Cheng 2016

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Stability of organic solar cells: challenges

and strategies
Published on 18 February 2016. Downloaded by New York University on 18/02/2016 22:45:08.
Cite this: DOI: 10.1039/c5cs00593k

Pei Chengac and Xiaowei Zhan*b
Organic solar cells (OSCs) present some advantages, such as simple preparation, light weight, low cost
and large-area flexible fabrication, and have attracted much attention in recent years. Although the
power conversion efficiencies have exceeded 10%, the inferior device stability still remains a great
challenge. In this review, we summarize the factors limiting the stability of OSCs, such as metastable
morphology, diffusion of electrodes and buffer layers, oxygen and water, irradiation, heating and
mechanical stress, and survey recent progress in strategies to increase the stability of OSCs, such as
Received 4th August 2015 material design, device engineering of active layers, employing inverted geometry, optimizing buffer
DOI: 10.1039/c5cs00593k layers, using stable electrodes and encapsulation. Some research areas of device stability that may
deserve further attention are also discussed to help readers understand the challenges and opportunities
www.rsc.org/chemsocrev in achieving high efficiency and high stability of OSCs towards future industrial manufacture.
1. Introduction environmentally friendly, is a good candidate. Especially, organic

solar cells (OSCs) present some advantages, such as simple prepara-
Developing renewable clean energy technologies is the focus of tion, light weight, low cost, flexibility and large-area fabrication, and
the 21st century. Solar energy, which is inexhaustible and have attracted much attention in recent years.1–11
Many strategies have been employed to achieve higher
a
Beijing National Laboratory for Molecular Sciences and CAS Key Laboratory of power conversion efficiency (PCE), for example, designing and
Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, synthesizing new electron donor and electron acceptor materials
b
Beijing 100190, China with broad photon absorption and high mobility;12–17 employing
Department of Materials Science and Engineering, College of Engineering,
versatile third components in the active layer to fabricate ternary
Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,
Peking University, Beijing 100871, China. E-mail: [email protected] blend OSCs;18–24 controlling the morphology of the active layer;25–31
c
University of Chinese Academy of Sciences, Beijing 100049, China using buffer layers between the active layer and electrodes;32–36 and
Pei Cheng received his BS degree in Xiaowei Zhan obtained a PhD

polymer materials and engineering degree in chemistry from Zhejiang
from Sichuan University in 2011. University in 1998. He was then a
Now he is a PhD student at the postdoctoral researcher at the
Institute of Chemistry, Chinese Institute of Chemistry, Chinese
Academy of Sciences. His research Academy of Sciences (ICCAS) from
interests are focused on organic 1998–2000, and in 2000 he was
solar cells. promoted to Associate Professor at
ICCAS. Dr Zhan worked in the
University of Arizona and the Geor-
gia Institute of Technology from
2002–2006 as a Research Associate
Pei Cheng Xiaowei Zhan and a Research Scientist. He has
been a full professor at ICCAS
since 2006. In 2012 he moved to Peking University. His research
interests are in the development of materials for organic electronics
and photonics. Prof. Zhan is an associate editor of Journal of
Materials Chemistry C and a Fellow of the Royal Society of Chemistry.
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
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designing and fabricating new device structures.37–42 As a result,

OSCs exhibit PCEs of up to 11%43 for single junctions and 12%44
for tandem junctions in a small device area (o0.1 cm2).
Economic assessment of OSCs and silicon solar cells
demonstrates that a competitive power output from OSCs can
be reached if efficiencies of ca. 7% can be achieved in large area
modules and if lifetimes of at least 5 years can be attained.45
Despite PCEs of ca. 7% (4 cm2)46 and ca. 5% (114.5 cm2)47 being
achieved in a large device area, the insufficient stability will be
the limiting factor for future industrial production.48–55 For
example, Heeger et al.56 fabricated a conventional OSC with the

structure of indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):
poly(styrene sulfonate) (PEDOT:PSS)/bulk heterojunction (BHJ) active
layer/aluminium (Al), but this device died after being stored in air for
25 h. Garcia-Belmonte et al.57 tested the stability of OSCs for over
8000 h (ca. 1 year) in a glove box and found a gradual reduction in
efficiency from about 3% to 1.5%. Krebs et al.58 studied the stability Fig. 1 Schematic diagram of the factors limiting the stability of OSCs.
of OSCs under continuous illumination (AM 1.5G, 1000 W m2) at
72 1C; after a 13 000 h (ca. 1.5 year) test, the device preserved only 2%
of its initial PCE. To achieve the goal of more than 5 year lifetime still
remains a great challenge.
In this review, we focus our discussion on the factors limiting
the stability of OSCs and recent developments in strategies to
increase the stability of OSCs, especially on those accomplished
in the last two years. Firstly, we summarize the factors that limit
stability, such as metastable morphology, diffusion of electrodes
and buffer layers, oxygen and water, irradiation, heating and
mechanical stress. Then, we survey and analyze strategies to
increase stability, such as material design, device engineering of
active layers, employing inverted geometry, optimizing buffer layers,
using stable electrodes and encapsulation. Finally, we propose the
strategies to overcome the challenges in achieving high stability and
the possible research directions in the near future.
Fig. 2 Simulated and measured short-circuit current. Black squares repre-

sent the relative short-circuit current as theoretically expected from the time-
2. Factors limiting the stability of OSCs dependent morphology probed by mGISAXS. The red line indicates the measured
normalized short-circuit current density. Error bars are estimated from the error
Different from the research environment in labs, there are a lot
in the structure parameters. (a–c) Visualisation of the inner film morphology at
of factors that can limit the stability of OSCs in the real world. the different times stated above as generated during the Monte-Carlo simula-
In this part, we discuss the factors that limit the stability of tion. The images represent an excerpt of 2.5 mm 2.5 mm. The red circles
OSCs during their whole lives in terms of metastable morphology, represent the domains of a pure material. The green cylinder walls represent,
diffusion of electrodes and buffer layers, oxygen and water, irradia- together with the red core, the active area of the solar cell where absorbed
photons contribute to charge carrier generation. Photons absorbed in the blue
tion, heating and mechanical stress (Fig. 1).
phase do not contribute. (d) Unit cell of a square lattice as assumed for predicting
the theoretical values of the normalized short-circuit current density.59 Reprinted
2.1. Metastable morphology and diffusion of electrodes and with permission from ref. 59. Copyright 2013, Wiley.
buffer layers
An active layer is the key component of OSCs, in which there are Employing high boiling point (BP) solvent additives in the active
generally two or three phases (the donor phase, the acceptor layer has been one of the main approaches in the last decade of OSC
phase and the donor/acceptor mixed phase). Phase separation research. Although these solvent additives increase PCE, they
is always metastable due to the strong mobility of organic decrease the device stability by forming a more unstable morphology
materials. Müller-Buschbaum et al.59 used micro-focused grazing of the active layer.60–64 Park et al.63 fabricated OSCs based on
incidence small angle X-ray scattering (mGISAXS) to probe the poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b 0 ]dithiophene-2,6-
metastable morphology of a polymer/fullerene blend. They proposed diyl][3-fluoro-2-[(2-ethylhexyl)-carbonyl]-thieno-[3,4-b]thiophene-
a model of morphological degradation (Fig. 2): the donor domains diyl]] (PTB7)/[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC71BM)
drift apart from each other (smaller domains vanish whereas larger without or with 3% 1,8-diiodooctane (DIO) (BP: 332 1C). After
ones grow). being stored in air for 300 h, devices without or with 3% DIO
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will change their photon absorption, energy levels and charge

carrier mobilities. Thirdly, the oxygen doping in the active layer
can enhance hole concentration, which results in an increase of
the density of deeper traps for electrons and a decrease of the
fill factor (FF) and the open circuit voltage (VOC).73,74
The ingress of water in the device is another important
factor limiting the stability (Fig. 4). Water can diffuse into the
device via the hygroscopic PEDOT:PSS buffer layer and metal
electrodes with an activation energy of 42 kJ mol1 (measured
and calculated by Arrhenius relation).75 Firstly, water can
damage the low WF metal electrodes as an oxidation agent.76

