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Suppressing photo-oxidation of non-fullerene

Cite this: J. Mater. Chem. A, 2019, 7,
25088
acceptors and their blends in organic solar cells by
exploring material design and employing friendly
stabilizers†
Jing Guo,a Yao Wu,a Rui Sun,a Wei Wang,a Jie Guo,a Qiang Wu,a Xiaofeng Tang,b
Chenkai Sun,c Zhenghui Luo,d Kai Chang,d Zhuohan Zhang,e Jun Yuan,f Tengfei Li,g
Weihua Tang, e Erjun Zhou, h Zuo Xiao, i Liming Ding, i Yingping Zou, f
Xiaowei Zhan, g Chuluo Yang, d Zhen Li, d Christoph J. Brabec,b
Yongfang Li c and Jie Min *a

Received 9th September 2019
Accepted 10th October 2019
DOI: 10.1039/c9ta09961a
rsc.li/materials-a
In addition to a high power conversion efficiency, ambient stability is another impact factor for the
successful commercialization of organic solar cells (OSCs). Understanding the role of photovoltaic
materials is the key to address this challenge, but no such studies have been systematically performed
on non-fullerene acceptors (NFAs). In this work, we firstly investigate the role of NFA photo-oxidation in
device degradation. Relevant investigation of physical dynamics underlines the effects on the device
performance for NFA photo-oxidation acting as trap states in exposed blends. In addition, taking ITIC as
an example, we shed some light on the possible mechanisms of NFA photo-oxidation, which cannot be
eliminated by relevant strategies and principles of material design. These results drive us to further
investigate the photobleaching rates of thirty-three NFAs, including fused-ring electron acceptors and
perylene diimide acceptor derivatives. Surprisingly, most of them show a higher optical density loss as
compared to their fullerene-based counterparts. In view of relevant comparative analysis in the
Discussion section, we further propose some design strategies to improve the photo-oxidation stability
of NFAs. More importantly, we also find a stabilizer (namely nickel chelate S6) that can effectively
suppress the photo-oxidation of NFAs and their blends and thus improve the ambient stability of OSCs.

1. Introduction
a
The Institute for Advanced Studies, Wuhan University, Wuhan 430072, China. E-mail:
min.jie@whu.edu.cn
As an important source of renewable energy for a sustainable
b
Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich- future, thin lm solution processed bulk heterojunction (BHJ)
Alexander University Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, organic solar cells (OSCs) have received signicant attention
Germany over the last decade due to their unique advantages for
commercial application, such as low cost, light-weight, exi-
c
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic
Solids, Institute of Chemistry, Chinese Academy of Sciences, 100190 Beijing, China
d
bility and easy mass manufacture.1–4 Tremendous progress have
Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, Department of
been achieved to boost the power conversion efficiencies (PCEs)
Chemistry, Wuhan University, Wuhan 430072, China
e
School of Chemical Engineering, Nanjing University of Science and Technology,
of OSCs increasing from 9% to over 15% in these few years,5–10
Nanjing 210094, China primarily due to the recent development of a range of high
f
College of Chemistry and Chemical Engineering, Central South University, Changsha performance fused-ring electron acceptor (FREA) materials
410083, China like 2,20 -((2Z,20 Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno
[1,2-b:5,6-b0 ]dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-
g
Department of Materials Science and Engineering, College of Engineering, Key
Laboratory of Polymer Chemistry and Physics of Ministry of Education, Peking
2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IDIC),11,12 3,9-
University, Beijing 100871, China
h
bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tet-
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003,
China rakis(4-hexylphenyl)-dithieno[2,3-d:20 ,30 -d0 ]-s-indaceno[1,2-b:5,6-b0 ]
i
Center for Excellence in Nanoscience (CAS), Key Laboratory of Nanosystem and dithiophene (ITIC),13 3,9-bis(2-methylene-((3-(1,1-dicyano-
Hierarchical Fabrication (CAS), National Center for Nanoscience and Technology, methylene)-6,7-diuoro)-indanone))-5,5,11,11-tetrakis(4-hex-
Beijing 100190, China ylphenyl)-dithieno[2,3-d:20 ,30 -d0 ]-s-indaceno[1,2-b:5,6-b0 ]dithiophene
† Electronic supplementary information (ESI) available. See DOI: (IT-4F),14 5Z,50 Z)-5,50 -(((4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-
10.1039/c9ta09961a

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b:5,6-b0 ]dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))
bis-(methanylylidene))bis(3-ethyl-2-thioxothiazolidin-4-one (O-
IDTBR),15 and 2,20 -((2Z,20 Z)-((12,13-bis(2-ethylhexyl)-3,9-diun-
decyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,00 300 :40 ,50 ]
thieno[20 ,30 :4,5]pyrrolo[3,2-g]thieno[20 ,30 :4,5]thieno[3,2-b]indole-
2,10-diyl)bis(me-thanylylidene))bis(5,6-diuoro-3-oxo-2,3-dihydro-
1H-indene-2,1-diylidene))dima-lononitrile (Y6).7 Since their
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current PCEs are close to the theoretical value of device effi-
ciency,16 the main Achilles heel is their limited operational
stability.17–20
The potential degradation routes of OSCs are manifold, and
some even deviate directly from their working principles. For
instance, Heumueller et al. demonstrated that amorphous
polymers generally lead to an open-circuit voltage (Voc) loss in
devices measured under illumination, resulting in burn-in
degradation caused by light-induced traps.19,21 Meanwhile, they
found that the electron affinity of fullerene derivatives can
dramatically inuence the rate of irreversible polymer photo-
bleaching in blend lms.22 In addition, the optimized BHJ
morphology generally is not in thermodynamic equilibrium,
and their photo-stability and thermal stability issues cannot be
solved completely.23,24 Besides, in most cases organic semi-
conducting materials can be easily photobleached in the pres-
ence of molecular oxygen, while their photo-oxidation generally
proceeds by radical mechanisms, thus resulting in irreversible
chemical reactions.18,25–29 In reality, in order to take full advan-
tage of the cost reductions of OSCs from roll-to-roll printing,
devices need to be fabricated under illumination in air and also
be made on inexpensive exible substrates. However, on one
hand, the environmental factors in the fabricating process will
unavoidably degrade the photovoltaic materials and their solar
modules. On the other hand, although commercial exible
substrates such as poly(ethylene terephthalate) (PET) and
poly(ethylene naphthalate) (PEN) provide a sufficient barrier
layer to oxygen, their oxygen transmission rates are several
orders of magnitude larger than the recommended trans-
mission requirements for OSCs of 103 cm3 m2 day1 atm1.20
Thus, enhancement of the inherent stability of photovoltaic
materials, as a signicant challenge for chemists and materials
scientists, can not only reduce the air permeability require-
ments and encapsulation cost but also prolong the service life of
devices. Actually, this challenge is no less important than the
further improvement of the device efficiency and photo-thermal
stability of photoactive layers.
