is yet incompletely understood. Also, full correlations of the
modified Eb in NFA-OSCs with increased εr to device performance
are yet lacking, despite the theoretical prediction that points to a
[39]
reduced Eb at larger εr. To some degree, the gap between the
theoretical and experimental studies can be related to the associ-
ated changes in morphology or transport properties with the
[37]
modified dielectric constant, which complicates our under-
standings.
2.2.2. Reduced bimolecular recombination and dielectric ef-
fect to increase VOC. Large Coulomb attraction force between the
electron and hole pairs (geminate or non-geminate) leads to
[41]
strong recombination, e.g., via bimolecular and trap-assisted
[42]
recombination pathways. Bimolecular recombination is rela-
tively strong in OSCs, compared to inorganic or hybrid perovskite
[43]
solar cells, acting the primary loss mechanism. Thus, reducing
the attraction between mobile carriers is preferred in OSCs. The
carrier loss due to recombination has been directly correlated to
the reduced fill factor (FF) and open circuit voltage (VOC) in OSCs,
[44]
especially when thick active layers are used.
The increased bimolecular recombination loss near VOC will
reduce the number of extracted carriers and negatively affect
Fermi level splitting, thus lowering the VOC. As shown in Figure 1, a
high rate of bimolecular recombination is the primary source of
energy loss in all types of OSCs. The VOC can be improved by re-
ducing bimolecular recombination. Increasing the high frequency
dielectric constant has been found helpful for decreasing the re-
duction factor (denoted as γ) for bimolecular recombination at
[23]
open-circuit, and is now emerging as a popular strategy for
[41]
increasing VOC. While a conclusive model describing how the
dielectric constant affects the VOC and PCE is yet to be fully elabo-
rated, increasing εr is at least expected to be beneficial for reduc-
ing the voltage loss. This correlation is elegantly observed in a
previous study where the authors plotted Vrec (the voltage loss
determined by the balance between generation and recombina-
www.cjc.wiley-vch.de 383
Recent Advances
tion rates at VOC) versus εr (see Figure 2a and ref [41]), where a
[41]
linear best fit to the data yields a slope of –0.088 V. The result
suggests that VOC loss could be modulated within a relatively wide
range upon changing εr, enabling to increase the VOC by ~0.1 V.
Interestingly, an exponential decrease of the bimolecular recom-
bination coefficient γ with increased εr was observed (see Figure
2b). This trend implies that a reduction of bimolecular recombina-
tion strength could be afforded by using higher εr OSC materials.
Figure 1 Schematic diagram to illustrate bimolecular dynamics repre-
senting the relationships among the dielectric constant, exciton binding
energy and charge recombination. Picture taken from ref [45].
Figure 2 (a) Vrec plotted versus dielectric constant εr with linear best fits
(slope = –0.088 V). (b) Recombination rate γ plotted versus εr with expo-
nential fit to guide the eye. The largest deviation from the fit occurs for
DTS:PC71BM without DIO, for which, unlike all other systems, the mor-
phology was not optimized through annealing or additive processing.
Figures taken from ref [41].
Cho et al. observed a similar trend that the voltage loss re-
duces when increasing εr of the donor polymer from 3.9 to 5
[45]
through addition of polar side chains. In bilayer OSCs, an 80 mV
increase of VOC was obtained with an increased εr, which was at-
tributed to the significant increase in carrier lifetime. One may
also anticipate that altering the strength and direction of dipoles
at the interface between the donor and the acceptor could signif-
[46]
icantly change the VOC. In addition to the impact bimolecular
recombination on voltage loss, dielectric effect has been clarified
as a major loss mechanism for VOC. A promising finding is envis-
aged that the VOC loss due to dielectric effect could be eliminated
with increasing the dielectric constant to 5. This enables to widen
the optimization window for VOC, in addition to the commonly
used energy level tuning.
2.2.3. Reduced energy loss in OSCs. In additional to the loss
due to carrier recombination, an additional possible photovoltage
loss is related to the extra energy used to separate the electron-
hole pairs in organic semiconductor characteristic of the inher-
ently low dielectric constants.
384 www.cjc.wiley-vch.de © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Fu et al.
[47]
Chen et al. showed the first experimental evidence on the
dependence of dielectric constants on energy losses Δ(eV) in OSCs.
The physical origin for the ΔV is interpreted by the relation Δ(eV) =
Eeff – qVOC (Eeff is the effective bandgap) with eVoc = eEeff–Eε +
kTln(np/NvNc). Obviously, Δ(eV) consists of two loss parts, includ-
ing the chemical potential energy loss to carrier recombination
(kTln(np/NvNc)) and the electric potential energy loss due to die-
lectric effect (Eε). Eε is indeed a function of the dielectric constant
of different polymers and fullerene BHJ systems, which indicates
that the loss is due to Coulomb interaction. It could be speculated
that the overall VOC loss is dependent on the dielectric properties.
It is worth noting that the VOC loss due to the dielectric effect is
larger than 0.3 V for systems with a small dielectric constant like
[24]
PCDTBT:PC71BM. While for systems as PDTS-iI:PC71BM which
has a larger dielectric constant (close to 5), the loss almost com-
[47]
pletely vanishes (see Figure 3).
Figure 3 (a) Potential energy loss Δ(eV) (= Eeff – qVOC) plotted as a func-
tion of dielectric constants. (b) Energy loss to dielectric effects Eε (=
Δ(eV)+kTln(np/NcNv)) plotted as a function of inverse order of dielectric
constants. The approximation of DOS values is not reflected in the error
bars. (c) Chemical structures of materials used in ref [47]. The seven pol-
ymers were blended with PC71BM individually to form bulk heterojunction
cells. Figures taken from ref [47].
2.3. Methods of increasing dielectric constants
Qualification of dielectric constant values is the basis for tun-
ing this parameter through chemical approaches. Among the vari-
ety of adopted test methods for εr, the widely used method is
based on the parallel-plate-capacitance measurement with im-
pedance spectroscopy. Regarding the modification of εr, many
groups are attempting different approaches to increase the die-
lectric constant in organic semiconductors without affecting other
[48-51]
opto-electrical properties, such as materials core modifica-
tion and side chain modification, which will be discussed in fol-
lows.
2.3.1. Measurement of dielectric constant. Parallel-plate-
capacitance measurement with impedance spectroscopy is a sim-
Chin. J. Chem. 2021, 39, 381－390
Dielectric Constant and Its Impacts on the Photovoltaic Efficiency Chin. J. Chem.