It was observed that large defects were appeared on the Al
Fig. 3 Schematic diagram of the diffusion of electrodes and buffer layers. electrode after the exposure of water.77,78 These defects can act
as pinholes to allow more ingress of water.79 Secondly, the
ingress of water into the interface of the active layer and the
preserved 61% and 39% of the original PCEs, respectively. The electrode can form a insulating metal oxide interlayer, leading
excessively aggregated PC71BM in the DIO-assisted degraded to a decrease of effective active layer/electrode interface area
film would block the formation of a suitable morphology which which is harmful to charge extraction.80 Thirdly, water diffusing
had enough donor/acceptor (D/A) interfaces and bi-continuous into the active layer can move PC61BM and thus induce excessive
networks. aggregation of fullerenes. The larger scale of phase separation
Like the donor and acceptor materials, the electrodes and decreases the D/A interfaces, which is harmful to exciton dis-
buffer layers also show mobility. As shown in Fig. 3, the indium sociation and causes a huge reduction in device performance.81
(In) of ITO can diffuse into the PEDOT:PSS layer65 and the In the real world, oxygen and water always simultaneously
active layer;66 the Al can diffuse into the PEDOT:PSS layer67 and diffuse into the device and limit the stability.82–85 For example,
the active layer;68 and the PEDOT:PSS layer can also diffuse into Durrant et al.82 tested the stability of poly[2-methoxy-5-(3 0 ,7 0 -
the active layer.69 Such diffusion of metals and buffer layers will dimethyl-octyloxy)]-1,4-phenylene vinylene (MDMO-PPV)/PC61BM
reduce the stability of OSCs by changing the energy levels of solar cells in air. The device preserved only 20% and 60% of its
buffer layers and acting as the traps for charge recombination. original PCE after being stored in the dark for 8 h or irradiated
for 3 h, respectively. In addition to MDMO-PPV/PC61BM solar
2.2. Oxygen and water cells, OSCs based on poly(3-hexylthiophene) (P3HT)/PC61BM
Oxygen can reduce the stability of OSCs (Fig. 4). Firstly, the metal are more widely used. Krebs et al.83 compared the stability of
electrodes (e.g. Al and calcium (Ca)) with a low work function P3HT/PC61BM solar cells tested under different atmospheric
(WF) can be oxidized by oxygen permeation. The electrically conditions: dry nitrogen (water o 1 ppm, oxygen o 1 ppm), dry
insulating metal oxide layer, which is formed between the oxygen (water o 1 ppm, oxygen 100%), humid nitrogen (90 5%
electrode and the buffer layer or the electrode and the active relative humidity, oxygen o 1 ppm) and an ambient atmosphere
layer, will create a transport barrier and eventually induce an (20 5% relative humidity, 20% oxygen). After continuous
S-shaped I–V curve and degrade the performance of the device.70 illumination for 200 h, the devices with all structures (normal
Secondly, the penetrative oxygen in the active layer takes part in geometry, inverted geometry, roll-to-roll (R2R) processed inverted
the various photo-oxidation reactions of donor71 and acceptor devices without or with simple encapsulation) tested in an ambient
materials.72 The changed structures of donor and acceptor materials atmosphere (with water and oxygen) were always unstable (Fig. 5).
2.3. Irradiation
A solar cell is a device that can convert light into electricity, but
most of the representative OSCs are unstable upon irradiation.
For example, MDMO-PPV/PC61BM-based solar cells maintained
half PCE after continuous illumination for 22 h.86 Rand et al.87
investigated the photodegradation of devices with another two
prototypical material systems, P3HT/PC61BM and poly(N-9 0 -
hepta-decanyl-2,7-carbazole-alt-5,5-(40 ,7 0 -di-2-thienyl-20 ,10 ,30 benzo-
thiadiazole)) (PCDTBT)/PC71BM. After continuous illumination for
500 h, both of them showed insufficient stability, the PCE of P3HT/
PC61BM decreased from 3.4% to 1.9% while the PCE of PCDTBT/
PC71BM decreased from 5.7% to 3.8%. In addition to different
materials, the solar cells also showed poor stability during
irradiation with different wavelengths of spectrum88 or different
Fig. 4 Schematic diagram of the diffusion of oxygen and water. light intensities.89
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Thirdly, these reactions can change the energy levels of donors

and acceptors. Since the donor and acceptor components are not
equally affected by these photo-oxidation reactions, a change in the
alignment of the energy levels of the donor and the acceptor due to
degradation is observed.100 Finally, these reactions lead to the
formation of persistent radical cations on the polymer chain, leading
to a ‘relaxed’ charge transfer state (polymer+–O2) and thus affecting
the performance of devices.101 In addition to photo-oxidation
reactions in the active layer, photo-oligomerization of fullerene
acceptors102 and photolysis of polymer donors91 are observed in
the active layer, which are also responsible for the instability of
OSCs upon irradiation. Photo-oxidation reactions can also occur
in the buffer layer103 and the active layer/electrode interface.104
Besides photochemical degradation, which changes the
structures of materials, photophysical degradation is another
Fig. 5 Curves showing the degradation as a function of illumination time important type of photodegradation. Yang et al.105 and Adachi
under different atmospheric conditions for device models with normal et al.106 concluded that photoinduced charge accumulation could
geometry (A) and inverted geometry (B) and R2R processed inverted be a severe problem resulting in photophysical degradation of solar
devices without encapsulation (C) and with simple encapsulation (D).83 cell performance. The energy diagram of OSCs and two trap sites in
the interfacial region of the active layer are shown in Fig. 6a and b.
The VOC was dependent on the difference between the lowest
The original reasons for the instability of the device upon
unoccupied molecular orbital (LUMO) level of the acceptor and the
irradiation are photochemical degradation and photophysical
highest occupied molecular orbital (HOMO) level of the donor when
degradation in the active layer, the buffer layer and the active
ohmic contacts were formed on both interfaces of the active layer/
layer/electrode interface. The main photochemical degradation
anode or cathode.107 After 8 h of illumination, photoinduced charge
is photo-oxidation reaction in the active layer. Researchers
carriers (holes and electrons) accumulated in the two trap sites,
proposed some possible photo-oxidation reactions of donors and
inducing the alleviation of the energy band slope and resulting in a
acceptors.90–96 The reactions of three prototypical materials (MDMO-
decrease of VOC (Fig. 6c).
PPV,91 P3HT92 and polyfluorenes (PFs)96) are shown in Chart 1.
These reactions in the active layer can induce some negative effects
on device performance. Firstly, the changed structures of donor or 2.4. Heating
acceptor materials decrease the photoabsorption, which is harmful In the real world, the working temperature of solar cells is
to exciton generation.97 Secondly, these reactions will lead to the usually relatively high due to heating by continuous illumination.
formation of sub-bandgap states of materials, which can increase In the active layer, attributed to the highly conjugated structures of
the energetic disorder in the active layer and may reduce device most donor and acceptor materials, the relative high working
performance by including Shockley–Reed–Hall recombination,
reduced hole mobility and the build-up of space-charge in traps.98,99
Fig. 6 Schematic energy diagram of bulk heterojunction organic solar cells