Many studies show that photo-oxidative degradation gener-
ally results in breaking of polymer chains, forms the chemical
defects of photovoltaic materials, reduces the molecular weight
of polymers, causes deterioration of mechanical properties, and
thus leads to rapid deterioration of device performance.18,27,30–33
In addition, under UV or visible illumination in air, [6,6]-
phenyl-C61-butyric acid methyl ester (PCBM) and other fullerene
derivatives have been shown to undergo photo-oxidation reac-
tions with two most commonly observed products of photo-
oxidation, epoxide and carbonyl, on the fullerene cage,22,27,33
which can severely deteriorate the electronic properties of
OSCs.17,20,34,35 In non-fullerene acceptors (NFAs), Luke et al.
recently reported a three-phase degradation process based on
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Journal of Materials Chemistry A
the analysis of the photostability of planar O-IDTBR and
nonplanar O-IDFBR.28 However, the studies regarding the
photo-oxidative stability of NFAs are lagging far behind their
fullerene-based counterparts even though their positive thermal
stability and photo-stability have been highlighted.1,6,36–42 On
one hand, the electronic properties of photo-oxidized NFAs and
their inuence on device performance and fundamental physics
are poorly understood. On the other hand, strategies to effec-
tively improve the photo-oxygen stability of materials and their
blends need to be further explored.28
Herein, we focus our endeavor to tentatively solve these two
questions as pointed out above. We rstly used the classical
NFAs, including IDIC, ITIC, IT-4F, O-IDTBR and Y6, to analyze
their photo-oxidation stability in OSCs based on two common
polymers as donors, including poly[(4,8-bis(5-(tripropylsilyl)thi-
ophen-2-yl)benzo[1,2-b:4,5-b0 ]dithiophene)-co-(5,6-diuoro-2-
(2-hexyldecyl)-4,7-di(thiophen-2-yl)-2H-benzo[d][1,2,3]triazole)]
(J71)43 and poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-
benzo[1,2-b:4,5-b0 ]dithiophene))-alt-(5,5-(10 ,30 -di-2-thienyl-50 ,70 -
bis(2-ethylhexyl)benzo[10 ,20 -c:40 ,50 -c0 ]dithiophene-4,8-dione))]
(PBDB-T).44 Surprisingly, the photo-oxidation stability of these
FREAs in devices is inferior to that of [6,6]-phenyl-C71-butyric
acid methyl ester (PC71BM) with the exception of a Y6 based
blend. Taking ITIC as an example, we systematically investigated
the degradation of a J71:ITIC blend when exposed to light in air.
Furthermore, we discussed the impact of photo-oxidized ITIC on
the corresponding blend morphology and its fundamental
physics. The relationship and difference between ITIC and
PC71BM in the photo-oxidation reaction mechanisms are also
analyzed. In the subsequent Discussion section, by introducing
thirty-three NFAs, we systematically analyze the correlation
between the material structure and photobleaching rate, and
provide some design strategies for improving the photo-oxida-
tion stability of NFAs. Importantly, by introducing six functional
stabilizers as stabilizing additives, we nd an effective and
universal approach to improve the photo-oxidation stability of
NFAs and their blends, thereby alleviating the above-mentioned
cost of barrier materials and relevant technical requirements.
2. Results and discussion
Impact of photo-oxidation of electron acceptors on device
performance
The OSCs in this study were constructed with a conventional
architecture. Solution-processed poly(3,4-ethyl-
enedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) and
a perylene diimide derivative (PDINO) were employed as hole
and electron transporting layers, respectively. The active layers
are composed of donor polymer J71, blended with ve different
FREAs (including ITIC, IDIC, IT-4F, O-IDTBR and Y6), respec-
tively, see Fig. 1A. In order to highlight the inuence of photo-
oxidation of FREAs, PC71BM as their fullerene counterpart has
been introduced. We rstly investigated the device performance
of J71:FREA solar cells under AM 1.5G illumination, while the
normalized PCEs of J71:FREA blends degraded in dry air as
a function of exposure time are depicted in Fig. 1B. As compared
to the device performance of the J71:PC71BM blend lm when
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Fig. 1 Molecule and device architectures as well as impact of photo-oxidation of different FREAs on device behaviors. (A) The investigated
polymer J71, fullerene PC71BM and non-fullerene acceptors, including ITIC, IDIC, IT-4F, O-IDTBR and Y6; (B) normalized PCE of J71 devices
based on degraded BHJ blends as a function of illumination time. (C) Schematic device architecture of solar cells as well as photo-oxidation
process of FREA based BHJ and LbL blends. (D) Normalized PCE of J71:ITIC devices processed with BHJ and LbL structures. There are two
differently processed LbL films: one is illuminating the J71/ITIC film before electrode deposition, and the other is illuminating the J71 film before
ITIC deposition. (E) Current density–voltage (J–V) characteristics of J71:ITIC devices, when their blends were exposed to air for different time
scales, illuminated under simulated AM1.5G illumination. (F) Normalized PCEs as a function of photo-oxidized ITIC (O-ITIC) fraction for degraded
J71:ITIC devices and pre-degraded ITIC devices.

exposed to oxygen, we were surprised to see that those of FREA
based devices with the exception of the J71:Y6 system exhibited
faster degradation over the time interval as compared to that of
the J71:PC71BM blend. Similar to these results, the solar cells
based on PBDB-T blended with four FREAs also exhibited
obvious PCE losses when its BHJ blends were exposed to
ambient conditions (Fig. S1, ESI†). Furthermore, we extended
our studies by blending ITIC with two other polymer donors
PTQ10 and P3HT, which were applied to construct a stable
photovoltaic system. Aer 30 minutes of exposure to light and
air, the photovoltaic performance of the corresponding aged
blends decreased dramatically (Fig. S2, ESI†). It should be noted
that the ambient temperature was controlled below 30  C
during the illumination of the lms.
