Adv Energy and Sustain Res - 2022 - Zhu

PERSPECTIVE
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Exciton Binding Energy of Non-Fullerene Electron

Acceptors
Yufan Zhu, Fuwen Zhao, Wei Wang, Yawen Li, Shiming Zhang,* and Yuze Lin*
usually in the range of 0.1–1.0 eV,[9] which

The past three years have witnessed the power conversion efficiency (PCE) of organic is much higher than those for perovskite
solar cells (OSCs) rocketing to over 18%, due to outstanding advantages of non- and inorganic semiconductors.[10] The high
fullerene acceptors (NFAs). However, large exciton binding energy (Eb) caused by Eb leads to large energy loss and severe
geminate recombination for OSCs.[9]
strong Coulombic force is still one of the main limiting factors for high-performance Furthermore, because of the large Eb and
OSCs. Thus, it is critical to reduce the Eb for further enhancement of device short exciton lifetime, it is necessary to
performance. Many strategies have been developed to reduce the Eb of organic employ a BHJ structure with bicontinuous
materials previously. In this perspective, the calculation methods for Eb and the interpenetrating networks with nanoscale
relationship between Eb and voltage loss (Vloss) are discussed. Then, the effects of phase separation to facilitate exciton disso-
ciation with the energy level difference,
the properties of small-molecule acceptors on Eb from the perspectives of fused-ring
leading to morphology control issues.
donor cores, end groups, side chains, and molecular packing are discussed. Finally, Thus, reducing Eb is one of the key issues
the potential directions for reducing Eb and pointing out the trade-off between Eb and to achieve highly efficient OSCs.
bandgaps/miscibility are put forward. It is hoped that this perspective could provide The past 3 years have witnessed the
a new thinking of a molecular design for the breakthrough of OSCs. power conversion efficiency (PCE) of
OSCs exceeding 18%[11,12] due to outstand-
ing advantages of non-fullerene acceptors
(NFAs) as follows: 1) strong absorption in
the visible and near-infrared (NIR) area, benefiting for high
1. Introduction short-circuit current density ( JSC); 2) adjustable energy levels
Bulk heterojunction (BHJ) organic solar cells (OSCs), consisting to achieve reduced energy loss and high open-circuit voltage
of mixed donor (D) and acceptor (A) in the active layer, have (VOC); and 3) various and simple chemical modifications.
attracted considerable attention, due to their potential advan- These advantages are believed to be closely related to its unique
structure, which consists of a fused ring donor unit with side
tages, such as portability, mechanical flexibility, and roll-to-roll
[1–4] chains attached to a bridged atom (C or N), and two strongly elec-
machinability. Upon excitation by incident light, an exciton,
[5] tron-withdrawing units at both ends. With considerable efforts
rather than free charge carriers, is generated in the active layer,
devoted to highly efficient NFAs, a large pool of NFAs have been
which is ascribed to the low relative dielectric constant (εr < 3–4)
developed, which offers a chance to investigate the Eb from the
of organic semiconductors. Then, the exciton, bound by strong
viewpoint of the structures of NFAs.
Coulombic force, can dissociate into free charge carriers under
Several strategies have been put forward to successfully adjust
the energy level difference at D/A interfaces.[6] This energy,
Eb via modifying the structure of NFAs. For example, Li et al.[13]
required to dissociate exciton into free charge carriers, is called
reported that using [1,2,5]oxadiazolo[3,4-d]pyridazine to replace
the exciton binding energy (Eb).[7,8] Eb for organic materials is
benzo[c][1,2,5]thiadiazole (BT) in NFAs results in the reduction
Y. Zhu, S. Zhang Y. Zhu, W. Wang, Y. Li, Y. Lin

Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Materials (IAM) Organic Solids, Institute of Chemistry
Jiangsu National Synergetic Innovation Chinese Academy of Sciences
Center for Advanced Materials (SICAM) Beijing 100190, P. R. China
Nanjing Tech University E-mail: linyz@iccas.ac.cn
Nanjing 211816, Jiangsu, P. R. China
E-mail: iamsmzhang@njtech.edu.cn F. Zhao
State Key Laboratory of Powder Metallurgy
The ORCID identification number(s) for the author(s) of this article Central South University
can be found under https://doi.org/10.1002/aesr.202100184. Changsha 410083, P. R. China
© 2022 The Authors. Advanced Energy and Sustainability Research pub- Y. Li, Y. Lin
lished by Wiley-VCH GmbH. This is an open access article under the terms University of Chinese Academy of Sciences
of the Creative Commons Attribution License, which permits use, Beijing 100049, P. R. China
distribution and reproduction in any medium, provided the original
work is properly cited.