(a) under the initial open circuit conditions, (b) under the initial short circuit
conditions, and (c) after degradation. The carriers, i.e., holes (open circle)
and electrons (filled circle), are accumulated in two trap sites (dashed line).
Alleviation of the energy band slope occurs, resulting in a decrease of VOC
Chart 1 Possible photo-oxidation reactions of MDMO-PPV, P3HT and PFs. (DVOC).106 Reprinted with permission from ref. 106. Copyright 2009, Wiley.
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temperature is still far below the decomposition temperatures of

most active materials.108–110 Thus, physical degradation is the
main type of heating induced degradation in the active layer.
Heating induced physical degradation of polymer donor/
fullerene acceptor blend is investigated as a model system.
Polymers have been proved to show mobility to some extent,
especially when the environmental temperature is higher than
their glass transition temperature (Tg).111,112 For example,
Lidzey et al.113 investigated the relationship between morphology
and heating temperatures. The effect of different heating tempera-
tures on the PCDTBT/PC71BM blend films was investigated and the

optical microscopy images of these films are shown in Fig. 7. Below
Fig. 8 TEM micrographs and electron diffraction patterns (insets) of 1 : 1
the Tg of PCDTBT (ranging from 100 1C to 145 1C under different TQ1/PC61BM films: (a) pristine, (b) annealed at 130 1C and (c) annealed at
conditions), the morphology barely changed (Fig. 7a and b), 150 1C.119 Optical microscopy images of P3HT/PC61BM blend films after
while coarse phase separation occurred in films when they were thermal annealing at 150 1C for 5 min (d), 30 min (e) and 60 min (f).120
annealed at a temperature above 155 1C (Fig. 7c and d). The Reprinted with permission from ref. 120. Copyright 2009, Wiley.
relationship between morphology and heating temperatures of
other representative D/A blends of P3HT/PC61BM,114–116 poly[2,3-
In addition to the different heating temperatures, Kim et al.120
bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl]
also investigated the relationship between fullerene aggregation/
(TQ1)/PC61BM117 and MDMO-PPV/PC61BM116 was also investigated,
crystallization and different heating times. As shown in Fig. 8d–f,
and similar results were obtained: the morphology of active layers
micrometer-sized PC61BM clusters began to appear after 5 min
became more unstable when the environmental temperature was
of thermal annealing at a high temperature of 150 1C. The
higher than the Tg of polymers.
number and the size of clusters gradually increased in the
The enhanced mobility of polymers above Tg not only
images as the annealing time increased. Heating induced many
influences the aggregation states of polymers, but also can assist
big size clusters (fullerene aggregation/crystallization) in the
the heating induced fullerene aggregation and crystallization, which
active layer which can sharply decrease the performance of OSCs
is another issue of physical degradation upon heating.118–121 Müller
due to inefficient exciton dissociation and charge transfer by
et al.119 studied the nucleation and growth of PC61BM crystals
decreased D/A interfaces. Besides the active layer, heating
in the TQ1/PC61BM blend films. As shown in transmission
induced degradation can also occur at the active layer/electrode
electron microscopy (TEM) images (Fig. 8a–c), both nucleation
interface122 and the buffer layer.123
and growth were strongly diffusion limited at lower tempera-
tures (approaching the Tg of the polymer). The growth rate
exponentially increased with temperature and the nucleation 2.5. Mechanical stress
rate displayed a maximum at around 150–170 1C, resulting in During the life cycle of OSCs, mechanical stress always exists.
the highest rate of PC61BM crystallisation at these temperatures. Stretchability and flexibility of the active components in OSCs
are crucial for devices fabricated in a large-scale R2R manner.124
But unfortunately, major OSCs are unstable with mechanical
stress.125–127
As shown in Fig. 9, mechanical stress can induce degradation
in the active layer, the buffer layer and active layer/buffer layer
interfaces. Firstly, the linear application of tension can induce
strain of organic materials. After the linear application of tension
(e = 20%), devices based on P3HT/PC61BM preserved only ca. 50%
of the original PCEs.128 Secondly, the decohesion process occurs
when mechanical stress is not enough to fracture a layer, which
can degrade the active layer and the buffer layer. These defects are
likely to suffer from the ingress of water and become the
centres of fracture. Dauskardt et al. found that the higher
content of moisture128 and higher temperature129 could accelerate
the decohesion rate. Thirdly, fracture of the active layer, the buffer
layer and the interface between the active layer and the buffer
layer is another mechanism of mechanical degradation.130,131 The
fracture can happen under relatively low mechanical stress due to
Fig. 7 Optical microscopy images of a PCDTBT/PC71BM (1 : 4) film on a
silicon/silicon oxide substrate that is (a) as-cast, or annealed for one hour at
the low cohesion energy of the active layer and the buffer layer and
(b) 130 1C, (c) 155 1C and (d) 200 1C. The scale bar in all images represents the low adhesion energy of the interface between the active layer
20 mm.113 Reprinted with permission from ref. 113. Copyright 2012, Wiley. and the buffer layer.
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test conditions are employed; ‘‘w’’ means ‘‘with’’; ‘‘w/o’’ means

‘‘without’’; ‘‘—’’ means ‘‘no data are available directly’’; ‘‘modulus’’
is the modulus of the active layer; the photovoltaic parameters after
stability tests are shown in brackets; ‘‘Z/Z0’’ is defined as the ratio of
PCE after and before the stability test. In some literature studies, we
can find PCE before the stability test and the ratio of PCE after and
before the stability test or a figure of PCE vs. aging time but without
PCE after the stability test. Thus, we provide the PCE before the
stability test and Z/Z0 in tables without PCE after the stability test.
The molecular structures of materials used in this review are shown
in Charts 2–6.
3.1. Material design of the active layer