In order to verify whether the photo-oxidation of NFAs is the
main reason of the attenuation of device performance, taking
ITIC as an example we comprehensively compared the above-
mentioned results with those of similar experiments using the
conventional structure of ITO/MoO3/J71:ITIC/PDINO/Al and the
inverted architecture of ITO/ZnO/J71:ITIC/MoO3/Ag, respec-
tively. The normalized PCEs of J71:ITIC devices based on active
layers degraded with increasing exposure time using different
interlayers are plotted in Fig. S3 in the ESI.† Note that the PCEs
of the fresh solar cells using PEDOT:PSS and MoO3 based
conventional structures, and ZnO based inverted structure are
11.26%, 5.04%, and 10.37%, respectively. Obviously, the trends
of degradation in the corresponding solar cells are identical to
that of conventional devices. Thus, in order to further clarify the
effects or respective contributions of donor materials and NFAs
to device attenuation, we investigated the PCEs of J71:ITIC
devices processed with layer-by-layer (LbL) structures as depic-
ted in Fig. 1C, which exhibit comparable device efficiencies with
BHJ solar cells (Fig. S4, ESI†). Note that there are two different
photo-oxidation LbL device fabrication processes: one is photo-
oxidation of the J71 layer prior to ITIC layer deposition, and
then deposition of the fresh ITIC layer for device fabrication; the
other is deposition of J71 and ITIC in sequence, and then
exposure of the fresh J71/ITIC LbL lm to light in air with ITIC

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Paper Journal of Materials Chemistry A

enriched on the surface.45 As presented in Fig. 1D, the J71/aged-
ITIC LbL lm exhibits worse stability than the aged-J71/ITIC
LbL lm when exposed to light in air, but shows a similar trend
of device attenuation to the J71:ITIC BHJ blend as a function of
illumination time. These results highlight the inuence of ITIC
photo-oxidation on the main degradation in relevant devices.
Besides, in order to identify the role of light or oxygen alone in
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only 10 seconds of light exposure, while its PCE was lost by ca.
70% within 1 minute of light exposure, and by more than 90%
in less than 10 minutes. All of the parameters, including Voc,
short-circuit current density (Jsc) and ll factor (FF), reduced
simultaneously. In addition, we applied photo-oxidized ITIC (O-
ITIC) that had been photo-oxidized in chlorobenzene (CB)
solution to fabricate the fresh solar cells. The detailed prepa-

the degradation of device performance, we investigated the
relevant J71:ITIC devices exposed to light in a nitrogen glovebox
for 60 minutes or exposed to dry air in the dark for 60 minutes.
Note that the ambient temperature is around 25  C. Both
photovoltaic performances of the corresponding solar cells
decreased slightly as depicted in Fig. S5,† and the photovoltaic
performance parameters are listed in Table S1 in the ESI.†
Combined with the similar surface morphologies of the inves-
tigated blends over the illumination time interval (Fig. S6, ESI†),
our results powerfully indicate that the main degradation
process of the J71:ITIC system as well as other FREA systems can
be mainly driven by the photo-oxidation of the corresponding
acceptor materials.
In order to further clarify the degradation behavior and
mechanisms of NFAs in devices, we again took the J71:ITIC
system as an example. Fig. 1E shows the evolution of the current
density–voltage (J–V) characteristics of J71:ITIC solar cells based
on their active layers exposed to light and oxygen for different
time periods, and the corresponding device parameters are
compiled in Table S2 in the ESI.† An overall PCE loss of
approximately 50% in the J71:ITIC solar cell can be found aer
ration process can be found in the Experimental section. The
relevant J–V characteristics of devices with different O-ITIC
fractions are presented in Fig. S7 in the ESI,† and the corre-
sponding photovoltaic parameters are concluded in Table S3.†
Notably, the J–V characteristics of the active layer blended with
different O-ITIC fractions (Fig. S7, ESI†) and the normalized
PCEs (Fig. 1F) are similar to those of J71:ITIC lms exposed to
ambient conditions as a function of illumination time. Based
on these results, it is expected that increased energetic disorder
or defects that result from ITIC photo-oxidation act as trap
states for electrons, which may also cause the main energy loss
discussed in the following section.
Impact of NFA photo-oxidation on physical dynamics
To gain insight into the effects of ITIC photo-oxidation on the
charge transport, space-charge-limited current (SCLC)
measurements were performed on electron-only devices with
the structure ITO/ZnO/J71:ITIC/Ca/Al made from J71:ITIC based
blends exposed in air for different time periods. Relevant carrier
mobilities in degraded J71:ITIC lms are measured by analyzing
the J–V characteristics of single carrier devices under dark

Fig. 2 Impact of ITIC photo-oxidation on blend film transport and recombination kinetics as well as relevant voltage losses. (A) Carrier transport
properties of blend films as a function of degradation time and the relevant mobilities are calculated by the SCLC method and from photo-CELIV
data. (B) Voc of devices based on different degraded films plotted against light intensity on a logarithmic scale. (C) Second order recombination
coefficient (left) and transient time (right) calculated from time delayed collection field photo-CELIV as a function of degradation time. (D)
Schematic illustrating how the density of electron states may evolve during photo-oxidation. The density of states (DOS) is predicted by charge
extraction measurements. (E) Experimental Voc compared to ideal Voc for devices without DE1(Egap  qECT), DE2(qDVrad,belowoc
gap
), and DE3(-
qDVnon-rad
oc ) energy losses.

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Journal of Materials Chemistry A
conditions (Fig. S8, ESI†).46 As shown in Fig. 2A top, the current
density at a given applied voltage drops signicantly with
extending exposure time of BHJ lms under illumination in air.