DOI: 10.1002/aesr.202100184
Adv. Energy Sustainability Res. 2022, 3, 2100184 2100184 (1 of 11) © 2022 The Authors. Advanced Energy and Sustainability Research
published by Wiley-VCH GmbH
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of Eb deduced from density functional theory (DFT) calculation. way to obtain Efund is by measuring the IP and EA through ultra-
However, the inner relationship between Eb and the structure of violet photoelectron spectroscopy (UPS) and inverse photoelec-
NFAs is complicated and has not been systematically investigated tron emission spectroscopy (IPES), respectively.[16] It should
yet. In this perspective, we discuss the methods to determine the be noted that using UPS and IPES must exclude nuclear relaxa-
Eb and the relationship between Eb and open-circuit voltage loss tion processes and yield electron and hole transport levels that
(Vloss) of OSCs. Then, we focus on the relationship between Eb are shifted of 100–150 meV with respect to the fully relaxed
and the structure of NFAs from the aspects of fused-ring donor polaron level relevant to carrier transport.[16] However, few
cores, end groups, and side chains, as well as molecular packing. studies have used these methods to obtain Efund in organic semi-
At last, we figure out the potential directions to reduce Eb for conducting materials due to the expensive equipment and
high-efficiency OSCs. We hope that this perspective could pro- complicated measurement.
vide a new view of molecule design for the breakthrough of Another method to obtain Efund is by measuring the oxidation
OSCs. and reduction potential through cyclic voltammetry (CV).[17]
According to Hartree Fook’s calculation and Koopmans’
theorem, IP can be considered as highest occupied molecular
2. The Calculation Methods of Eb orbital (HOMO) energy level and EA can be considered as lowest
unoccupied molecular orbital (LUMO) energy level in consider-
The Eb for a material M (homogeneous or heterogeneous) is ing molecular orbits theory.[18] Therefore, in many cases, Eb is
defined as the energy required for the process. normally expressed as
M ¼ Mþ þ M (1) opt
E b ¼ LUMO HOMO E g ¼ E g E g
opt
(4)
where M* is the lowest excited state of the material in the solid where Eg is the energy difference between HOMO and LUMO
material and Mþ and M represent noninteracting holes and energy levels. However, for CV measurement, an equally and
electrons in the material. Considering energy state change of likely more important issue is that the effective (low-frequency)
a system absorbing light, Eb is calculated by the energy difference εr in the electrolyte solution is generally quite a bit larger than in
between the fundamental gap (Efund) and optical gap (Egopt).[14] an organic solid. This will lead to the deviation that the electro-
E b ¼ E fund E g
opt
(2) chemical gap (Eox Ered, Eox is the oxidation potential and Ered is
the reduction potential) is generally quite a bit smaller than the
opt Efund, and thus Eb will be underestimated. However, due to the
As shown in Figure 1, E g is the energy from the ground state
universality of this method, there are still many studies to
(S0) to the first optically allowed excited state (S1), which is often
measure Eg by CV so far.
determined experimentally from the absorption band edge. Efund
In addition, there is another classical way to calculate Eb with
is the energy difference between ionization potential (IP) and
some basic parameters, which can be easily measured.
electron affinity (EA).
E b e2 =ð4πε0 εr RÞ (5)
E fund ¼ IP EA (3)
opt where e is the elementary charge, ε0 is the vacuum dielectric
The E g is accessible by absorption measurement, whereas constant, and R is the average electron–hole distance.[19,20]
Efund is relatively difficult to acquire accurately.[15] One direct This method is limited as R is usually the distance between elec-
trons and holes in a single molecule obtained by quantum-
chemical calculations. εr is acquired by measuring the relation-
ship between frequency (a common frequency for the compari-
son of εr values is 1 MHz this frequency is chosen because its
time scale is comparable to that of nongeminate recombination
(1 μs), which is the main loss mechanism to reduce with higher
dielectric values.)[21] and capacitance in the film. This method of
calculating Eb is generally used in inorganic semiconductors.
Due to the disorder of organic materials in thin films, it is
not suitable for most organic semiconductors.