[52]
ple and efficient method. The material sandwiched between
two metallic parallel electrodes is subject to a small perturbation
of low amplitude AC signal with sweeping 0.1—1 MHz usually
from MHz range down to tenths of Hz. From the obtained imped-
ance response value, the capacitance value can be obtained by
[52]
the following formula,
1 −𝑍′′ −𝑍′
𝐶= = +𝑖 (2)
𝑖𝜔𝑍𝛼 𝜔|𝑍|2 𝜔|𝑍|2

where ω is the angular frequency, 𝑖 2 = −1 and 𝑍 𝛼 is defined as

the impedance complex function indicating impedance value at a
particular frequency. The equation for the dielectric constant is
given by,
𝐶(𝜔)
𝜀𝑟 (𝜔) = = 𝜀r ′ − 𝑖𝜀r ′′ (3)
𝐶0

where C0 is the capacitance of the empty capacitor, given by C0 =

–12
ε0A/d withε0 ≈ 8.854×10 F/m, A is the area of the materials
sandwiched between the electrodes and d is the thickness. In
Equation 2, the real part corresponds to the relative dielectric
constant εr of tested materials, and the imaginary part includes
loss mechanisms such as conductance and relaxation processes. It
should be noted that the capacitive response is not only related to
[53]
the dielectric properties of the body. In some semiconductors,
due to a specific electrical conductivity, accurately determining εr
[52]
will require extra carefulness.
Impedance analysis is used to measure the dielectric constant
through applying an AC electric field with varied frequencies to
the device to determine the resistance. In Equation 3, the real
part of the impedance is denoted as Z’, and the reactance, namely
the imaginary part of the impedance is denoted as Z’’. After cor-
rections of the series resistance Rs (≈10 Ω) and system inductance
L (≈ 6 μH) of the tested device, the capacitance (Ccor) is calculated
from the measured impedance spectrum according to the rela-
tion,
1 𝑍′′ −𝜔
𝐶 r = − [(𝑍′ )2 (𝑍′′ −𝜔 )2
] (4)
𝜔 −
Figure 4 (a) Synthesis route for FTQ. (b) Photovoltaic J-V curves of
TQ:PCBM and FTQ:PCBM devices (1 : 3 w/w) under the illumination of AM
1.5 G (100 mW/cm2). Figures taken from ref [56].
The strategy of core-modification via fluorination has been
[61]
applied to other material systems. For example, Xu et al. syn-
thesized five types of fluorinated NDI polymeric acceptors and
found that among the fluorinated polymers, the devices based on
the acceptors with higher dielectric constants yielded JSC and FF
and fill factors that are considerably higher than those with lower
[57]
dielectric constants. Jia et al. reported the results of changing
the degree of fluorination on the PT backbone (see Figure 5) and
according photovoltaic properties of those based on the final
products (P6T-F00, P6T-F50, P6T-F75, and P6T-F100). They found
that the dielectric constant increased with increasing degree of
fluorination and meanwhile the degree of crystallinity, absorption
coefficient, hole mobility could be enhanced.

where 𝜔 is the angular frequency as, ω = 2πf, and f is the fre-

quency. Frequency-independent geometric capacitance is deter-
mined by impedance measurements in the dark with a large re-
verse bias (e.g., –1.5 V) on a diode device that exhibits high shunt
resistance. Based on the relation,
𝐶g 𝑑
𝜀= (5)
𝜀0 𝐴

where Cg is the geometric capacitance, d is the film thickness, A is

[24]
the device area, Hughes et al. have identified frequency-inde-
1 6
pendent impedance values in the frequency range of 10 —10 Hz
for OSCs. The results help elucidate the timescale relevant to free
charge carrier lifetime in organic semiconductors.
2.3.2. Materials core modification. Böttcher et al. has pro-
posed an effective method for enhancing the dielectric constant
[55]
via reformation on the materials core. It was found that adding
polar groups to the materials core could improve the dielectric
constant. Baring the similar concept, Lu et al. utilized a fluorine Figure 5 (a) Chemical structure of newly developed P6T-Fx polymers. (b)
substituted thiophene-quinoxaline copolymer to synthesize novel Dielectric constant and exciton binding energy of newly developed P6T-Fx
[56]
materials FTQ (see Figure 4), which shows a better perfor- polymers. (c) JSC, FF and PCE as a function of fluorination degree of the
mance in OSCs than those based on non-fluorinated TQ. The P6T-Fx polymers. Pictures taken from ref [57].
fluorinated FTQ not only has a deeper-lying HOMO energy of
–5.51 eV (compared to the HOMO of TQ at –5.36 eV), but favora- In addition to increasing the degree of fluorination of the ma-
bly presents a larger dielectric constant (εr = 5.5) than that in TQ terial, adding cyano groups to the main chain tends to be an ef-
(εr = 4.2). As a result, the FTQ/PCBM based OSC outperforms the fective route for the increase of dielectric constant. It is based on
[58-59]
one based on TQ/PCBM, showing an enlarged Voc (from 870 mV the consideration of the large dipole moment of cyano groups.
[60]
to 932 mV) and PCE that is 25% higher than that in the TQ/PCBM As an example, Zhang et al. substituted the cyano group for the
devices. hydrogen group in PB3T-C66 to obtain PB3TCN-C66, and found