Here we also investigated the charge carrier mobility m of the
devices by employing the technique of photoinduced charge
carrier extraction by linearly increasing voltage (photo-CELIV,
Fig. S9, ESI†).45,47–49 Although the fresh device shows an average
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mobility value of 1.25  104 cm2 V1 s1 (Fig. 2A bottom), the
exposed blends also show the continuous reduction of the total
carrier mobility in devices. These results imply a correlation
between the transport properties of exposed lms and corre-
sponding photovoltaic performance. Note that details of the
measurement techniques in the SCLC and photo-CELIV
methods are given in Note 1 in the ESI.†
In order to analyze the recombination dynamics of exposed
blends, we studied the relative recombination losses as a func-
tion of light intensity and provided the basic knowledge in ESI
Note 2.† The light intensity dependence of Voc of solar cells with
various exposure time periods of active layers under illumina-
tion intensities ranging from 107 to 2 mW cm2 are plotted in
Fig. 2B. The gradually increased slope S values from 1.27 kT/q
for 0 min to 1.96 kT/q for 30 min of Voc of J71:ITIC degraded
devices imply that the trap-assisted recombination losses are
clearly increased. This is also in agreement with the results of
light intensity dependence of Voc of J71:ITIC:O-ITIC devices with
various O-ITIC fractions (Fig. S10, ESI†). In addition, photo-
CELIV measurements with delayed collection elds were
employed to further identify the recombination dynamics of
relevant degraded blends. The initial density of photogenerated
carriers (n(0)) and the effective 2nd order recombination coeffi-
cient (sB) are calculated by tting the corresponding time-
nð0Þ
dependence of the charge carrier density (nðtÞ ¼  t g ,
1þ
sB
where g is the time-independent parameter.).45,46 Moreover, the
transient time (ttr) by using a formula (ttr ¼ d2/mV, ttr ¼ d2/mV
where d is the lm thickness) was also analyzed.48 Thus, a deep
insight is gained by analyzing sB in parallel to ttr, as these two
material parameters are independent of each other. As pre-
sented in Fig. 2C, it can be concluded that the gradually
extended exposure time periods resulted in the increased 2nd
order recombination coefficient and transient time in relevant
devices based on blends exposed to light in air. These ndings
further underpin the role of photo-oxidative ITIC acting as
a trap existing in blends, where the increased exposure time
periods lead to generation of a more defect-rich microstructure.
In order to probe the effect of ITIC photo-oxidation on
performance degradation with respect to energetic losses and
understand the origin of the Voc reductions in relevant devices
based on photo-oxidized blends, we turn our attention to
characterizing trap states. Transient photocurrent (TPC) and
charge extraction (CE) techniques provide an estimate of the
distribution of trapped charges in the density of states (DOS) of
the semiconductor. Mobile charges generally leave the device
immediately while trapped charges leave the device more slowly
and thus contribute to the current at longer times. Note that
details of the measurement techniques in the TPC and CE
25092 | J. Mater. Chem. A, 2019, 7, 25088–25101
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methods are given in ESI Note 3.† As shown in Fig. S11,† TPC
indicates that degraded devices contain more trapped charges
than the fresh ones. Furthermore, in order to obtain indepen-
dent evidence for this observation, we performed a CE
measurement, which measured the density of photogenerated
charges at open circuit. Fig. S12† shows how the CE curves
change in response to exposure time periods of blends. The
devices based on the exposed blends consistently display
a lower photocurrent in the time interval compared to the fresh
device, which is in accordance with their device performance
(Fig. 1E). In addition, Fig. S13† suggests that the degraded
devices can reach a lower Voc compared to the fresh one at
a given density of photogenerated charges, which is expected
because the photooxidative-induced defects or traps can result
in smaller quasi-Fermi level splitting. Thus, these analyses can
prove our hypothesis that the density of electron states may
evolve during photo-oxidation of blends (Fig. 2D). This trend is
also demonstrated by the photo-oxidation of fullerene-based
active layers.27 Besides, combining transient photovoltage (TPV)
and CE techniques, we are able to determine the charge carrier
density in relation to the carrier lifetime via the equation (s ¼
s0(n0/n)l, where s0 and n0 are constants and l is the so-called
recombination exponent.).50,51 Based on this point, we can
calculate the non-geminate recombination order R (R ¼ l + 1) in
relevant devices without and with O-ITIC doping, as shown in
Fig. S14 in the ESI.†21,47 The tting of the data yield R ¼ 2.11 for
the fresh device without O-ITIC doping, indicating a mecha-
nism close to an ideal bimolecular recombination, justied by
the FF of 71.12% as well as a high PCE of over 11% (Table S3†).
In addition, we obtained R ¼ 2.73 for the 0.7% O-ITIC blend and
R ¼ 3.47 for the 3.5% O-ITIC blend. The longer carrier lifetimes
at xed charge density existed in the O-ITIC based solar cells are
associated with the more bulk traps as compared to the fresh
J71:ITIC solar cells.
Here we further investigated the electroluminescence (EL)
spectra and the EQEPV (the spectral photovoltaic external
quantum efficiency) using Fourier-transform photocurrent
spectroscopy (FTPS) measurements on a series of J71:ITIC
devices, which were exposed to light and air for various time
periods. The introduction of energy losses in devices and rela-
tive logic formula and methodology are also presented in ESI
Note 4.† Details of the measurement results are given in Fig. S15
and S16.† The voltage loss DVoc due to radiative and non-
radiative recombination (Fig. S15a, ESI†) can be described with
the following equation: qDV ¼ DE1 + DE2 + DE3 ¼ (Egap  qECT) +
qDVrad,below
oc
gap
+ qDVnon-rad
oc .52 Furthermore, Table S4† summa-
rizes the values measured and calculated from FTPS and EL
measurements, and Fig. 2E presents the contributions to Voc
losses regarding the difference and relationship of the optical
band (Egap), CT state, Voc and the three terms of energy losses. In
general, the difference between the resulting radiative-limit
Voc,rad and the measured Voc can be assigned to non-radiative
recombination losses (DVoc,non-rad). The relative size of the
DVoc,non-rad component for solar cells with different exposure
time periods should reect the degree of non-radiative recom-
bination in blends. It can be found that the main energy losses
due to non-radiative recombination signicantly increase with
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Paper
extending exposure time interval. As expected, the voltage losses
measured by the FTPS technique are mirrored in the carrier
transport properties and carrier recombination lifetime. Over-
all, the results of the charge transport and recombination
dynamic analysis as well as the discussion of energy losses in
relevant devices underline the effects of NFA photo-oxidation
acting as trap states in exposed blends on device performance.