3.1.1. Molecular skeletons of donors. Rational design of
the molecular skeletons of donor materials is an effective
Fig. 9 Schematic diagram of the device under mechanical stress.
strategy to increase the stability of OSCs, such as substituting
the oxidizable units with photo-oxidation stable units, controlling
In addition to the degradation of the active layer and the the crystallinity of polymers, adjusting the rigidity/flexibility of
buffer layer under mechanical stress, mechanical stress induced polymer chains, inducing the self-assembly of polymer chains
degradation of electrodes will be another big problem when and increasing the degree of polymerization of polymers (Fig. 10).
changing the substrates from glass to flexible materials. The photovoltaic properties of devices with different molecular
skeletons of donor materials before and after the stability tests are
listed in Table 1, and the molecular structures of donor materials
3. Strategies to increase the stability of with different molecular skeletons are shown in Chart 2.
OSCs Substitution of the oxidizable units by photo-oxidation
stable units can improve photo/air stability.142–147 For example,
In this section, we focus our discussion on the recent developments Krebs et al.143 tested and mapped the photo/air stability in air
in strategies to increase the stability of OSCs, especially on those for a wide range of donor polymers. The rule-of-thumb photo-
accomplished in the last two years. Mainly six types of strategies are stability ranking of donor and acceptor units for donor poly-
included: material design of the active layer (molecular skeletons mers used in OSCs was mapped (Fig. 11). Based on this study,
and side chains of donors, and fullerene/non-fullerene acceptors), abandoning the exocyclic double bonds, quaternary carbon
device engineering of the active layer (ternary blends and processing atoms and readily cleavable bonds (such as C–N or C–O) and
methods), employing inverted geometry, optimizing buffer using the aromatic polycyclic units in the molecular skeleton
layers (hole/electron transport layers), using stable electrodes were recommended for enhancing the photo/air stability.
(new transparent/back electrodes) and encapsulation. To study Son et al.145 substituted the readily cleavable bonds (C–O) with
the stability of OSCs, stress (such as air, light, heat and aromatic polycyclic units. With the substitution of benzodithio-
mechanical) is usually employed. In the real world, OSCs phene (BDT) units by dithienothiophene (DTT) units in a
actually suffer from several types of stresses at the same time. diketopyrrolopyrrole (DPP)-based donor polymer, the OSCs
To chart the stability of OSCs working in the real world, the showed much better photo/air stability. After the stability test,
international summit on OPV stability (ISOS) protocols were the PCE of PDPPDTT/PC71BM solar cells preserved 80% of its
developed.132–141 There are three main ISOS protocols for OSCs: original value. In contrast, the PCE of PDPPBDT/PC71BM solar
ISOS-1 in 2008 (Denver, USA), ISOS-2 in 2009 (Amsterdam, The cells preserved only 50% of its original value.
Netherlands) and ISOS-3 in 2010 (Roskilde, Denmark). Each Enhancing the crystallinity of donor polymers provides
ISOS protocol is composed of some more specific protocols another approach to increased photochemistry stability.148–151
(different combinations of test conditions: light source, tem- McGehee et al.148 tested the stability of OSCs based on the
perature, humidity, etc.). In addition, each specific ISOS proto- amorphous PCDTBT donor polymer and the crystalline KP115
col has three different levels to meet the capabilities of a wider donor polymer. The PCDTBT/PC71BM solar cell lost 16% efficiency
range of laboratories/groups. Furthermore, the reporting of after aging for 60 h, while the solar cell based on KP115/PC71BM lost
device lifetime is also addressed in the ISOS protocols. The only 5% efficiency. This work proposed that the spatial separa-
ISOS protocols are very important for OSCs’ research and future tion of electrons and holes in crystalline polymers may reduce a
industrial production. But so far, almost all literature studies possibly trap-assisted recombination, while in amorphous poly-
related to the stability research of OSCs were published without mers consisting of mostly mixed phases, the close spatial
ISOS protocols due to the insufficient promotion of these useful distance of electrons and holes may lead to increased non-
ISOS protocols. In this review, the photovoltaic properties of geminate recombination. Unlike the crystalline donor polymer,
devices without and with the strategies before and after the which can enhance the photochemistry stability of OSCs, the
stability tests are listed in Tables 1–10. In these tables, various amorphous polymer donor is a good choice for mechanical
Table 1 The photovoltaic properties of devices with different molecular skeletons of donor materials before and after the stability tests
Chem Soc Rev
Test conditions
Mechanical Modulus JSC PCE Z/Z0
Active layer Air Light Heat stress Strategy (GPa) VOC (V) (mA cm2) FF (%) (%) Ref.
PDPPBDT/PC71BM w (170 h) w (170 h) w/o w/o w/o — 0.74(—) 7.1(—) 0.62(—) 3.3(—) 50 145
Change donor to: PDPPDTT — 0.70(—) 13.5(—) 0.63(—) 5.9(—) 80
PCDTBT/PC71BM w/o w (60 h) w/o w/o w/o — 0.87(0.84) 10.4(10.2) 0.60(0.53) 5.4(4.5) 84 148
Change donor to: KP115 — 0.62(0.61) 13.1(12.8) 0.64(0.63) 5.2(4.9) 95
PDPP2FT/PC61BM w w/o w/o Tension w/o 2.76 0.72(—) 8.3(—) 0.43(—) 2.5(—) — 152
Change donor to: PDPP2FT-seg-2T 1.60 0.70(—) 8.4(—) 0.48(—) 2.8(—) —
DPPT-TT/PC61BM w w/o w/o Strain (20%) w/o — — — — — 20 153
This journal is © The Royal Society of Chemistry 2016