Chin. J. Chem. 2021, 39, 381－390 © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH www.cjc.wiley-vch.de 385
Recent Advances Fu et al.

that B3T-C66 and PB3T-C66:IT-4F blends exhibited εr of 2.75 and citon dissociation, non-geminate charge recombination (e.g., bi-
2.54 at 1 kHz, respectively. In comparison, the cyano-group based molecular) and eventual photovoltaic behaviors are yet to be clar-
PB3TCN-C66 donor and its blends with IT-4F acceptor exhibited ified, which will call for further investigations.
higher values of εr of 4.31 and 3.60 at the same frequency. The
increased FF and JSC that led to a PCE of 11.2% (see Figure 6),
compared to the PCE of 2.3% with low dielectric constant blends
PB3T-C66:IT-4F was attributed to the reduced exciton binding
energy that promotes exciton separation and reduces geminate
and nongeminate recombination. However, it should be noted
that while the efficiency improvements are connected to the
modified cores in the donor or acceptor molecules possessing
larger dielectric constants, core modification in some cases con-
currently changes the materials energy level, which may generate
unpredictable or even negative impacts on the materials proper-
ties and eventual device performance.

Figure 7 (a) Chemical structure of the acceptors (ITIC and ITIC-OE) and
the polymer donor (PBDB-T). (b) Determined relative dielectric constants
of ITIC-OE, ITIC, and PBDB-T at different frequencies. Pictures taken from
ref [11].

Figure 6 (a) Synthesis routes for PB3T-C66 and PB3TCN-C66. (b) J-V
curves of the optimized polymer:IT-4F solar cells. Pictures taken from ref
[60].

2.3.3. Side chain modification. Compared to the modification

of the material core, adding a polar group to a side chain instead
of the core tends to be more controllable for the dielectric con-
stant. Liu et al. reported the synthesis of a new non-fullerene
accepter with oligoethylene oxide containing side chains (ITIC-OE)
[11]
(see Figure 7). The resultant compound displays a high dielec-
[32]
tric constant value of 9.5. Jahani et al. reported a side-chain
modification for fullerene derivatives via introducing the triethy-
lene glycol monoethyl ether (TEG) side chains, with which the
dielectric constant increased by 46% (see Figure 8). Differing the
core-modification discussed earlier, the utilization of TEG side
chains merely affects the optical properties, electron mobility and
energy levels. Other successful examples in improving dielectric
[63]
constants can refer to the study by Hughes et al, where εr in-
creases from 3.00 to 3.84. Cho et al. found another way to in- Figure 8 (a) Chemical structures of PTEG-1, PTEG-2 and PP. (b) Dielectric
crease the dielectric constant, afforded by introducing a cyano constant versus frequency at room temperature of PTEG-1, PTEG-2 and PP.
[64] Pictures taken from ref [32].
moiety to the side chains. These results have demonstrated the
viability of side-chain modification for increasing the dielectric
constant in conjugated molecules. However, how to increase the 2.4. Factors affecting the preciseness of dielectric constant
dielectric constant while maintaining other favored properties is determination
still of challenge. In the perspective of device performance in In the measurement for dielectric constants of organic semi-
OSCs, the exact correlations among the dielectric constant, ex- conductors, there are some factors that are needed to be taken in