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Possible mechanisms of NFA photo-oxidation
Taking ITIC as an example, here we shed some light on the
possible mechanisms of NFA photo-oxidation, and compared
them with that of fullerene derivatives (e.g. PC71BM), as depic-
ted in Fig. 3. Fig. 3A shows the matrix-assisted laser desorption/
ionization time-of-ight (MALDI-TOF) mass spectrometry
spectra of a neat ITIC lm aer 10 h exposure to light in air. It
can be easily found that photo-oxidized ITIC species (with up to
4 oxygen atoms) in the exposed ITIC lm were formed. The
investigated photo-oxidized species is also found by using FTIR
absorption spectra of the degraded ITIC lm, which show
a dramatic appearance of hydroxyl and carbonyl groups around
3500–3000 cm1 and 1700 cm1 (Fig. 3B), respectively. In
addition, X-ray photoelectron spectroscopy (XPS) measure-
ments show that there is an obvious increase of the carbon–
oxygen (C–O) bond in surface compositions aer 10 h illumi-
nation (Fig. 3C). An analysis of the C–O bond areas reveals that
a total of 15.3% photo-oxidized ITIC (O-ITIC) was found in the
relevant ITIC lm. A similar trend in the J71:ITIC blend is also
found as shown in Fig. S17 in the ESI.† This result indicates that
oxygen atoms are chemically attached to the ITIC under illu-
mination in air, thus resulting in a dramatic structural change
upon photo-oxidation.18,26,33 Besides, chemical processes related
to degradation may lead to a reduction of average molar mass
due to macromolecular chain bond scission. Fig. 3A also shows
some pieces of broken molecules like the breaking of the cyano
group in acceptor units and the rupture of end groups. This
phenomenon is also demonstrated by the FTIR absorption
spectra. During irradiation of the pristine ITIC, the intensity of
signals in FTIR absorption spectra related to CH2 at 2929 cm1
(nas) and 2846 cm1 (ns), C^N at about 2216 cm1, and C]C at
1536 cm1 and 1395 cm1 groups, shown in Fig. 3B, immedi-
ately starts to decrease which is related to the destruction of the
p-conjugated system of ITIC.26 This phenomenon should be
identical to the photo-oxidation behavior of other NFAs.
Chemical processes related to degradation leads to a reduc-
tion of average molar mass due to macromolecular chain bond
scission. This reminds us to further investigate and discuss the
differences and relationships between fullerene derivatives and
NFAs. Fig. 3D exhibits photographs of photo-oxidized ITIC and
PC71BM pristine lms upon different times of exposure, while
Fig. 3E shows the absorption spectra of photo-oxidized ITIC and
PC71BM lms. As compared to the PC71BM lm, the absorption
peak of ITIC signicantly decreases in intensity and blue-shif-
ted aer a period of exposure to light in air. It is attributed to
a loss in conjugation along the molecular backbone supported
by the MALDI-TOF and FTIR measurements. In contrast,
oxidation of the fullerene cage is not expected to obviously
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reduce absorption as appreciably. Notably, the absorption
reduction caused by photo-oxidation of NFAs cannot directly
explain the respective amount of irreversible performance
reduction in OSCs. Due to the different electron affinity of
photovoltaic materials, the photochemical reactions of acceptor
materials are slightly different with the photo-degradation
processes of their blends.34 These results suggest that the
molecular structure of ITIC could provide more active photo-
oxidation reaction sites, such as the double bond between the
donor and acceptor units, the double bond on thiophene or
bithiophene outlying central building blocks, side chains of
donor units and so on, as depicted in Fig. 3F. Moreover, it is not
possible to clear out the whole photochemical reactions in such
a very complicated situation. Thus, theoretical principles and
effective approaches for designing new NFAs and suppressing
photo-oxidation of NFAs and their blends are very important
and urgent, which will be discussed in the following section.
3. Discussion
Suppressing photo-oxidation of NFAs via material design
In order to nd effective strategies to improve the photo-
oxidation stability of NFAs, we select thirty-ve acceptors,
including thirty-three NFAs and two fullerene derivatives
(PCBM and PC71BM) for comparison, as depicted in Fig. 4A. The
provenances of materials are provided in Table S5 in the ESI.†
Thin lms of acceptor materials on quartz were made by spin-
coating from solution and the UV-visible absorption spectrum
of each lm was measured at various time periods during
continuous illumination with a xenon arc lamp exposed to an
ambient atmosphere. The lamp provides an illumination
intensity of 100 mW cm2 (one sun illumination) and a spec-
trum that contains a wide spectral range from 300 to 1100 nm
and has a close spectral match with the AM 1.5G spectrum over
the visible wavelengths (Fig. S18, ESI†). In this work, we used
three different lms for each component to study its photo-
oxidation behavior. The lms of NFAs and fullerene derivatives
were found to photo-bleach at substantially different rates
varying from minutes to days. The time evolution of relevant
pristine lm absorption is shown in Fig. S19a–S53a in the ESI.†
The normalized optical density loss per hour was calculated for
each component by tting the initial slope of the decay in the
lm absorption maxima, normalized by the initial peak
absorption before aging (Fig. S19b–S53b, ESI†). Note that the
time period corresponding to the 20% loss in optical density
was used for the t. As a result, Fig. 4B provides the photo-
bleaching rates of NFAs and fullerene derivatives. It is found
that the photo-bleaching rates of the investigated NFAs with the
exception of IDIC-4F,53 IDIC-4Cl,53 O-IDTBR and l-IDTBTRh54
are slower than those of PCBM and PC71BM.
It is well known that the amounts of NFAs, which contain ve
key constituent components including donor units, acceptor
units, conjugated bridges, side chains, and heteroatom substi-
tutions, have been developed to tune the blend morphology and
improve the optoelectronic properties.55–60 Based on this view,
the differences of photo-bleaching rates in these NFAs pre-
sented in Fig. 4B can also provide some promising inspiration
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Fig. 3 The analysis of possible chemical reactions of NFA photo-oxidation. (A) Negative ion mode MALDI-TOF measurement of the neat ITIC film
degraded under one sun in dry air for 10 hours. (B) FTIR spectra of fresh and aged ITIC films with different exposure durations under one sun illu-
mination in dry air (range: wavenumber from 4000 cm1 to 400 cm1). (C) XPS O(1s) spectrum of fresh pristine ITIC films before and after 10 h
exposure to light in air. (D) Photographs of photo-oxidized ITIC and PC71BM pristine films upon different times of exposure. (E) UV-visible spectra of
photo-oxidized ITIC and PC71BM pristine films upon different times of exposure. (F) The primary photo-oxidation reaction sites of ITIC and PC71BM.