In addition to this experiment method, Eb can be calculated
theoretically. For instance, Nayak et al. studied the shapes and
radius of some small organic conjugated molecules with the
B3LYP hybrid DFT method.[15] Kraner et al. pointed out that
Eb was the difference between the Coulomb interactions of
Figure 1. Illustration of gap energies in the molecular case: S0 denotes the
the electron–hole pair and the kinetic energy of these quasi-
singlet electronic ground state and S1 is the first optically allowed excited
state (considered here to be accessible via one-photon absorption). Egopt particles and assumed that the kinetic energy is half of the
is the energy difference between the two energy levels from S0 to S1. Efund Coulomb interactions.[22] Furthermore, they designed a triad
is the difference between IP and EA. The electron–hole pair binding energy, molecule and predicted that it had a very small Eb (about
Eb, is given by Efund Egopt. 39 meV) by utilizing the long-range, corrected hybrid density
functional CAM-B3LYP.[23] However, this research only focused donor/acceptor interfaces as electron–hole pairs. Such interfacial
on a single molecule. It is far from reality, as intermolecular electron–hole pairs are generally referred to as CT states, which
interaction in film, related to molecular packing and arrange- can be observed by the determination of the transient absorption.
ments, cannot be ignored. It needs extra energy to overcome the Coulomb force between the
hole in the donor and the electron in the acceptor and separate
the CT states in OSCs, which is the binding energy of CT
3. The Relationship between Eb and Vloss in OSCs states.[27] The energy level offset, formed between the donor
and the acceptor, would contribute to the separation of CT states.
3.1. Vloss in OSCs Therefore, the binding energy of CT states is generally less than
Eb in OSCs.
Due to the large binding energy for Frenkel exciton, the Vloss of
OSCs is considered to be a large and unavoidable loss.[24] The
Vloss in OSCs is defined as 3.3. Relationship between Eb, CT States, and Vloss
Eg In BHJ OSCs, CT states are the active centers of charge sepa-

V loss ¼ V OC (6)
q ration and recombination. In fullerene-based OSCs, charge
separation occurs at donor/acceptor interfaces and is consid-
where Eg is the lowest optical bandgap among the donor and ered to be driven by HOMO(D)–HOMO(A) or LUMO(D)–
acceptor components and q is the elementary charge.[24] In LUMO(A) energy level offsets (ΔEHOMO or ΔELUMO). This
the framework of Shockley–Queisser detailed balance energy consumption requirement is generally regarded as a
model,[25,26] the overall Vloss can be divided into three parts. basic limitation of OSC efficiency. A large energy level offset is
SQ
usually related to suppressing the CT states recombination loss,
V loss ¼ ΔV oc þ ΔV rad
oc þ ΔV oc
nonrad
(7) but it also reduces the electronic bandgap of the blend
SQ (IPdonorEAacceptor), limiting the VOC of devices. Conversely, a
where ΔV oc is the minimum Vloss while assuming an ideal small energy level offset can increase VOC, but it will limit the
semiconductor, ΔV radoc comes from the absorption below the opti- charge separation efficiency. Therefore, the trade-off between
cal gap in a real device, and ΔV nonrad
oc is the Vloss due to non- VOC and JSC is often observed in OSCs.[24] Recently, it has been
SQ
radiative recombination.[25] The first term, ΔV oc , is the reported that CT states can hybridize with singlet exciton states
detailed balance Vloss limit under the given solar irradiation near under low energy level offset in high-efficiency NFA-based sys-
the earth’s surface and omnipresent blackbody radiation at room tems.[28,29] The hybridization will make the CT states electroni-
temperature. It is initially proposed to be 0.25–0.30 eV for an cally couple with the singlet states, which has high oscillator
ideal semiconductor, solely depending on its optical gap under strength for radiative transition, and thus improves the radiative
standard working conditions. For ΔV rad oc , sub-band gap states,
efficiency of the blend to reduce the nonradiative recombination
such as the charge transfer (CT) states and the band-tail states, loss. Although the energy of CT states is closely related to Eb and
will provide additional transitions below the optical gap, and Vloss, there is no necessary connection between Eb and Vloss.
thereby extend the optical response to a lower energy region Though it has been reported that, in some NFA systems, lower
and reduce the maximum achievable voltage. The ΔV nonrad Eb is accompanied by a reduction in energy loss, the inner rela-
oc
can be approximately quantified as follows. tionship is unclear yet.