386 www.cjc.wiley-vch.de © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH Chin. J. Chem. 2021, 39, 381－390
Dielectric Constant and Its Impacts on the Photovoltaic Efficiency
account to warrant the accuracy of results. Representative factors
may include the AC frequency, DC bias, illumination, choice of
contacts, and device quality (e.g., shunt resistance), etc. To assure
the reliability of capacitive measurements for ε, an independent
measurement, e.g., by using ellipsometry is often carried out to
confirm the results. In the case of BHJ films where the donor and
acceptor coexist, there are many factors that can affect the accu-
racy of determined εr. As an example, we have evaluated the die-
lectric properties of two representative blended films (see Figure
9a). The results indicate that the values of εr in the compared
blends slightly vary with the applied frequency of AC perturbation
signals. In order to verify if these results truly reflect the differ-
ence of εr between the studied materials, elliptical polarization
spectroscopy was performed, which shows consistent tendencies
in the change of dielectric constants (see Figure 9b). Here, care
needs to be taken for the measurements with ellipsometry as the
surface smoothness critically affects the results and data inter-
[64]
pretation.
Figure 9 (a) Relative dielectric constant of BHJs films containing IT-4F
and ITIC acceptors measured at different frequencies. (b) Extracted εr of
thin films based on the same BHJs and neat accepter materials as a func-
tion of light wavelength using ellipsometry method. Pictures taken from
ref [64].
2.4.1. Alternating current frequency. Impedance spectrosco-
py (IS) is a sensitive technique, which can be performed in batches
with capturing multiple processes. However, the issue of decon-
[65]
volution should be concerned. In a typical measurement pro-
cess with IS, the response of the sample gradually accumulates
with the change in the frequency of applied AC fields: at low fre-
quencies, the impedance analyzer will collect all the signals that
increase with frequency; however, some contributing species will
not be able to make changes to the field. Fast enough responses
essentially freeze their response and their contribution will be
ignored. In order to obtain the true and reliable dielectric con-
stant of the material, it is necessary to understand the polariza-
tion contributing to the overall capacitance and to “mute” those
unwanted polarizations. In low frequency domains, the polariza-
tion could be affected by ionic conduction or injection of charge
carriers, both of which cannot describe the intrinsic response of
the material to the field. For this reason, it is preferable that the
measurement of the dielectric constant of organic materials is
5 6
carried out in the high frequency regimes, e.g., between 10 —10
Chin. J. Chem. 2021, 39, 381－390 © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem.
[62]
Hz. At the same time, great cares are needed to exclude the
impact of existing background or injected charge carriers in the
device.
2.4.2. Direct current biasing. Impedance measurements for
OSC materials can be highly sensitive to DC bias and thus the in-
fluence of DC bias needs to consider. If there is an ohmic contact
in the semiconductor film, the DC bias applied on the film may
sensitively affect the density of charge carriers due to charge in-
jection. As the bias on the electrodes increases, more charge car-
riers will diffuse from the contacts into the semiconductor layer
and the device is getting more far away from behaving a capacitor.
In this scenario, the injected charge carriers from the contacts can
complicate the characteristics measured by impedance spectros-
copy, which may cause deviations in the determined relative die-
lectric constant from true values. To increase the accuracy, an
appropriate DC bias should be adopted to minimize the impact of
injected carriers in the device, which is emphasized in a recent
[63]
study by Nguyen group.
2.4.3. The effect of illumination. In high-performance OSCs
based on donor:acceptor blends, light excitation is more sensitive
to generation of charge carriers. Therefore, the presence of light
can introduce additional capacitance into the impedance meas-
urement and cause deviations in results. In order to eliminate the
impacts of light, it will be necessary to perform impedance meas-
urements in dark. As an example, the capacitance in the
P3HT:PC61BM blends was found to increase by 64% at 1 kHz under
2
1 sun illumination (100 mw/cm ) and by 26% under 0.25 sun illu-
[63]
mination, as shown in Figure 10. Note that the artificial effects
by illumination tend to be reduced in pristine materials, due to
the reduced efficiency to generate free charges under irradiation.
Figure 10 Influence of light on the capacitance of (a) pristine P3HT and
(b) P3HT:PC61BM blend. Picture taken from ref [63].
2.5. Future development of high dielectric constant OSC
materials
While the smart synthesis has led to donor and acceptor ma-