Change donor to: P3HT — — — — — 50
P3HT/PC61BM w/o w/o 150 1C (5 h) w/o w/o — 0.62(0.63) 6.8(3.9) 0.66(0.44) 2.8(1.1) 39 160
Change donor to: PPP-P3HT — 0.62(0.63) 8.1(7.2) 0.69(0.66) 3.4(3.0) 88
PCDTBT/PC71BM w/o w (36 h) w/o w/o w/o — 0.90(—) 9.6(—) 0.60(—) 5.2(—) 30 163
Change donor to: L-PCDTBT — 0.91(—) 10.9(—) 0.71(—) 7.0(—) 82
Table 2 The photovoltaic properties of devices with different molecule side chains of donor materials before and after the stability tests
Test conditions
Mechanical Modulus JSC Z/Z0
Active layer Air Light Heat stress Strategy (GPa) VOC (V) (mA cm2) FF PCE (%) (%) Ref.
96% RR P3HT/PC61BM w/o w/o 150 1C (11 h) w/o w/o — — — — 3.7(—) 54 171
Change donor to: 90% RR P3HT — — — — 3.4(—) 85
RRa P3HT/PC61BM w/o w (60 h) w/o w/o w/o — 0.91(0.87) 4.2(4.1) 0.40(0.37) 1.5(1.3) 87 148
Change donor to: RR P3HT — 0.56(0.56) 10.7(10.5) 0.72(0.70) 4.4(4.2) 95
P3HT/PC61BM w/o w/o 150 1C (24 h) w/o w/o — 0.59(—) 9.3(—) 0.58(—) 3.2(—) 28 173
Change donor to: P3HT-Br10 — 0.58(—) 10.2(—) 0.57(—) 3.4(—) 76
PPDTBT/PC71BM w/o w/o 130 1C (200 h) w/o w/o — 0.81(—) 10.4(—) 0.61(—) 4.9(—) 41 183
Change donor to: PPDT2FBT — 0.86(—) 11.4(—) 0.74(—) 7.1(—) 89
PBDTDPP-1/PC61BM w/o w (110 h) 50 1C (110 h) w/o w/o — 0.66(—) 15.9(—) 0.49(—) 5.1(—) 65 185
Change donor to: PBDTDPP-2 — 0.70(—) 12.1(—) 0.52(—) 4.4(—) 80
PCPDTBT-1/PC71BM w/o w/o 85 1C (650 h) w/o w/o — 0.59(—) 9.5(—) 0.44(—) 2.5(—) 26 187
Change donor to: PCPDTBT-2 — 0.59(—) 7.9(—) 0.43(—) 2.1(—) 55
P3HT/PC61BM w w/o w/o Strain (10%) w/o 2.02 0.37(0.04) 5.5(0.66) 0.29(0.22) 0.59(0.01) 2 188
Change donor to: P3DDT 0.47 0.50(0.58) 2.1(1.9) 0.28(0.30) 0.29(0.33) —
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Table 3 The photovoltaic properties of devices with different acceptor materials before and after the stability tests
Test conditions
P3HT/PC61BM w/o w/o 150 1C (10 h) w/o w/o — 0.63(—) 10.4(—) 0.64(—) 4.2(1.8) 43 195
Change acceptor to: TPA-PC61BM — 0.65(—) 9.9(—) 0.62(—) 4.0(4.0) 100
PDTSTzTz/PC61BM w/o w (27 h) w/o w/o w/o — — — — 3.1(2.3) 74 197
Change acceptor to: bisPC61BM — — — — 3.7(3.5) 95
P3HT/PC61BM w/o w/o 150 1C (20 h) w/o w/o — 0.59(—) 10.5(—) 0.68(—) 4.2(1.9) 45 200
Change acceptor to: NC60BA — 0.82(—) 9.9(—) 0.67(—) 5.4(4.6) 85
PBDTTT-C-T/PC71BM w/o w (180 h) 75 1C (180 h) w/o w/o — 0.63(—) 7.0(—) 0.44(—) 1.9(—) 50 207
Change acceptor to: DC-IDT2T — 0.80(—) 3.1(—) 0.40(—) 0.99(—) 85
PBDTTTPD/PC61BM w w/o w/o Tension w/o 1.76 0.96(—) 11.2(—) 0.57(—) 6.1(—) — 211
Change acceptor to: P(NDI2HD-T) 0.43 1.06(—) 11.2(—) 0.56(—) 6.6(—) —
Table 4 The photovoltaic properties of devices with different third components before and after the stability tests
Test conditions
PTB7/PC61BM w/o w/o 150 1C (16 h) w/o w/o — 0.71(0.62) 11.2(4.5) 0.68(0.32) 5.5(0.9) 16 218
Third component: BABP — 0.71(0.73) 12.3(10.8) 0.66(0.59) 5.8(4.6) 79
Third component: PCBS — 0.60(0.58) 9.8(9.5) 0.65(0.66) 3.8(3.6) 95
PCDTBT/PC61BM w/o w/o 85 1C (1 h) w/o w/o — 0.93(—) 10.1(—) 0.56(—) 5.2(—) 75 226
Third component: (PCB)2C2 — 0.93(—) 10.0(—) 0.62(—) 5.8(—) 90
P3HT/PC61BM w w/o w/o Tension w/o 4.37 0.60(—) 6.7(—) 0.59(—) 2.4(—) — 230
Third component: PC71BM 1.53 0.61(—) 6.6(—) 0.50(—) 2.0(—) —
P3HT/OXCBA w/o w/o 150 1C (72 h) w/o w/o — 0.87(0.49) 9.3(7.5) 0.61(0.44) 4.9(1.6) 33 233
Third component: P3HT-g-P2VP — 0.89(0.84) 9.3(9.2) 0.63(0.60) 5.2(4.7) 90
PCDTBT/PC71BM w (45 h) w (45 h) w/o w/o w/o — 0.88(—) 11.3(—) 0.55(—) 5.5(—) 35 241
Third component: Al NPs — 0.88(—) 12.1(—) 0.56(—) 6.0(—) 50
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Table 5 The photovoltaic properties of devices with different processing methods before and after the stability tests
Chem Soc Rev
Test conditions
P3HT/PC61BM w (75 h) w (75 h) w/o w/o w/o — — — — — 55 242
Methods: change D/A ratio — — — — — 70
P3HT/PC61BM w (10 h) w (10 h) w/o w/o w/o — 0.58(0.54) 9.1(2.7) 0.57(0.37) 3.0(0.5) 17 244
Methods: change solution temperature — 0.58(0.57) 10.2(6.6) 0.62(0.52) 3.6(2.0) 56
P3HT/PC61BM w (0.5 h) w (0.5 h) w/o w/o w/o — — — — — 0 245
Methods: change solvent — — — — — 35
PCDTBT/PC61BM w/o w/o 80 1C (1000 h) w/o w/o — — — — 5.3(—) 61 247

Methods: wire bar coating — — — — 5.3(—) 74
PCDTBT/PC61BM w/o w/o 80 1C (160 h) w/o w/o — — — — — 64 249
Methods: light exposure — — — — — 85
Methods: low temperature drying — 0.62(0.54) 11.5(7.3) 0.63(0.54) 4.4(2.2) 50
PTB7-TH/PC71BM w (720 h) w (720 h) w/o w/o w/o — 0.80(—) 17.3(—) 0.67(—) 9.3(—) 0 252
Methods: alcohol treatment — 0.79(—) 18.3(—) 0.62(—) 9.0(—) 85
Table 6 The photovoltaic properties of devices with conventional and inverted geometries before and after the stability tests
Test conditions
P3HT/PC61BM w (1 h) w/o w/o w/o w/o — — — — — 20 260
Inverted geometry — — — — — 95
P3HT/PC61BM w (48 h) w/o w/o w/o w/o — 0.64(—) 9.1(—) 0.67(—) 3.9(—) 0 261
Inverted geometry — 0.62(—) 10.9(—) 0.63(—) 4.3(—) 95
PTB7/PC71BM w (48 h) w/o w/o w/o w/o — — — — — 30 263
N(Ph-2T-DCN-Et)3/PC71BM w (360 h) w/o w/o w/o w/o — 0.94(—) 7.8(—) 0.46(—) 3.4(—) 5 265
SubPc/C60 w (44 h) w/o w/o w/o w/o — 1.0(0.82) 3.9(1.5) 0.49(0.24) 1.9(0.3) 16 266
w (96 h) Inverted geometry — 0.99(0.98) 4.7(4.4) 0.41(0.40) 1.9(1.7) 89
PCDTBT/PC71BM w (10 h) w/o w/o w/o w/o — 0.88(—) 9.1(—) 0.57(—) 4.6(—) 10 267
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Table 7 The photovoltaic properties of devices with different hole transport layers before and after the stability tests
Review Article
Chem. Soc. Rev.