for NFA design. From this perspective, we also analyze and FOIC61 and their derivatives based on different end groups
summarize how to improve the photo-oxidation stability of (Fig. S54, ESI†) can be systematically investigated. By comparing
NFAs via material design. In the acceptor units, IDIC, ITIC, IDIC-4F and IDIC-4Cl, IT-4F and IT-4Cl,62 and F8IC63 and C8IC,64

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Fig. 4 The Investigated non-fullerene and fullerene acceptors as well as their photo-bleaching rate. (A) Molecular structures of the investigated
acceptors. (B) Photo-bleaching rate of acceptor materials, including non-fullerene acceptors and fullerene derivatives.
we nd that the NFAs based on chlorine-substituted end groups
are much more stable than uorine-substituted acceptor units
in FREAs. Moreover, 3,9-bis(2-methylene-(5&6-methyl-(3-(1,1-
dicyanomethylene))-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-
dithieno[2,3-d:20 ,30 -d0 ]-s-indaceno[1,2-b:5,6-b0 ]-dithiophene (IT-
M),65 IT-DM,65 3,9-bis(4-(1,1-dicyanomethylene)-3-methylene-2-
oxo-cyclopenta[b]thiophen)-5,5,11,11-tetrakis(4-hexylphenyl)-
dithieno[2,3-d0 :2,3-d0 ]-s-indaceno[1,2-b:5,6-b0 ]-dithiophene (ITCC),66
ITTC67 and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-cyclo-
pentane-1,3-dione[c]-1-methyl-thiophe))-5,5,11,11-tetrakis(4-hex-
ylphenyl)-dithieno[2,3-d:20 ,30 -d0 ]-s-indaceno-[1,2-b:5,6-b0 ]-dithio-
phene (MeIC)10 have the same order of magnitude of the photo-
bleaching rate as ITIC based on 2-(3-oxo-2,3-dihydroinden-1-
ylidene)malononitrile (INCN) units as end-capping groups,
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indicating that methyl-INCN, dimethyl-INCN, and thiophene-
fused end groups (CPTCN) as well as methyl-CPTCN and Cl-
CPTCN may not be able to enhance the photo-oxidation
stability of FREAs. This conclusion is also demonstrated by the
FOIC, F8IC and T8IC acceptors based on larger fused-rings,
which show a similar trend of the photo-bleaching rate.
Besides, O-IDTBR based on two dual acceptor units, including
an ethyl-rhodanine unit and a benzothiadiazole unit, is more
stable than IDIC based on INCN as the end group. Surpris-
ingly, 2,20 -((2Z,20 Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-
12,13-dihydro[1,2,5]thiadiazolo[3,4e]thieno [200 ,300 :40 ,50 ]thieno
[20 ,30 :4,5]pyrrolo[3,2-g]thieno[20 ,30 :4,5]thieno[3,2-b]indole-2,10-
diyl)bis(methanylyli-dene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-
diylidene))dimalononitrile (Y5)68 without F atom substitutions
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shows a slightly lower optical density loss than Y6 with F-sub-
stituted INCN units, probably due to the different absorption
spectra resulting in a difference in the number of photons
absorbed in relevant lms. In the donor units, the photo-
bleaching rate of IHIC69 based on six-fused rings as the core is
about one order lower than that of ITIC based on seven-fused
rings as the core. However, by comparing IT-4F and F8IC, IT-4Cl
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and C8IC, and ITTC and T8IC with the same fused-ring struc-
ture, we nd that extending the core from seven- to eight-fused
rings can improve the stability of FREAs. However, in the per-
ylene diimide (PDI) acceptor derivatives the thiophene based
PDI molecule is more stable than PDI NFAs based on benzo-
dithiophene (BDT) units as cores. Interestingly, introducing
pyrene-fused units into PDI acceptor derivatives can effectively
weaken the difference of photo-oxidation rates between thio-
phene-based and BDT-based PDI acceptors. Besides, some
FREAs based on special cores, including COi8DFIC,60 Y6, and
INPIC-4F,70 also show a faster photo-oxidation rate than their
fullerene counterparts (Fig. 4B). Despite, the above-mentioned
results suggest that replacing common central building blocks
with other units with stronger electron-donating ability is an
useful way to suppress photo-bleaching of FREAs.
Fine-tuning of the molecular structure, which in some
cases resulted in huge differences in device performance, can
also greatly change the photo-oxidation rate of the acceptor
materials. In the alkyl side chains or end chains, for example,
l-IDTBTRh based on alkoxybenzene units as side chains is
more stable than the octyl-substituted O-IDTBR molecule. In
addition, the photo-bleaching rate of alkylthiophene-
substituted 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-
indanone))-5,5,11,11-tetrakis(4-hexylthienyl)-dithieno[2,3-d:20 ,30 -
d0 ]-s-indaceno[1,2-b:5,6-b0 ]-dithiophene (ITIC-Th)71 is slightly
higher than that of alkylbenzene-substituted ITIC. Importantly,
by introducing terminal hexyl chains into thieno[3,2-b]thio-
phene (TT) moieties of the indacenodithieno[3,2-b]thiophene
(IDTT) core, the corresponding ITC6-IC72 shows a lower optical
density loss, probably due to the increased steric hindrance of
the double bond between the donor and acceptor units in
FREAs.32,55 Notably, the differences of photo-bleaching rates
between IT-4Cl without octyl-substitutions and NCBDT-4Cl73
with octyl substitutions attached to the benzene-ring of the IDTT
core are not obvious. In these few years, more and more atten-
tion has also been paid to the isomerization design of NFAs.54
Here we also nd that the isomers of FREAs can signicantly
make a difference in photo-oxidation stability, like ITTC and
ITCNTC74 acceptors. Much to our surprise, the geometric shape
of the angular indaceno[2,1-b:6,5-b0 ]dithiophene (a-IDT) and
linear IDT (l-IDT) subunits (a-IDTBTRh and l-IDTBTRh) can play
a pivotal role in governing the photo-oxidation stability with
a photo-bleaching rate of 287% for a-IDTBTRh and a photo-
bleaching rate of 0.04% for l-IDTBTRh, approximately four
orders of magnitude difference. Note that a-IDT is an analog of l-
IDT via intramolecular annulation, in which the central phenyl
ring was linked to the b-position of the thiophene ring but fused
on its a-position. Further research based on these two isomers is
underway. It should be also noted that applying non-fused
electron structures is another strategy to improve the photo-
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oxidization stability of relevant NFAs.75 Overall, our results
indicate that ne-tuning and isomerization of the molecular
structure can effectively improve the photo-oxidation stability of
NFAs, which is relatively unfamiliar in previous studies.