terials with high dielectric constants, the increase of εr is accom-
panied by the sacrifice of other important properties such as
crystallinity, microstructure, phase separation, recombination,
reduced hole/electron mobilities. As an example, Reynolds and
coauthors introduced polar cyan groups to the end of DTS-TPD
polymer side chains. Although the introduction of cyan groups
increases the dielectric constant of the polymer, a poor JSC was
observed in OSCs, due to the higher energetic disorder in hole
[66]
transport which limits the enhancement of device performance.
Recently, Nguyen and coworkers reported the effect of increasing
www.cjc.wiley-vch.de 387
Recent Advances
dielectric constant on charge recombination and they found that
the minor change (increase) of dielectric constant cannot be at-
tributed to the considerably reduced charge trapping sites or
[63]
modification of relevant physical processes. These efforts sug-
gest that seeking new methods that can effectively increase the
dielectric constant in OSC materials without sacrificing other ben-
eficial properties, e.g., the morphology, is highly important for
obtaining further improvement of efficiencies.
The relevance of dielectric constant to the OSCs performance
[45]
has been revisited for BHJs with NFAs recently. Through intro-
ducing polar side chains oligoethylene oxide (OE) to replace alkyl
side chains of ITIC NFAs, the modified acceptor ITIC-OE upon
blending the polymer donor PBDBT can deliver a PCE of 8.5%,
which is the highest value for NF-OSCs employing high dielectric
constants materials. However, the efficiency is still lower than the
reference cell based on the low-dielectric constant ITIC accep-
[67]
tor. The results were explained by the over-large phase separa-
tion to hamper the exciton diffusion and charge generation. These
negative factors need to be considered in the future design of
high dielectric constant OSC materials. Also, further investigations
are still needed to elaborate the correlation of εr and dissociation
of CT-states in OSCs. We anticipate that through rational materials
design and device engineering, the merits of large dielectric con-
stant may be translated into the boost of PCEs in low energy off-
set NF-OSCs, given that the reduction of Eb with high εr promotes
interfacial exciton dissociation (in low-offset BHJs) and elongates
the CT-exciton lifetime. All these predictions on the modified
processes are essential for the gains of photon-harvesting effi-
ciency. Given the dielectric effect for the VOC loss discussed above,
the correlations of dielectric properties and voltage loss in
NF-OSCs are to be better understood, especially in low-offset
NF-OSCs. With these efforts, new improvement strategies for
reducing the voltage loss in OSCs could be informed.
Regarding the currently existing approaching for regulating
the dielectric constant of OSCs materials via the introduction of
polar groups, efforts can be directed toward approaches for how
to increase εr with maintaining the favored morphology, e.g., the
appropriate phase separation and satisfactory charge transport
properties. In this perspective, further exploration on structural
modification for donor and acceptor materials with new polar
functional groups could be helpful.
3. Conclusions and Perspectives
In this review, we have overviewed the significance of dielec-
tric constants of organic bulk heterojunctions for the photovoltaic
performance in OSCs. We discussed how the increase of dielectric
constant could benefit the processes of exciton dissociation, sup-
pression of bimolecular recombination loss and gains of photo-
current and photovoltage in OSCs in a theoretical perspective. We
have linked these potential merits to some of the experimental
efforts aimed to increase the dielectric constant toward greater
photovoltaic efficiencies. We further summarized principles of
commonly adopted testing methods for determining the dielectric
constant with capacitive measurements and highlighted the fac-
tors that could affect the accuracy of results. Existing synthetic
approaches based on core and side chain modification targeted
for reaching larger dielectric constants were also discussed. Fu-
ture efforts were advised on better understanding the correla-
tions of dielectric properties with voltage losses and charge gen-
eration processes in non-fullerene OSCs, which may allow for ex-
panding the optimization windows toward high-efficiency NF-OSCs.
Acknowledgement
This work was supported by the National Natural Science
388 www.cjc.wiley-vch.de © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Fu et al.
Foundation of China (Nos. 21875012, 21674006).
References
[1] Green, M. A.; Emery, K.; Hishikawa, Y.; Warta, W.; Dunlop, E. D. Pro-
gress in Photovoltaics: Research and Applications. Solar Cell Efficien-
cy Tables 2013, 41, 1–11.
[2] Tang, C. W. Two-layer Organic Photovoltaic Cell. Appl. Phys. Lett.
1986, 48, 183–185.
[3] Yu, G.; Pakbaz, K.; Heeger, A. J. Semiconducting Polymer Diodes:
Large Size, Low Cost Photodetectors with Excellent Visible-ultraviolet