kT
ΔV nonrad ¼ lnðEQEEL Þ (8)
oc
q 4. Effect of the Structure of NFAs on Eb of
Excitons
where q is the elementary charge, k is the Boltzmann constant, T
is the temperature, and EQEEL is the external quantum efficiency Eb of excitons is closely related to the molecular structure of
of electroluminescence. Regardless of the methods used to cate- materials in the active layer. We discussed the relationship
gorize the Vloss, the ΔV nonrad
oc , stemming from nonradiative between Eb and the structure of NFAs benefiting from the large
recombination, dominates the Vloss in most OSCs and has pool of the reported NFAs in this section. To obtain more reliable
spurred tremendous efforts to mitigate this loss. trends in Eb, the molecule and its Eb for comparison need to be
acquired from the same article. Moreover, the rest of the material
3.2. Binding Energy of CT States remains unchanged to study the effect of a certain structural unit
on Eb. We extracted the required data from a number of studies
For organic semiconductors, the low εr contributes to their high and use Equation (3) to calculate Eb to investigate the relationship
Eb, which results in a large Coulombic interaction between between Eb and the structure of NFAs. The data of Eb for relevant
tightly bound excitons.[21] These excitons are mainly separated molecules are listed in Table 1.
by CT at organic donor/acceptor interfaces, driven by energetic
offsets between donor and acceptor energy levels. A BHJ blend 4.1. Effect of Conjugated Backbones on Eb
morphology is typically employed to facilitate photogenerated
excitons to access this interface. Following exciton separation, Because of the great success of 4,9-dihydro-s-indaceno[1,2-
charges may either dissociate into free charges or remain at b:5,6-b 0 ]dithiophene (IDT) unit as an electron-donating core
Table 1. Eg, Egopt, and Eb for NFAs (Eb was calculated by Equation (3)). the conjugated fused rings on Eb. Figure 2 shows the chemical
structures of the different conjugated units of the NFAs dis-
Acceptor Eg Egopt Eb Ref. cussed in this section. Many research groups have reported
IDIC 1.79 a)
1.62 b)
0.17 [32] various models to calculate the Eb of molecules to find the rela-
tionship between the number of fused rings and Eb. Zhu
IEIC 1.60a) 1.57b) 0.03 [33]
et al.[27] used the systemically optimized time-dependent
ITIC 1.75a) 1.59b) 0.16 [34]
DFT and took into account the solid-state polarization effect
a) b)
INIC 1.57 1.57 / [35] to calculate Eb of six kinds of molecules, including IDIC,[32]
NFBDT 1.57a) 1.56b) 0.01 [36] IEIC,[33] ITIC,[34] INIC,[35] and NFBDT.[36] Figure 3a shows
F6IC 1.64a) 1.36b) 0.28 [44] Eb for molecules with different conjugated lengths. The results
F8IC1 1.44a) 1.32b) 0.12 [43]
demonstrate that Eb decreases with the increased number of
a) b)
fused rings on the backbones when the side chains and end
F10IC1 1.39 1.29 0.10 [43]
groups remain unchanged. For example, Eb of INIC, which
Y6 1.55a) 1.33b) 0.22 [40] has two more thiophene rings on the backbones, is smaller
BP5T-4 F 1.75a) 1.34b) 0.39 [45] than that of NFBDT. The results from the calculation indicate
ABP4T-4 F 1.80a) 1.37b) 0.43 [45] that extending conjugation of the main chain leads to a
BP6T-4 F 1.76 a)
1.39 b)
0.37 [46] decreased isotropic component of the molecule polarizability
(α).[37]As the εr increases when α decreases,[38] extending fused
ABP6T-4 F 1.73a) 1.36b) 0.37 [46]
rings in the donor core reduces Eb. These results are also
IT-DM 1.76a) 1.63b) 0.13 [49]
verified in other systems. Zheng et al.[39] simulated the calcu-
IT-CF 1.64a) 1.57b) 0.07 [49] lation of Y6-series molecules and compared Eb of BTPTT-
IT-4 F 1.57a) 1.54b) 0.03 [49] 4F(Y6),[40] BTP6T-4F, BTPTT-4F-2T, and BTPTT-4F-TT-TT6
IT-IC-0 F 1.70 a)
1.59b) 0.11 [50] on the basis of DFT with the tuned ωB97X/6-31G(d)/PCM
IT-IC-2 F 1.69a) 1.56b) 0.13 [50]
theory level.[41,42] The calculation results of Eb for these mol-
ecules are shown in Figure 3b. It showed that Eb decreased
IT-IC-3 F 1.61a) 1.54b) 0.07 [50]
effectively by either increasing the number of fused rings of
a) b)
IT-IC-4 F 1.59 1.55 0.04 [50] the main chain or increasing the π bridge linkage element.