Test conditions
P3HT/OXCBA w (120 h) w/o w/o w/o w/o — 0.85(—) 10.3(—) 0.60(—) 5.2(—) 55 282
Transport layer: PEDOT:PSS with PS NPs — 0.84(—) 10.3(—) 0.60(—) 5.2(—) 86
TQ1/PC71BM w (240 h) w/o w/o w/o w/o — 0.90(—) 9.2(—) 0.66(—) 5.5(—) 0 283
Transport layer: MoO3–PEDOT:PSS — 0.89(—) 10.3(—) 0.70(—) 6.4(—) 80
PCDTBT/PC71BM w (860 h) w/o w/o w/o w/o — 0.88(—) 10.1(—) 0.67(—) 6.0(—) 5 285
Transport layer: MoOx — 0.89(—) 10.9(—) 0.67(—) 6.5(—) 50
pDTG-TPD/PC71BM w (60 h) w/o w/o w/o w/o — 0.83(—) 12.7(—) 0.64(—) 6.8(—) 15 287
Transport layer: NiOx — 0.82(—) 13.9(—) 0.68(—) 7.8(—) 50
Transport layer: GO — 0.60(—) 9.7(—) 0.58(—) 3.4(—) 75
P3HT/PC61BM w (2400 h) w/o w/o w/o w/o — 0.60(—) 9.9(—) 0.72(—) 4.1(0.3) 7 301
Transport layer: APS — 0.59(—) 9.2(—) 0.68(—) 3.7(2.8) 76
PTB7/PC71BM w w/o w/o Avulsion w/o — 0.76(—) 15.4(—) 0.65(—) 7.6(—) — 304
Transport layer: PEDOT:PSS with PS NPs — 0.76(—) 16.1(—) 0.60(—) 7.4(—) —
Table 8 The photovoltaic properties of devices with different electron transport layers before and after the stability tests
Test conditions
Transport layer: CrOx — 0.56(—) 11.6(—) 0.55(—) 3.5(—) 69
Transport layer: PTMAHT:SDS — 0.62(—) 9.5(—) 0.68(—) 4.0(—) 75
PTB7-TH/PC71BM w (8760 h) w/o w/o w/o w/o — 0.79(—) 18.0(—) 0.56(—) 7.9(—) 77 314
Transport layer: ZMO — 0.79(—) 17.4(—) 0.61(—) 8.3(—) 93
Transport layer: E-ZnO — 0.61(—) 11.9(—) 0.71(—) 5.1(—) 96
P3HT/PC61BM w (4380 h) w/o w/o w/o w/o — 0.60(0.61) 11.1(7.9) 0.60(0.47) 4.0(2.3) 58 319
Transport layer: ZnO/PEIE — 0.62(0.63) 10.6(9.1) 0.62(0.62) 4.1(3.6) 88
P3HT/ICBA w/o w (640 h) w/o w/o w/o — 0.75(—) 10.0(—) 0.53(—) 3.9(—) 38 329
Transport layer: PA-modified ZnO — 0.77(—) 10.1(—) 0.64(—) 4.9(—) 73
P3HT/PC61BM w/o w (8 h) w/o w/o w/o — 0.57(0.47) 8.9(7.7) 0.63(0.60) 3.2(2.2) 69 330
Transport layer: ZnO/Al — 0.59(0.58) 8.0(6.7) 0.70(0.68) 3.3(2.7) 82
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Table 9 The photovoltaic properties of devices with different transparent/back electrodes before and after the stability tests
Chem Soc Rev
Test conditions
Mechanical DR/R0 JSC Z/Z0
Active layer Air Light Heat stress Strategy (%) VOC (V) (mA cm2) FF PCE (%) (%) Ref.
PTB7-F20/PC71BM w w/o w/o Bending w/o 35 0.68(—) 15.2(—) 0.56(—) 5.8(—) — 339
Transparent electrode: ZnO/AgOx 1.33 0.68(—) 16.4(—) 0.58(—) 6.3(—) —
PTB7/PC71BM w w/o w/o Bending w/o 68.8 0.74(—) 16.1(—) 0.62(—) 7.4(—) 22 341
Transparent electrode: AgNWs 3.3 0.74(—) 16.0(—) 0.61(—) 7.2(—) 98
PTB7-TH/PC71BM w w/o w/o Bending w/o — 0.78(—) 13.4(—) 0.62(—) 7.4(—) — 345
Transparent electrode: CP-AgNWs/cPI 10 0.78(—) 13.9(—) 0.62(—) 7.5(—) 95
P3HT/PC61BM w w/o w/o Bending w/o — 0.62(—) 8.6(—) 0.60(—) 3.2(—) — 350