Sensitivity. Appl. Phys. Lett. 1994, 64, 3422.
[4] Zhang, D.-Y.; Wang, J.-Q.; Zhang, X.-N.; Zhou, J.-Y.; Zafar, S.-U.; Zhou,
H.-Q.; Zhang, Y. Sequential Molecular Doping of Non-fullerene Or-
ganic Solar Cells without Hole Transport Layers. J. Mater. Chem. C
2020, 8, 158–164.
[5] Zhang, S.; Qin, Y.; Zhu, J.; Hou, J. Over 14% Efficiency in Polymer So-
lar Cells Enabled by a Chlorinated Polymer Donor. Adv. Mater. 2018,
30, 1880868.
[6] Yuan, J.; Zhang, Y.-Q.; Zhou, L.-Y.; Zhang, G.-C.; Yip, H.-L.; Lau, T.-k.;
Lu, X.-H.; Zhu, C.; Peng, H.-J.; Jonhnson, P. A.; Leclerc, M.; Cao, Y.;
Ulanski, J.; Li, Y.-F.; Zou, Y.-P. Single-Junction Organic Solar Cell with
over 15% Efficiency Using Fused-Ring Acceptor with Electron-Defi-
cient Core. Joule 2019, 3, 1140–1151.
[7] Li, S.-X.; Zhan, L.-L.; Sun, C.-K.; Zhu, H. M.; Zhou, G.-Q.; Yang, W.-T.;
Shi, M.-M.; Li, C.-Z.; Hou, J.-H.; Li, Y.-F.; Chen, H.-Z. Highly Efficient
Fullerene-Free Organic Solar Cells Operate at Near Zero Highest Oc-
cupied Molecular Orbital Offsets. J. Am. Chem. Soc. 2019, 141, 3073–
3082.
[8] Zhou, R.-M.; Jiang, Z.-Y.; Yang, C.; Yu, J.-W.; Feng, J.-R.; Adil, M. A.;
Deng, D.; Zou, W.-J.; Zhang, J.-Q.; Lu, K.; Ma, W.; Gao, F.; Wei, Z.-X.
All-small-molecule Organic Solar Cells with over 14% Efficiency by
Optimizing Hierarchical Morphologies. Nat. Commun. 2019, 10,
5393.
[9] Rasi, D. D. C.; Janssen, R. A. J. Advances in Solution-Processed Mul-
tijunction Organic Solar Cells. Adv. Mater. 2019, 31, 1806499.
[10] Zheng, Z.; Hu, Q.; Zhang, S.-Q.; Zhang, D.-Y.; Wang, J.-Q.; Xie, S.-K.;
Wang, R.; Qin, Y.-P.; Li, W.-N.; Hong, L.; Liang, N.-N.; Liu, F.; Zhang, Y.;
Wei, Z.-X.; Tang, Z.-Y.; Russell, T. P.; Hou, J.-H.; Zhou, H.-Q. A Highly
Efficient Non-Fullerene Organic Solar Cell with a Fill Factor over 0.80
Enabled by a Fine-Tuned Hole-Transporting Layer. Adv. Mater. 2018,
30, 1801801.
[11] Liu, X.; Xie, B.-M.; Duan, C.-H.; Wang, Z.-J.; Fan, B.-B.; Zhang, K.; Lin,
B.-J.; Colberts, F. J. M.; Ma, W.; Janssen, R. A. J.; Huang, F.; Cao, Y. A
high dielectric Constant Non-fullerene Acceptor for Efficient Bulk-
heterojunction Organic Solar Cells. J. Mater. Chem. A 2018, 6, 395–
403.
[12] Mannsfeld, S. C.; Tee, B. C.; Stoltenberg, R. M.; Chen, C. V. H.;
Barman, S.; Muir, B. V.; Sokolov, A. N.; Reese, C.; Bao, Z. Highly Sensi-
tive Flexible Pressure Sensors with Microstructured Rubber Dielectric
Layers. Nat. Mater. 2010, 9, 859.
[13] Newaz, A. K. M.; Puzyrev, Y. S.; Wang, B.; Pantelides, S. T.; Bolotin, K.
I. Probing Charge Scattering Mechanisms in Suspended Graphene by
Varying Its Dielectric Environment. Nat. Commun. 2012, 3, 734.
[14] DiBenedetto, S. A.; Facchetti, A.; Ratner, M. A.; Marks, T. J. Molecular
Self-Assembled Monolayers and Multilayers for Organic and Uncon-
ventional Inorganic Thin-Film Transistor Applications. Adv. Mater.
2009, 21, 1407–1433.
[15] Baranovskii, S. D.; Wiemer, M.; Nenashev, A. V.; Jansson, F.; Gebhard,
F. Calculating the Efficiency of Exciton Dissociation at the Interface
between a Conjugated Polymer and an Electron Acceptor. J. Phys.
Chem. Lett. 2012, 3, 1214–1221.
[16] Zacher, B.; Gantz, J. L.; Richards, R. E.; Armstrong, N. R. Organic Solar
Cells—At the Interface. J. Phys. Chem. Lett. 2013, 4, 1949–1952.
[17] Bauer, W.; Westfall, G. University Physics with Modern Physics, 2nd
Ed., McGraw Hill, 2014.
Chin. J. Chem. 2021, 39, 381－390
 Dielectric Constant and Its Impacts on the Photovoltaic Efficiency
[18] CRC Handbook of Chemistry and Physics, 97th Ed., Ed.: Haynes, W.
M., CRC Press, 2016–2017.
[19] Li, Q.; Cao, R.-G.; Cho, J.; Wu, G. Nanocarbon Electrocatalysts for
Oxygen Reduction in Alkaline Media for Advanced Energy Conversion
and Storage. Adv. Energy Mater. 2014, 4, 20527–20535.
[20] Brus, V. V.; Proctor, C. M.; Ran, N. A.; Nguyen, T. Q. Capacitance
Spectroscopy for Quantifying Recombination Losses in Non-Fullerene
Small-Molecule Bulk-Heterojunction Solar Cells. Adv. Energy Mater.
2016, 6, 1502250.
[21] Brazovskii, S.; Kirova, N. Physical Theory of Excitons in Conducting
Polymer. Chem. Soc. Rev. 2010, 39, 2453–2465.
[22] Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal Solvation
Model Based on Solute Electron Density and on a Continuum Model
of the Solvent Defined by the Bulk Dielectric Constant and Atomic
Surface Tensions. J. Phys. Chem. B 2009, 113, 6378–6396.
[23] Koster, L. J. A.; Shaheen, S. E.; Hummelen, J. C. Pathways to a New
Efficiency Regime for Organic Solar Cells. Adv. Energy Mater. 2012, 2,
1246–1253.
[24] Hughes, M. P.; Rosenthal, K. D.; Dasari, R. R.; Luginbuhl, B. R.; Yurash,
B.; Marder, S. R.; Nguyen, T.-Q. Charge Recombination Dynamics in
Organic Photovoltaic Systems with Enhanced Dielectric Constant.
Adv. Funct. Mater. 2019, 29, 1901269.
[25] Abramavicius, V.; Pranculis, V.; Melianas, A.; Inganäs, O.; Gulbinas, V.;
Abramavicius, D. Role of Coherence and Delocalization in Photo-in-
duced Electron Transfer at Organic Interfaces. Sci. Rep. 2016, 6,
32914.
[26] Li, S.-X.; Liu, W.-Q.; Li, C.-Z.; Shi, M.-M.; Chen, H.-Z. Efficient Organic