IT-IC-6 F 1.62a) 1.51b) 0.11 [50] We calculated Eb of the reported molecules according to
YA1 1.92c) 1.73c) 0.19 [51] Equation (3) and found the same pattern with the DFT calcula-
YA2 1.95c) 1.75c) 0.20 [51] tion results mentioned earlier. Zhan et al.[43] reported a series of
fused-ring small molecule acceptors, namely F6IC,[44] F8IC1, and
YA3 2.00c) 1.80c) 0.21 [51]
c)
F10IC1. According to the data reported in the literature, it was
YA4 2.03 1.82c) 0.21 [51]
found that Eb gradually decreased with the increased number of
Y21 2.03c) 1.83c) 0.20 [51] fused rings under the condition of unchanged end groups and
BTP-4Cl 1.49a) 1.35b) 0.14 [52] side chains. Reduced Eb facilitates exciton dissociation.[10] As a
C8-ITIC 1.72 a)
1.55 b)
0.17 [57] result, exciton dissociation efficiency is increased with more
ITIC 1.72a) 1.61b) 0.11 [57]
fused rings in the conjugated structure. The JSC/Jsat (saturated
photocurrent) ratios for the F6IC-, F8IC1-, and F10IC1-based
Y6-O 2.04a) 1.52b) 0.52 [59]
devices are calculated to be 93.7%, 95.6%, and 96.9%, respec-
Y6 1.86a) 1.37b) 0.49 [59] tively. As for asymmetric NFAs, BP5T-4F possesses one more
BTP-Ph 1.79 a)
1.36 b)
0.43 [58] fused ring than ABP4T-4 F, leading to smaller Eb.[45] After that,
BTP-Th 1.82a) 1.34b) 0.48 [58] another two NFAs, ABP6T-4F and BP6T-4F, based on nonacyclic
BTP-C11 1.78a) 1.32b) 0.46 [58] electron acceptors were developed by the same group.[46] Due to
the extension of conjugated units, Eb of these two molecules are
Y6-4O 1.63d) 1.39b) 0.24 [67]
d) b)
further decreased.
Y6 1.65 1.35 0.30 [67]
The asymmetric structure generally has a higher εr compared
opt
to the symmetric isomer with the same number of fused rings in
Calculated by CV; b)Calculated by Eg ¼ 1240=λedge , where λedge is the absorption
a)
the donor unit. According to Equation (4), the larger εr is, the
edge of the thin film c)Calculated by DFT; d)Calculated by UPS and IPES.
smaller Eb will be obtained. As a result, better exciton dissocia-
tion can be expected. For instance, Jen et al.[46] designed an asym-
in DC-IDT2T and fluorene as a core in NFAs,[30] the most metric isomer of BT and developed the fused-ring electron
common strategy to tune the optical physical properties of acceptors, ABP6T-4F. The εr of ABP6T-4F is 2.22 times higher
NFAs is increasing the number of conjugated rings in the than that of BP6T-4F (1.78). As a result, ABP6T-4F presents a
fused core. Extending the donor core promises to enhance smaller Eb compared to BP6T-4F. It may be one of the reasons
intramolecular charge transfer (ICT), thus enhancing for more effective exciton dissociation in ABP6T-4F-based
HOMO energy level and expanding the absorption to NIR devices.
region.[31] According to the calculation of Eb, extending conju- As summarized in Figure 3c, increasing the number of fused
gated rings has an impact on Eg and Egopt, resulting in varia- rings in the donor core, replacing different fused ring blocks, and
tion of Eb. Therefore, it is necessary to explore the influence of introducing an asymmetric structure can decrease Eb effectively.
Figure 2. The chemical structures of the NFAs with different conjugated units.
Figure 3. a) Eb of IDIC, IEIC, ITIC, INIC, and NFBDT. Data were taken from ref. [27]. b) Eb of BTPTT-4F, BTPTT-4Cl, BTPTT-4F-2T, andBTPTT-4F-TT. Data
were taken from ref. [39]. c) Effect of conjugated backbones on Eb.