Suppressing photo-oxidation of NFAs via introducing
stabilizers
Considering the results and analysis of optical density loss of
FREAs in the previous sections, it's very difficult to gure out the
whole reaction routes due to multiple photo-degradation by-
products on one hand. On the other hand, the photochemical
processes not only include the photo-oxidation reaction, but
also under the same conditions trigger various chemical reac-
tions without oxygen participation, including the breaking of
chemical bonds via light absorption,20 photo-induced side
chain rearrangement (like the photo-Fires reaction),26 chain
scission, crosslinking, etc.35,76 Thus, objectively speaking, it will
become very difficult to solve the photo-oxidation issues
through material design.
Here we focus our endeavor to choose some common
stabilizers in anticipation of their abilities to inhibit photo-
oxidation of NFAs and their blends. Fig. 5A shows the molecular
structures of small molecule stabilizers, which are commer-
cially available stabilizing additives for increasing the longevity
of industrial products. Generally, their stabilization mecha-
nisms are fully understood in biology and food industries; here
we selected six different stabilizers including hydroperoxide
decomposers (2,2,6,6-tetramethylpiperidinooxy (S1) and
tris(2,4-di-ter-butylphenyl)phosphite (S3)),77,78 singlet and/or
triplet quenchers (zinc dibutyldithiocarbamate (S5) and nickel
dibutyldithiocarbamate (S6)),79,80 free-radical scavengers (S6)81
and single oxygen quenchers (2,6-di-t-butyl-4-methylphenol
(S2), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxypheny)
propionate] (S4) and S6).82,83 Fig. 5B depicts the autoxidation
cycle of NFAs and their primary reactive sites as discussed in
Fig. 3F as well as the points of attack of stabilizing additives. As
expected, the successful application of these stabilizers in other
elds served as motivation to elucidate whether these stabi-
lizers could also be employed to suppress photo-oxidation
reactions of NFAs. Continuing with the ITIC as an example, we
further analyzed the effects of these stabilizers on the photo-
aging behavior of continuously irradiated ITIC lms blended
with 2 wt% stabilizers S1–S6. As shown in Fig. 5C, as compared
to the pristine ITIC lm, the additive doped ITIC lms are more
stable. Among these six stabilizers, S6 as a nickel chelate is the
best quencher of reactive oxygen species (ROS), probably due to
a low oxidation potential (Eox ¼ 74 mV vs. Fc/Fc+).84 Fig. 5D
shows the changes of absorption spectra in the exposed ITIC
lms without and with 2 wt% S6, and Fig. 5E provides the
degradation kinetics of the ITIC lm as a function of the weight
fraction of S6. Aer 6 h exposure to light and air, a plain ITIC
lm photo-bleaches by about 80%, while under the same
conditions lms containing 10 and 20 wt% S6 photo-bleach to
a much lesser extent. In addition, Fig. 5F exhibits the photo-
graphs of photo-oxidized ITIC lms upon different times of
exposure in air without and with 2 wt% S6. Since
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Fig. 5 Suppressing photo-oxidation of NFAs and their blends as well as relevant devices through stabilizers. (A) The chemical structures of the
stabilizers studied in this work. (B) Autoxidation cycle of NFAs and points of attack of stabilizing additives (ROS: reactive oxygen species; RH:
pristine NFA; R*: carbon centered radical formed by H-abstraction; H-donor: pristine polymer donor). The reactive sites mainly include three
parts: alkene based units, cyclopentadiene based units (e.g. thiophene) and alkyl chain based units. The ROS quencher or stabilizers can
effectively inhibit the presence of ROS, and avoid the decomposer of NFAs. In addition, under illumination, free NFA radicals are formed. R* will
quickly react with ground state molecular oxygen, O2, forming chain-initiating, oxygen-centered radicals, which further react to form hydro-
peroxides by hydrogen abstraction and thus open a second cycle.84,85 Antioxidants can be introduced to induce termination steps for autoxi-
dation, forming stable radicals that suppress the autoxidation cycles. (C) Degradation kinetics of light-soaked ITIC pristine films in air without and
with the 2 wt% stabilizers as pointed out above. (D) Photo-bleaching behavior of ITIC without and with 2 wt% S6. (E) Degradation kinetics of ITIC
as a function of the weight fraction of S6. (F) Photographs of photo-oxidized ITIC films upon different times of exposure in air without and with 2
wt% S6. (G) Degradation kinetics of NFAs IDIC, IT-4F and O-IDTBR without and with 2 wt% S6 in air under illumination with a solar simulator
(Fig. S16†). (H) Degradation behavior of ITIC and its J71:ITIC blends in the absence/presence of S6 under illumination of a one sun simulator in air.
(I) Current density–voltage characteristics of J71:ITIC blends with the different contents of S6. (J) Semi-logarithmic representation of the Voc
dependence on light intensity in relevant devices without and with 2 wt% S6. (K) Depiction of the temporal evolution of PCE of unencapsulated
devices with a device structure of ITO/ZnO/J71:ITIC/MoO3/Ag which were continuously light soaked in dry air using a solar simulator (100 mW
cm2; an average of six devices).