Solar Cells with Non-Fullerene Acceptors. Small 2017, 13, 1701120.
[27] Walker, B.; Tamayo, A. B.; Dang, X.-D.; Zalar, P.; Seo, J.-H.; Garcia, A.;
Tantiwiwat, M.; Nguyen, T.-Q. Nanoscale Phase Separation and High
Photovoltaic Efficiency in Solution-Processed, Small-Molecule Bulk
Heterojunction Solar Cells. Adv. Funct. Mater. 2009, 19, 3063–3069.
[28] Qin, P.-L.; Fang, G.-J.; Ke, W.-J.; Cheng, F.; Zheng, Q.; Wan, J. W.; Lei,
H. W.; Zhao, X.-Z. In Situ Growth of Double-layer MoO3/MoS2 Film
from MoS2 for Hole-transport Layers in Organic Solar Cell. J. Mater.
Chem. A 2014, 2, 2742–2756.
[29] Yao, H.; Qian, D.; Zhang, H.; Qin, Y.; Xu, B.; Cui, Y.; Yu, R.; Gao, F.; Hou,
J. Critical Role of Molecular Electrostatic Potential on Charge Genera-
tion in Organic Solar Cells. Chin. J. Chem. 2018, 36, 491–494.
[30] Cheng, P.; Zhang, M.-Y.; Lau, T.-K.; Wu, Y.; Jia, B.-Y.; Wang, J.-Y.; Yan,
C.-Q.; Qin, M.; Lu, X.-H.; Zhan, X.-W. Realizing Small Energy Loss of
0.55 eV, High Open-Circuit Voltage >1 V and High Efficiency >10% in
Fullerene-Free Polymer Solar Cells via Energy Driver. Adv. Mater.
2017, 29, 1605216.
[31] Tamai, Y.; Fan, Y. L.; Kim, O. V.; Ziabrev, K.; Rao, A.; Barlow, A.;
Marder, S. R.; Friend, R. H.; Menke, S. M. Ultrafast Long-Range
Charge Separation in Nonfullerene Organic Solar Cells. ACS Nano
2017, 11, 12473–12481.
[32] Horst, J.-W.; Bobbert, P. A.; Michels, M. A. J.; Bässler, H. Calculation
of Excitonic Properties of Conjugated Polymers Using the Bethe–
Salpeter Equation. J. Chem. Phys. 2001, 114, 6950–6957.
[33] Liu, J.; Chen, S.-S.; Qian, D. P.; Gautam, B.; Yang, G.-F.; Zhao, J.-B.;
Bergqvist, J.; Zhang, F.-L.; Ma, W.; Ade, H.; Inganäs, O.; Gundogdu, K.;
Gao, F.; Yan, H. Fast Charge Separation in a Non-fullerene Organic
Solar Cell with a Small Driving Force. Nat. Energy 2016, 1, 16089.
[34] Baumeier, B.; Rohlfing, M.; Andrienko, D. Electronic Excitations in
Push–Pull Oligomers and Their Complexes with Fullerene from
Many-Body Green’s Functions Theory with Polarizable Embedding. J.
Chem. Theory Comput. 2014, 10, 3104–3110.
[35] Ferguson, A. J.; Kopidakis, N.; Shaheen, S. E.; Rumbles, G. Dark Carri-
ers, Trapping, and Activation Control of Carrier Recombination in
Neat P3HT and P3HT:PCBM Blends. J. Phys. Chem. C 2011, 115,
23134–23148.
[36] Gregory, H. W. The Structure of Electronic Excitation Levels in Insu-
lating Crystals. Phys. Rev. 1937, 52, 191.
[37] Zhao, F.-W.; Wang, C.-R.; Zhan, X.-W. Morphology Control in Organic
Solar Cells. Adv. Energy Mater. 2018, 8, 1703147
Chin. J. Chem. 2021, 39, 381－390 © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem.
[38] Han, G.-C.; Yi, Y.-P. Local Excitation/Charge-Transfer Hybridization
Simultaneously Promotes Charge Generation and Reduces Nonradia-
tive Voltage Loss in Nonfullerene Organic Solar Cells. J. Phys. Chem.
Lett. 2019, 10, 2911–2918.
[39] Zhang, M.; Lu, R.-C.; Yuan, H.-X.; Amin, K.; Mao, L.-J.; Yan, W.; Wei,
Z.-X. Nanowire Array-Coated Flexible Substrate to Accommodate
Lithium Plating for Stable Lithium-Metal Anodes and Flexible Lithi-
um−Organic Batteries. ACS Appl. Mater. Interfaces 2019, 11, 20873–
20880.
[40] Zhang, G.-R.; Clarke, T. M.; Mozer, A. J. Bimolecular Recombination
in a Low Bandgap Polymer:PCBM Blend Solar Cell with a High Dielec-
tric Constant. J. Phys. Chem. C 2016, 120, 7033–7043.
[41] Collins, S. D.; Proctor, C. M.; Ran, N. A.; Nguyen, T.-Q. Solar Cells:
Understanding Open-Circuit Voltage Loss through the Density of
States in Organic Bulk Heterojunction Solar Cells. Adv. Energy Mater.
2016, 6, 1501721.
[42] Kirchartz, T.; Pieters, B. E.; Kirkpatrick, J.; Rau, U.; Nelson, J. Recom-
bination via Tail States in Polythiophene: Fullerene Solar Cells. Phys.
Rev. B: Condens. Matter 2011, 83, 115209.
[43] Wang, Y.-F.; Zhan, X.-W. Layer-by-Layer Processed Organic Solar Cells.
Adv. Energy Mater. 2016, 6, 1600414.
[44] Zhao, W.-C.; Li, S.-S.; Yao, H.-F.; Zhang, S.-Q.; Zhang, Y.; Yang, B.; Hou,
J.-H. Molecular Optimization Enables Over 13% Efficiency in Organic
Solar Cells. J. Am. Chem. Soc. 2017, 139, 7148–7151.
[45] Cho, N.; Schlenker, C. W.; Knesting, K. M.; Koelsch, P.; Yip, H. L.; Gin-
ger, D. S.; Jen, A.-K. Y. High-Dielectric Constant Side-Chain Polymers
Show Reduced Non-Geminate Recombination in Heterojunction So-
lar Cells. Adv. Energy Mater. 2014, 4, 1301857.
[46] Argonne National Laboratory. Control and Characterization of Indi-
vidual Grains and Grain Boundaries in Graphene Grown by Chemical
Vapour Deposition. Nat. Mater. 2011, 10, 456–461.
[47] Chen, S.; Tsang, S.-W.; Lai, T.-H.; Reynolds, J. R.; So, F. Organic Pho-
tovoltaic Cells: Dielectric Effect on the Photovoltage Loss in Organic
Photovoltaic Cells. Adv. Mater. 2014, 35, 6045.
[48] Lu, Y.; Xiao, Z.; Yuan, Y.; Wu, H.; An, Z.; Hou, Y.; Gao, C.; Huang, J.
Fluorine Substituted Thiophene–Quinoxalinecopolymer to Reduce
the HOMO Level and Increase the Dielectric Constant for High Open-
circuit Voltage Organic Solar Cells. J. Mater. Chem. C 2013, 1, 630–
637.
[49] Constantinou, I.; Yi, X.; Shewmon, N. T.; Klump, E. D.; Peng, C.;
Garakyaraghi, S.; Lo, C. K.; Reynolds, J. R.; Castellano, F. N.; So, F.