4.2. Effect of the End Groups on Eb class of IDTT-based fluorinated molecules, increasing the fluorine
atoms of the IT-IC-nF end group could reduce Egopt and deepen
The end groups of NFAs not only influence the molecular energy LUMO energy level, as shown in Figure 5a. It turns out that from
levels (especially LUMO energy levels) and optical gaps through IT-IC-2F to IT-IC-4F, Eb decreases. However, it should be noted
ICT,[47] but also influence the dipole moment (μ) of NFAs. Eb was that there is some exceptional case. Eb increases for IT-IC-6F, and
affected by the end groups of NFAs, because Eb is related to the Eb of the IT-IC-2F is larger than that of IT-IC-0F. Although Eb of
energy levels and μ.[48] It is impossible to distinguish the effect of IT-IC-6F is not the lowest, as shown in Figure 5b, IT-IC-6F-based
energy levels and μ. The μ is the product of the distance between devices afford the highest JSC. In fact, the μ is a vector quantity. A
the center of a molecule’s positive and negative charges and the large μ on the whole molecule can be achieved, only when the
amount of charge q in the center. dipoles of the substituents on end groups are in the same direc-
tion. Therefore, it is necessary to study the effect of fluoride on
~
μ ¼ q ~
r (9) dipole distance and Eb. Furthermore, IT-IC-4F affords the lowest
Eb but not the highest JSC, suggesting a balance between Eb and
Therefore, the dipole of the substituent bond to the carbon and other photovoltaic parameters (e.g., VOC).
the position of the substituent on the end groups determine the μ These results are similar for the Y series NFAs. Muhammad
of the molecule. We summarized the tendency of Eb toward the et al.[51] designed four novel Y series NFAs (YA1, YA2, YA3,
different kinds of fluorine substitution on the end groups from the and YA4 shown in Figure 4) through terminal modification of
reported NFA series. For IDTT series, we take IT-DM, IT-CF, and the recently reported Y21 molecule, and calculated Eb of them
IT-4F, for instance (Figure 4). Eb gradually decreased from the through the charge distribution on the molecules. The result from
electron-donating group to the electron-withdrawing group on the calculation indicates that Eb decreases with the large dipole of
end groups.[49] The OSC based on IT-4F with the smallest Eb the substituent on the end groups in Y series. For example, BTP-
exhibits the highest JSC. For IT-IC-nF series (Figure 4),[50] another 4Cl (Figure 4), with Cl at the end group,[52] exhibits smaller Eb
Figure 4. The chemical structures of NFAs with the different end groups.
Figure 5. a) Eb, Eg, and Egopt of the PBDB-TF:ITIC-nF-based OSCs. Data were taken from ref. [50]. b) Eb and photovoltaic metrics of the PBDB-TF:ITIC-nF-
based OSCs. Data were taken from ref. [50]. c) Effect of the end groups on Eb.
compared to the fluorinated counterpart Y6. As is well known, In fact, as the μ is a vector, the dipole of the substituent must be
fluorine has a stronger electron-withdrawing ability than chlorine. as large as possible in the same direction to enhance the μ of the
The reason for the abnormal reduction of Eb may be that the μ of entire molecule. As shown in Figure 5c, the large μ design of the
the chloro-carbon bond is larger than that of the fluorocarbon molecule will increase the molecular polarizability and reduce Eb.[54]
bond. The dipole direction in BTP-4Cl turns opposite compared
to that in Y6. The reduced Eb suppresses recombination loss, 4.3. Effect of the Side Chains on Eb
which contributes to improved VOC. In contrast, a large μ facili-
tates the charge separation and helps to achieve a high fill factor In NFAs, side chains are usually attached to the sp3 hybrid atoms
(FF) in the device.[53] C and Si or sp2 hybrid N atoms in the donor moiety to increase
Figure 6. The chemical structures of NFAs with different side chains.
the solubility in the processing solvents, and to prevent excessive energy levels unchanged. Compared to Y6, Y6-O suffers higher
aggregation of NFAs for ideal morphology.[31] The large steric Eb. However, with the number of oxygen atoms in the side chain
hindrance and free rotation for the side chains will disturb increasing, εr increases and Eb decreases. Lin et al.[60] reported a
the intermolecular π–π stacking and lead to a low crystallinity.[55] new NFA named Y6-4O, which introduces an asymmetric highly
Intermolecular aggregation often has a great influence on Eb. for polarizable oligo-(ethylene glycol) side chain onto the pyrrole unit
example, Wei et al.[56]reported that the 3D packing crystal of the of Y6. As shown in Figure 7a, at the frequency of 1 kHz, Y6-4O
OSCs can effectively reduce Eb with an extremely weak Eb of exhibits a εr of 5.13, obviously higher than that of Y6 (3.36). As a
0.04 eV calculated in 4TIC. We discussed the side chains in this result, Eb decreases with the oligo-(ethylene glycol) side chain.
part because the side chains can change the εr of the molecule The PCE of Y6-4O (15.2%) is the highest among NFAs with a
and regulatory molecular aggregation and thus affect Eb. The εr greater than 5 (Figure 7b).
chemical structures of the different side chains of the NFAs As summarized in Figure 7c, by introducing aryl groups on the
are shown in Figure 6. side chains, the molecular aggregation can be adjusted to affect Eb.