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photoluminescence (PL) is usually a much more sensitive probe
of degradation than UV/vis absorption, we also compare the
evolution of PL spectra of the illuminated ITIC lms without
and with 2 wt% S6 (Fig. S55†). Surprisingly, in the rst 30 min, 2
wt% S6 inhibits almost fully the photo-oxidation of a thin lm
(change of <1% PL intensity), while during the same exposure
time period the PL intensity of the un-doped ITIC lm was
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reduced to 60% of its original level. All these data deliver an
intuitive message of the role of S6 playing in the ITIC lm when
exposed to light in air, which can effectively suppress the
breaking of molecular backbones. Besides, the photo-oxidation
kinetics of lms of IDIC, IT-4F and O-IDTBR, and of the corre-
sponding blends with 2 wt% S6 (Fig. 5G, derived from the
reaction spectra, see Fig. S56–S58†) further reveal its general
applicability in protecting NFAs against photo-bleaching.
Fig. 5H shows the temporal evolution of the optical density
of lms processed from the polymer J71, NFA ITIC and their
blends without and with 2 wt% S6. It is found that 2 wt% S6
cannot signicantly inhibit the photo-oxidation of J71, as
shown in Fig. S59.† The photo-oxidation degradation of the
J71:ITIC blend can also be signicantly suppressed by addition
of S6. The changes of the optical density of the corresponding
lms are presented in Fig. S60.† Thus, the suppression of the
photo-bleaching rate of ITIC phases in unstable blends not only
conrms the antioxidative ability of S6, but also provides
insight into the non-sacricial mechanisms of stabilization by
S6. Besides, similar trends can be found for other NFAs
(including IDIC, IT-4F and O-IDTBR) and their blends with
polymer J71 (Fig. S61–S63†). These results further suggest that
an additional stabilizing effect of S6 in these systems is based
on the reduction of 1O2 concentration, either by quenching of
1
O2 itself and/or quenching of triplet excited states of the
sensitizer.84
In addition to the photovoltaic materials in lms, we also
evaluated the impact of S6 additives on the photovoltaic
performance of relevant devices based on J71:ITIC blends
without and with various contents. Fig. 5I shows the J–V char-
acteristics of fabricated devices with up to 2 wt% S6 integrated
into J71:ITIC blends, and Table S6† presents the relevant
photovoltaic parameters. Devices containing 2 wt% S6 exhibits
a PCE of 6% but the photovoltaic performance drops slightly as
compared to the reference devices, which is predominately
related to a drop in Jsc and FF. We attribute the loss in Jsc and FF
to the occurrence of trap-assisted recombination in the pres-
ence of S6. This conclusion emerges from the slope of light
intensity dependence of Voc measurements as depicted in
Fig. 5J, which for doped devices containing 2 wt% S6 increased
to 1.30 kT/q compared to 1.13 kT/q for un-doped devices.
Furthermore, we conducted the investigations of the protective
nature of S6 in unencapsulated J71:ITIC solar cells containing 2
wt% stabilizer for evaluating the S6 role of improving the photo-
oxidation stability of devices. It is apparent that the S6 doped
devices exhibit higher ambient stability as compared to the
devices without S6 measured under one sun illumination in air,
as presented in Fig. 5K. Similar improvements were observed
for other J71:NFA solar cells with their active layers directly
exposed to light and oxygen for different time periods as shown
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in Fig. S60d–S63d,† highlighting the technological relevance of
S6 in increasing the resilience of OSCs towards light and
oxygen.
4. Conclusion
In summary, we investigate the impact of photo-oxidation of
classical acceptors, including ITIC, IDIC, IT-4F, O-IDTBR and
Y6, on device behaviors, and nd that the photovoltaic param-
eters of corresponding solar cells based on J71 and PBDB-T as
donor materials degraded dramatically when their BHJ blends
were illuminated in air within a few minutes. Taking the
J71:ITIC system as an example, we systematically analyze the
degradation nature of relevant devices, mainly resulting from
the ITIC photo-oxidation rather than the other factors (e.g. J71
photo-oxidation, interfacial layers and device structures).
Furthermore, we establish a relationship between the presence
of specic oxidative defects and the resulting change in the
electronic properties of relevant J71:ITIC devices based on their
blends exposed in air for different time periods. Meanwhile we
depict the impact of ITIC photo-oxidation on charge transport
and recombination kinetics as well as relevant energy losses in
relevant blends. Notably, our results suggest that exposure of
NFAs to oxygen provokes the irreversible intercalation of oxygen
atoms and breaking of molecular backbones. Taking ITIC and
PC71BM as an example, we shed some light on the possible
mechanisms of NFA photo-oxidation. Based on this analysis,
our ndings highlight the highly photoactive nature of NFAs
which must be taken into account for the choice of the
manufacturing process for industrial products.
The large difference of photo-bleaching rates of ITIC and
PC71BM lms investigated drives us to further construct theo-
retical principles and nd effective approaches for designing
new NFAs and suppressing photo-oxidation of NFAs and their
blends. For this purpose, we collected thirty-three NFAs and two
fullerene derivatives, and measured and analyzed relevant
photo-bleaching rates. As a result, some inspiration for guiding
the design of new NFAs for weakening photochemical reactions
is provided, although these strategies do not solve the photo-
oxidation issue fundamentally. Fortunately, we have shown that
a nickel chelate S6 can act as a potent antioxidizing agent for
a wide range of NFAs and their blends. The photovoltaic and
physical measurements of J71:ITIC devices suggest implications
on the recombination behavior at higher loadings of S6 addi-
tives, most likely due to trap state formation. But importantly,
the S6 doped device shows better photo-oxidation stability as
compared to the un-doped device, indicating that using S6 and
other similar compounds as antioxidants can represent a cost-
effective route toward organic solar cells with extended
longevity. For this, we strongly anticipate that similar
compounds can be tailored to prevent energetic trapping and
further enhance the stabilization efficiency. Ultimately, in their
current state, the long term stability of organic solar cells will be
not only reliant on effective barrier layers and successful
encapsulation, but also depends on the choice of highly stable
photovoltaic materials and/or effective and harmless stabilizers.
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Conflicts of interest
The authors declare no competing nancial interests.
Acknowledgements
This work was nancially supported by the National Natural
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Science Foundation of China (NSFC) (Grant No. 21702154 and
51773157) and supported by the Fundamental Research Funds
for the Central Universities (2042017kf0269). We also thank the
opening project of the Key Laboratory of Materials Processing
and Mold for support.
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