Organic Photovoltaics: Self-Organization of Polymer Additive, Poly(2-
vinylpyridine) via One-Step Solution Processing to Enhance the Effi-
ciency and Stability of Polymer Solar Cells. Adv. Energy Mater. 2017,
7, 1601947.
[50] Breselge, M.; Severen, I. V.; Lutsen, L.; Adriaensens, P.; Manca, J.;
Vanderzande, D.; Cleij, T. J. Comparison of the Electrical Characteris-
tics of Four 2,5-substituted Poly(p-phenylene vinylene) Derivatives
with Different Side Chains. Thin Solid Films. 2006, 26, 328–332.
[51] Zhang, S.; Zhang, Z.-J.; Liu, J.; Wang, L.-X. Fullerene Adducts Bearing
Cyano Moiety for Both High Dielectric Constant and Good Active
Layer Morphology of Organic Photovoltaics. Adv. Funct. Mater. 2016,
26, 6107–6113.
[52] Torabi, S.; Jahani, F.; Severen, I. V.; Kanimozhi, C.; Patil, S.; Havenith,
R. W. A.; Chiechi, R. C.; Lutsen, L.; Vanderzande, D. J. M.; Cleij, T. J.;
Hummelen, J. C.; Koster, L. J. A. Strategy for Enhancing the Dielectric
Constant of Organic Semiconductors Without Sacrificing Charge Car-
rier Mobility and Solubility. Adv. Funct. Mater. 2014, 25, 150–157.
[53] Knapp, E.; Ruhstaller, B. The Role of Shallow Traps in Dynamic Char-
acterization of Organic Semiconductor Devices. J. Appl. Phys. 2012,
112, 024519.
[54] Bisquert, J.; Belmonte, G. G.; Pitarch, Á.; Bolink, H. J. Negative Capac-
itance Caused by Electron Injection through Interfacial States in Or-
ganic Light-emitting Diodes. Chem. Phys. Lett. 2006, 422, 184–191.
[55] Böttcher, C. J. F.; Belle, O. C.; Bordewijk, P.; Rip, A. Theory of Electric
Polarization, Elsevier Scientific, New York, NY, 1978.
[56] Lu, Y.; Xiao, Z.; Yuan, Y.; Wu, H.; An, Z.; Hou, Y.; Gao, C.; Huang, J.
www.cjc.wiley-vch.de 389
Recent Advances
Fluorine Substituted Thiophene–Quinoxalinecopolymer to Reduce
the HOMO Level and Increase the Dielectric Constant for High
Open-circuit Voltage Organic Solar Cells. J. Mater. Chem. C 2013, 1,
630–637.
[57] Jia, X.-E.; Liu, G.-C.; Chen, S.-S.; Li, Z.-C.; Wang, Z.-F.; Yin, Q.-W.; Yip,
H.-L.; Yang, C.; Duan, C.-H.; Huang, F.; Cao, Y. Backbone Fluorination
of Polythiophenes Improves Device Performance of NonFullerene
Polymer Solar Cells. ACS Appl. Energy Mater. 2019, 2, 7572–7583.
[58] Luo, B.-B.; Pu, Y.-C.; Lindley, S. A.; Yang, Y.; Lu, L.-Q.; Li, Y.; Li, X.-M.;
Zhang, J.-Z. Organolead Halide Perovskite Nanocrystals: Branched
Capping Ligands Control Crystal Size and Stability. Angew. Chem. Int.
Ed. 2016, 55, 8864 –8868
[59] Ricciardulli, A. G.; Yang, S.; Feng, X.-L.; Blom, P. W. M. Solution-Pro-
cessable High-Quality Graphene for Organic Solar Cells. ACS Appl.
Mater. Interfaces 2017, 9, 25412–25417.
[60] Zhang, B.; Yu, Y.-G.; Zhou, J.-D.; Wang, Z.-F.; Tang, H.-R.; Xie, S.-K.; Xie,
Z.-Q.; Hu, L.-Y.; Yip, H.-L.; Ye, L.; Ade, H.; Liu, Z.-T.; He, Z.-C.; Duan,
C.-H.; Huang, F.; Cao, Y. 3,4-Dicyanothiophene—a Versatile Building
Block for Efficient Nonfullerene Polymer Solar Cells. Adv. Energy
Mater. 2020, 10, 1904247.
[61] Xu, X.-F.; Lia, Z.-J.; Wang, J.-K.; Lin, B.-J.; Ma, W.; Xia, W.-J.; Anders-
son, M. R.; Janssen, R. A. J.; Wang, E.-G. High-performance
All-polymer Solar Cells Based on Fluorinated Naphthalene Diimide
Acceptor Polymers with Fine-Tuned Crystallinity and Enhanced Die-
lectric Constants. Nano Energy 2018, 45, 368–379.
[62] Nowick, A. S.; Vaysleyb, A. V.; Liu, W. Identification of Distinctive Re-
gimes of Behaviour in the AC Electrical Response of Glasses. Solid
State Ionics 1998, 105, 121–128.
390 www.cjc.wiley-vch.de © 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Fu et al.
[63] Hughes, M. P.; Rosenthal, K. D.; Ran, N. A.; Seifrid, M.; Bazan, G. C.;
Nguyen, T.-Q. Charge Recombination Dynamics in Organic Photovol-
taic Systems with Enhanced Dielectric Constant. Adv. Funct. Mater.
2018, 28, 1801542.
[64] Zhang, X.-N.; Zhang, D.-Y.; Zhou, Q.; Wang, R.; Zhou, J. Y.; Wang, J.-Q.;
Zhou, H.-Q.; Zhang, Y. Fluorination with an Enlarged Dielectric Con-
stant Prompts Charge Separation and Reduces Bimolecular Recom-
bination in NON-Fullerene Organic Solar Cells with a High Fill Factor
and Efficiency > 13%. Nano Energy 2019, 56, 494–501.
[65] Orazem, M. E.; Tribollet, B. Electrochemical Impedance Spectroscopy,
Wiley, New York, 2011.
[66] Xu, B.; Yi, X.-P.; Huang, T.-Y.; Zheng, Z.-L.; Zhang, J.-X.; Salehi, A.;
Coropceanu, V.; Ho, C. H. Y.; Marder, S. R.; Toney, M. F.; Bredas, J.-L.;
So, F.; Reynolds, J. R. Donor Conjugated Polymers with Polar Side
Chain Groups: The Role of Dielectric Constant and Energetic Disorder
on Photovoltaic Performance. Adv. Funct. Mater. 2018, 28, 1803418.
[67] Mabrouk, S.; Zhang, M.-M.; Wang, Z.-H.; Liang, M.; Bahrami, B.; Wu,
Y.-G.; Wu, J.-H.; Qiao, Q.-Q.; Yang, S.-F. Dithieno[3,2-b:2’,3’-d]pyr-
role-based Hole Transport Materials for Perovskite Solar Cells with
Efficiencies over 18%. J. Mater. Chem. A 2018, 6, 7950–7958
Manuscript received: June 13, 2020
Manuscript revised: September 7, 2020
Manuscript accepted: September 16, 2020
Accepted manuscript online: September 20, 2020
Version of record online: December 30, 2020
Chin. J. Chem. 2021, 39, 381－390