Heeney et al.[57] synthesized C8-ITIC by replacing phenylalkyl With the increase of the number of oxygen atoms in the side chain,
side chains with alkyl side chains of ITIC. With the same Eg, C8- εr of the molecule will increase, leading to the reduction of Eb.
ITIC has a smaller Egopt leading to a larger Eb. Similar results were
found in the Y series NFAs. Yan et al.[58] developed BTP-Th and
BTP-Ph by introducing thiophene and benzene ring units at the β 5. Effect of the Molecular Packing on Eb
site of the thiophene group of Y6 (BTP-C11), respectively. It is
The optical and electrical properties of organic materials are
found that the thiophene and benzene units on the side chains
deeply affected by molecular packing structures in the solid state.
introduce more steric hindrance and thus slightly reduce the crys-
In general, organic materials will form two kinds of aggregates in
tallinity of the molecule. Compared to Y6, phenyl side chain (BTP-
the solid state: H- and J-aggregates. These aggregations cause
Ph) decreases Eb to 0.43 eV, while thiophene side chain (BTP-Th)
molecules to form dimers and thus split energy levels.
increases Eb. As a result, BTP-Ph-based devices offer a superior
According to Kasha’s molecular exciton model,[60] when NFAs
photovoltaic performance than BTP-Th and Y6, which should
form H-aggregates, the singlet energy of the dimer state is higher
be partially ascribed to the reduced Eb of BTP-Ph. By introducing
than that of the single molecule. As for J-aggregates, when the
aromatic hydrocarbons on the alkyl chain, the molecular stacking slip angle is less than 54.7 , the singlet energy of the dimer state
method can be adjusted to affect Eb.[56] is lower than that of the single molecule.[60] For most of the
In contrast, alkoxy chains influence the Eb. Y6-O, an analogue NFAs, it is usually easy to form J-aggregates in the film.
of Y6, is obtained by substituting the alkyl chains with alkoxy Therefore, the film absorption of most NFAs redshifts, compared
chains at the outer thiophene β site.[59] Alkoxy replacement obvi- with solution absorption. Thus, the molecular packing will affect
ously improves the LUMO energy levels and keeps HOMO the Eb of organic materials.[61] For example, Zheng et al.[62]
Figure 7. a) ϵr versus frequency of Y6 and Y6-4O, and b) the recently reported OSCs based on high-dielectric-constant organic semiconductors.
Reproduced with permission.[67] Copyright 2021, American Chemical Society. c) Effect of the side chains on Eb.
Figure 8. The chemical structures of SubPc, 4TIC, and DPP-DTP-based copolymers.
calculated the Eb values of the single molecule and dimer of sub- the potential directions: 1) How to balance Eb with bandgaps of
phthalocyanine chloride (SubPc) (Figure 8) and found that dimer NFAs? As discussed in Section 3.2, fluorination of the end group
s3 packing state of SubPc had the smallest Eb. Wei et al.[56] reduces Eb, but the LUMO energy of NFAs declines at the same
reported that the 3D packing crystal of the OSCs could effectively time. As a result, reduced Eb increases JSC but decreases VOC.
reduce Eb with an extremely weak Eb of 0.04 eV calculated in Thus, the balance between Eb and bandgaps needs to be taken into
4TIC (Figure 8). Moreover, they further calculated the Eb values consideration. 2) How to balance Eb with miscibility? Increasing εr
of IDIC in three different crystal phases and demonstrated that a by introducing highly polarizable side chains is an effective way to
higher backbone packing dimensionality was beneficial for decrease Eb. However, the highly polarizable side chains may
obtaining a smaller Eb.[63] decrease the miscibility of NFAs with the donor. It may lead to
inferior photovoltaic performance due to morphology issue.
Therefore, how to balance Eb with miscibility needs attention.