Transparent electrode: AgNW–graphene — 0.61(—) 9.9(—) 0.54(—) 3.3(—) —
P3HT/PC61BM w/o w (1000 h) w/o w/o w/o — — — — — 28 355
Transparent electrode: Ag — — — — — 96
PTB7/PC71BM w (170 h) w/o w/o w/o w/o — 0.75(—) 14.6(—) 0.65(—) 7.1(—) 75 362
Back electrode: Ag — 0.75(—) 14.8(—) 0.72(—) 8.0(—) 96
PTB7-TH/PC71BM w (24 h) w/o w/o w/o w/o — 0.76(—) 16.3(—) 0.70(—) 8.7(—) 75 35
Back electrode: Au — 0.76(—) 15.8(—) 0.71(—) 8.6(—) 99
Table 10 The photovoltaic properties of devices with different encapsulation materials before and after the stability tests
Test conditions
P3HT/PC61BM w (1056 h) w/o 85 1C (1056 h) w/o w/o — — — — — — 366
Encapsulation: epoxy resin — 0.60(—) 6.0(—) 0.61(—) 2.2(—) 90
PTB7/PC71BM w (3500 h) w/o w/o w/o w/o — 0.75(—) 13.3(—) 0.73(—) 7.3(—) 0 370
Encapsulation: multilayered MoO3/MgF2 — 0.75(—) 10.0(—) 0.72(—) 5.4(—) 60
PCDTBT/PC71BM w (24 h) w/o w/o w/o w/o — — — — 5.4(0.4) 7 372
Encapsulation: rGO — — — — 5.5(5.2) 95
P3HT/PC61BM w (150 h) w/o w/o w/o w/o — — — — — 15 375
Encapsulation: epoxy resin/glass — — — — — 60
P3HT/PC61BM w (636 h) w/o w/o w/o w/o — 0.61(—) 8.5(—) 0.57(—) 3.0(—) — 381
Encapsulation: ZnO/UV resin — 0.60(—) 8.5(—) 0.55(—) 2.8(—) 80
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Chart 2 The molecular structures of donor materials with different molecular skeletons or different molecular side chains.
robustness of OSCs. Lipomi et al.152 demonstrated that decreasing As shown in Fig. 12, after the infliction of a large strain of 20%,
the crystallinity of the donor polymer could increase the mechanical DPPT-TT/PC61BM blend film exhibited worse mechanical com-
compliance of donor polymers without deleteriously affecting pliance compared with P3HT/PC61BM blend film due to the
their optoelectronic properties. Random copolymerization of the fused rings on its molecular skeleton. As a result, the PCE of
diketopyrrolopyrrole unit flanked by two furan rings (DPP2F), DPPT-TT/PC61BM solar cells preserved only 20% of its original
thiophene (T) and bithiophene (2T) could create a new polymer value after the large strain. Rigidity/flexibility of polymer chains
donor PDPP2FT-seg-2T, which showed lower crystallinity com- not only affects the mechanical robustness, but also shows an
pared with PDPP2FT. As a result, the tensile moduli of active obvious influence on thermal stability. Changing the relatively
layers were decreased from 2.76 to 1.60 GPa after changing the flexible units to relative rigid units of donor polymers can
polymer donor from PDPP2FT to PDPP2FT-seg-2T which showed increase the rigidity of molecular skeletons, resulting in higher
better stretchability. Tg of polymers (reduced mobility of polymers) which benefits
In addition to decreasing the crystallinity of the donor polymer, the thermal stability.154 For example, PFs and F82T have
increasing the flexibility of molecular skeletons also benefits the relatively low Tgs of 72 1C155 and 80 1C,156 respectively. Inser-
mechanical robustness. Bao et al.153 concluded that the fused tion of rigid benzothiadiazole (BT) units into the molecular
rings in the molecular skeleton could decrease the flexibility of skeletons of PFs and F82T can significantly increase the Tgs to
polymer chains, which was harmful to mechanical compliance. 135 1C (F8BT)157 and 123 1C (F8TBT),158 respectively. As a result,
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Chart 3 The molecular structures of fullerene and non-fullerene acceptor materials.
solar cells based on F8TBT/PC61BM exhibited good stability absence of burn-in loss. As a result, the solar cells based on
under heating.159 higher MW L-PCDTBT (59 kDa)/PC71BM blend exhibited much
Block copolymerization which can induce the self-assembly better photochemistry stability compared with the solar cells
of polymer chains is a valid strategy to increase thermal based on PCDTBT (21 kDa)/PC71BM blend. Wegner et al.164
stability.160–162 For example, Dai et al.160 fabricated OSCs based investigated the relationship between Tg and the degree of
on block copolymer (PPP-P3HT)/PC61BM blend which could polymerization. In line with the classical Fox-Flory equation,
form a well-defined double-channel-like structure. As shown in their results demonstrated that Tg could be increased by
Fig. 13, due to the good miscibility between the amorphous PPP increasing the degree of polymerization, which was beneficial
and PC61BM molecules (strong interaction between alkoxy side to achieving better thermal stability of OSCs. Dauskardt et al.165
chains of PPP and PC61BM), the PPP-P3HT block copolymer investigated the relationship between mechanical robustness
could act as an effective structure-directing template for geometrical and the degree of polymerization. Increasing the MW of P3HT
manipulation of PC61BM location. After continuous heating at could increase intermolecular bonding and the probability of
150 1C for 5 h, the PCE of PPP-P3HT/PC61BM solar cells preserved chain entanglement, leading to a greater degree of plastic
88% of its original value due to the slower formation of PC61BM deformation before cohesive failure occurred. As a result, the
aggregations. By contrast, the short-circuit current density ( JSC), FF active layer cohesion values were as high as B 17 J m2 with a
and PCE of P3HT/PC61BM solar cells decreased from 6.8 mA cm2, high MW P3HT (100 kDa)/PC61BM blend, which exhibited much
0.66 and 2.8% to 3.9 mA cm2, 0.44 and 1.1%, respectively, after the better mechanical stability compared with that (1 to 2 J m2) of
stability test. a low MW P3HT (28 kDa)/PC61BM blend.
Unlike the strategies we discussed above (one strategy could 3.1.2. Molecular side chains of donors. Rational design of
only improve one type of stability), increasing the degree of the molecular side chains of donor materials (employing cleavable
polymerization of the donor polymer can simultaneously improve side chains, regioregular (RR)/regiorandom (RRa) side chains, cross-
the photochemistry, thermal and mechanical stabilities.163–165 For linkable side chains, longer side chains, etc.) is also an effective
example, Lee et al.163 improved the photochemistry stability of strategy to increase the stability of OSCs (Fig. 14). The photovoltaic
PCDTBT/PC71BM solar cells by increasing the molecular weight properties of devices with different molecular side chains of donor
(MW) of PCDTBT. Higher MW of PCDTBT could eliminate the materials before and after the stability tests are listed in Table 2, and
trap-embedded fractions which significantly suppressed the the molecular structures of donor materials with different side
photoactivated trap-width broadening and led to the almost chains are also shown in Chart 2.
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Chart 4 The molecular structures of other donor and acceptor materials used in this review.
Chart 5 The molecular structures of third components used in the active layer.
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Chart 6 The molecular structures of buffer layers.
Fig. 10 Schematic diagram of the strategies to design the molecular

skeletons of donor materials.
Alkyl side chains facilitate the dissolution and assembly of

the donor polymer, but once the devices have been fabricated,
these alkyl side chains are actually useless and will limit the
stability. Thus, modification of alkyl side chains to thermally
cleavable side chains can simultaneously increase the thermal
and photo/air stabilities.166–169 For example, Krebs et al.167 Fig. 11 Rule-of-thumb photostability ranking of donor and acceptor units
synthesized a donor polymer with thermally cleavable side for donor polymers used in OSCs (these are representative molecules of
chains (PhxSDT-DTZ). The solubilising side chains (ester the stated families).143
groups with alkyl chains) on the dithienylthiazolo[5,4-d]thiazole
(DTZ) unit were thermally removable through ester elimination
at around 200 1C which significantly decreased the mobility of group168 also investigated the relationship between the
the polymer donor. As shown in Fig. 15, the optical microscopic photo/air stability and thermally cleavable side chains. Because
images of PhxSDT-DTZ/PC61BM films before and after thermal the side chains were often attacked by reactive oxygen species,
annealing at 150 1C indicated a high thermal stability. PhxSDT- thermally cleaved side chains could avoid these photo-oxidation
DTZ/PC61BM films showed a homogeneous nature after heating reactions and therefore increase the photo/air stability. By
for 96 h. In stark contrast, heating of a P3HT/PC61BM film this strategy, the photo/air stability of P3HT was significantly
induced a morphological change even after only 4 h. The same increased.
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Fig. 12 Optical micrographs of DPPT-TT/PC61BM (a and b), and P3HT/ Fig. 15 Optical microscopy images of PhxSDT-DTZ cleaved/PC61BM
PC61BM (c and d) on poly(dimethylsiloxane) (PDMS)/PEDOT:PSS substrates (a and b) and P3HT/PC61BM (c and d) films before (a and c) and after
at 0% strain (a and c) and 20% strain (b and d).153 Reprinted with permission (b and d) the stability test.166
from ref. 153. Copyright 2012, Elsevier.
Reducing the polymer regioregularity is another effective

strategy to increase thermal stability.170–172 Fréchet et al.171
fabricated solar cells based on 96% RR P3HT/PC61BM and 90%
RR P3HT/PC61BM, respectively. They concluded that the stronger
driving force for crystallization of high-RR P3HT induced a larger
extent of phase segregation, which could develop many large
PC61BM crystals to the detriment of device performance. As a
result, after the stability test, the PCE of 90% RR P3HT/PC61BM
solar cells preserved 85% of its original value. In contrast, the
PCE of 96% RR P3HT/PC61BM solar cells preserved only 54% of
its original value. However, reducing the polymer regioregularity is
not a good choice for increasing the photochemistry stability.148,150
McGehee et al.148 compared the photochemistry stability of RRa
P3HT/PC61BM and RR P3HT/PC61BM. The RRa P3HT/PC61BM
solar cell lost 13% efficiency after aging for 60 h, while the solar
Fig. 13 Schematic representation of the donor/acceptor double-channel cell based on RR P3HT/PC61BM lost only 5% efficiency. The
network structure of the novel PPP-P3HT/PC61BM hybrid system.160
Reprinted with permission from ref. 160. Copyright 2015, Elsevier.
better photochemistry stability of RR P3HT/PC61BM solar cells
was attributed to higher crystallinity of RR P3HT which may
reduce a possibly trap-assisted recombination.
Employing cross-linkable side chains, which can freeze the
morphology of the active layer, to replace the alkyl side chains
is a widely used strategy to increase the thermal stability.
Notably, alkyl bromide (Br) functionalized side chains are most
popular.173–178 There is a radical-based mechanism in this Br
involved cross-linking reaction: homolytic cleavage of the carbon–
bromine covalent bonds happens with direct exposure to 254 nm
ultraviolet (UV) light,179 then cross-linking occurs with abstraction
of a proton by the bromine radical from the side chains of adjacent
polymers, followed by coupling of the alkyl radicals.178 For example,
Fréchet et al.173 fabricated solar cells based on P3HT-Br10/PC61BM
blend (P3HT-Br10 is a copolymer containing 10% of the cross-
linkable brominated unit), which showed much better thermal
stability compared to conventional devices utilizing a P3HT/PC61BM
blend. As shown in the optical microscopy and grazing incidence
Fig. 14 Schematic diagram of the strategies to design the molecule side wide angle X-ray scattering (GIWAXS) (Fig. 16), no PC61BM crystallite
chains of donor materials. was found in the cross-linked P3HT-Br10/PC61BM blend film
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Fig. 17 Illustration of different formations of polymer aggregates based