6. Summary and Outlook For example, the number, the length, and the position of the
highly polarizable side chains are suggested to be carefully consid-
Since 2015, OSCs have been greatly developed with the maxi- ered. 3) What is the relationship between Eb and the structure of
mum PCE exceeding 18% and gradually approaching that of donor molecules? The structure of donor molecules also affects
inorganic solar cells. Although great achievements in OSCs have their Eb. However, it is hard to summarize the regulation between
been made recently, large Eb, the main factor limiting the pho- Eb and donors, as the related literature are limited. Therefore, we
tovoltaic performance of OSCs, calls for much attention. In this appealed to investigate the effect of donor molecules on Eb as well.
perspective, the relationship between molecular structure and Eb
of NFAs is discussed as follows: 1) The donor moiety. Extending
the donor core of NFAs is an effective way to enhance absorption Acknowledgements
and decrease Eb. In addition, the asymmetric structure can
decrease Eb by improving εr. 2) The electron-withdrawing end Y.Z. and F.Z. contributed equally to this work. The authors thank the
National Natural Science Foundation of China (No. 52173189) for financial
groups. Increasing the electron-withdrawing capacity of end
support.
groups or halogen atomic substitution may enhance the μ of
the molecule. The larger μ is, the smaller Eb will be achieved.
3) The side chains. Side chains affect the εr of NFAs, thus chang-
Conflict of Interest
ing Eb. At present, an ethylene glycol chain instead of an alkyl
chain can effectively decrease Eb by increasing εr. Introducing The authors declare no conflict of interest.
highly polarizable side chains seems an effective way to reduce
Eb by enhancing εr of NFAs.
It should be noted that the methods to reduce Eb are more
than the molecular design of NFAs. For instance, from the view-
Keywords
point of the donor, Janssen et al.[64] reported that introducing 2,5- exciton binding energy, fused-ring electron acceptors, non-fullerene
dihydropyrrolo-[3,4-c]pyrrole-1,4-dione (DPP) and dithieno[3,2- acceptors, organic photovoltaics, organic solar cells
b:2 0 ,3 0 -d]pyrrole (DTP) (Figure 8) into the polymer donor can Received: November 22, 2021
effectively reduce Eb. In terms of interfacial modification, inor- Revised: January 22, 2022
ganic high-k nanostructured materials are introduced to decrease Published online: February 7, 2022
Eb by reducing Coulomb interaction.[65,66]
Eb has a significant influence on the performance of OSCs.
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Yufan Zhu received a B.S. degree in materials science and engineering from the Dalian University of
Technology in 2018. Now he is an M.E. student at the Institute of Advanced Materials (IAM), Nanjing
Tech University. His research interest focuses on non-fullerene acceptors in organic solar cells.
Fuwen Zhao received a Ph.D. in physical chemistry from the Institute of Chemistry, Chinese Academy of
Sciences (ICCAS) in 2017, followed by a Marie Curie postdoc fellowship at Linköping University. Now
she is a full professor at Central South University. Her current research interests include the fabrication
of high-performance organic solar cells and device physics in solar cells.
Shiming Zhang received a Ph.D. in 2009 from ICCAS and subsequently began postdoctoral research
within the Department of Chemistry at Northwestern University under the supervision of Prof. Tobin J.
Marks and Antonio Facchetti. He worked at KAUST (Saudi Arabia) as a postdoctoral fellow from 2011 to
2012, after which he worked in Silecs International and Win Tech Nano Singapore from 2012 to 2015. In
2015, he joined the Institute of Advanced Materials (IAM) and began his professorship at Nanjing Tech
University (Nanjing Tech) as a professor. His research interests include organic/flexible electronics and
microelectronics-packaging materials.
Yuze Lin is currently a professor in the Laboratory of Organic Solids, ICCAS. He received his B.S. degree
in chemistry from Beijing Institute of Technology in 2009, and a Ph.D. in polymer chemistry and physics
from ICCAS in 2014. Before he joined ICCAS as a principal investigator in 2019, Dr. Lin conducted
postdoctoral research at the University of Nebraska-Lincoln and the University of North Carolina at
Chapel Hill. Now his research interests include organic/hybrid optoelectronic materials and devices for
applications in energy harvesting and sensing.

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PERSPECTIVE

Exciton Binding Energy of Non-Fullerene Electron

usually in the range of 0.1–1.0 eV,[9] which

Y. Zhu, S. Zhang Y. Zhu, W. Wang, Y. Li, Y. Lin

Eg In BHJ OSCs, CT states are the active centers of charge sepa-

Figure 6. The chemical structures of NFAs with different side chains.

Figure 8. The chemical structures of SubPc, 4TIC, and DPP-DTP-based copolymers.

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