on backbone side chain distribution. In the BHJ these aggregates mediate
the transport of PC61BM which can either pass through the aggregates or
around them in a circuitous path.185
original value. Maes et al.187 reported that the stability of OSCs

Fig. 16 Optical microscopy images (a and b) and GIWAXS patterns (c and d)
of P3HT-Br10/PC61BM blends after 24 h of annealing at 150 1C following
under thermal stress was enhanced by the insertion of alcohol
exposure to UV for 30 min (a and c) and P3HT/PC61BM blends after 24 h of moieties on the side chains (PCPDTBT-2). A relative PCE of
annealing at 150 1C (b and d). Dark areas in optical microscopy images are PCPDTBT-2/PC71BM up to 55% of its starting value could be
PC61BM-rich regions. The scale bar is 25 mm.173 Reprinted with permission from maintained after 650 h at 85 1C due to the optimized interface of
ref. 173. Copyright 2009, Wiley.
the active layer/top electrode, whereas the reference PCPDTBT-1/
PC71BM device exhibited a relative PCE of only 26%.
after 24 h of annealing at 150 1C. As a result, the PCE of P3HT-Br10/ Mechanical stability can be controlled by the side chain
PC61BM solar cells preserved 76% of its original value after the engineering of the donor polymer.188,189 Lipomi et al.188 investigated
stability test. In contrast, the PCE of P3HT/PC61BM solar cells the relationship between the mechanical stability and the length of
preserved only 28% of its original value. In addition to P3HT/ the alkyl side chains. As shown in Fig. 18, when the strain of 10%
PC61BM solar cells, this strategy can also be used in low-bandgap was applied, major cracks on the surface of the P3HT (C6 side
polymer/fullerene solar cells.178 Besides Br, other groups such as chains)/PC61BM blend film could be observed (Fig. 18a); no cracks
alkenyl,180,181 azide175 and oxetanes178 can also be used as reactive were observed for P3DDT (C12 side chains)/PC61BM (Fig. 18b).
groups in cross-linkable side chains. As a result, the P3DDT/PC61BM solar cell exhibited a similar PCE
In addition to employing thermally cleavable side chains, to its original value after the stability test. In contrast, the PCE of
controlling the polymer regioregularity and using cross-linkable the P3HT/PC61BM solar cell preserved only 2% of its original
side chains, employing other side chains can also increase value. Similar to the results of the strain test, the tensile modulus
thermal stability by introduction of non-covalent conformational (0.47 GPa) of P3DDT/PC61BM was much lower than that of P3HT/
locking,182,183 suppression of fullerene diffusion184,185 and opti- PC61BM (2.02 GPa), which demonstrated that better stretchabil-
mization of the interface between active layer/electrodes.186,187 ity of active layers could be achieved by increasing the length of
Woo et al.183 synthesized a polymer donor with non-covalent the alkyl side chains of the polymer donor.
conformational locking to enhance thermal stability. Fluorine 3.1.3. Fullerene and non-fullerene acceptors. Fullerene
(F) side chains were introduced in the polymer (PPDT2FBT) to (C60, C70) and fullerene derivatives (PC61BM, PC71BM, indene-C60
interact with sulfur (S) atoms and hydrogen (H) atoms. This bisadduct (ICBA)) are widely used as electron acceptors in OSCs due
interaction could lock the molecular conformation and decrease to their ultrafast charge transfer at D/A interfaces, high electron
the mobility of the polymer. As a result, after continuous heating mobility and good ability to form a favorable nanoscale network
at 130 1C for 200 h, the PCE of PPDT2FBT/PC71BM solar cells with donor polymers.190–193 However, the spheroidal structure of
preserved 89% of its original value. In contrast, the PCE of fullerenes not only improves the efficiency, but also reduces the
PPDTBT/PC71BM solar cells preserved only 41% of its original stability. Under irradiation, the 2+2 cycloaddition between two
value. Tierney et al.185 investigated the relationship between the
side chains and PC61BM diffusion. As shown in Fig. 17, the
aggregates of the polymer with linear alkyl side chains
(PBDTDPP-2) were densely packed, which was likely to reduce
the PC61BM diffusion rate by the increased diffused path. In
contrast, aggregates of the polymer with linear alkoxy side chains
(PBDTDPP-1) were not densely packed due to the rotational
freedom and steric hindrance of the alkoxy side chains, which
increased the PC61BM diffusion rates. Because the excessively
aggregation of fullerene caused by continuous heating would
decrease the efficiency, the PCE of PBDTDPP-2/PC61BM solar Fig. 18 Photographs of (a) P3HT/PC61BM and (b) P3DDT/PC61BM devices
cells preserved 80% of its original value after heating, while the under 10% strain.188 Reprinted with permission from ref. 188. Copyright
PCE of PBDTDPP-1/PC61BM solar cells preserved 65% of its 2014, Wiley.
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fullerene moieties leads to the formation of dimers. Under heating, As shown in Fig. 20, the well-proportioned morphology was
the dimers disappear, and the fullerenes easily diffuse and maintained for the P3HT/NC60BA blend after heating at 150 1C for
excessively aggregate to big clusters (crystallization). Dimeriza- 20 h due to the amorphous nature of NC60BA. In contrast, uneven
tion can lead to very rapid losses in PCE over a short timeframe, PC61BM crystals appeared in the P3HT/PC61BM case indicating that
and crystallization drives ultimate device failure.185 Thus, the thermal-driven crystallization for PC61BM did exist. As a result, the
main strategy of the design of photo/thermal stable acceptors is to PCE of P3HT/NC60BA solar cells preserved 85% of its original value
avoid the dimerization and crystallization, including employing after the stability test, while the PCE of reference P3HT/PC61BM solar
bigger side chains of fullerene, using bisadduct fullerene derivatives cells decreased from 4.2% to 1.9%.
and introducing nonspherical structures (Fig. 19). The photovoltaic Using non-fullerene materials203–206 as acceptors in OSCs is a
properties of devices with different acceptor materials before and new strategy to increase photo- and thermal stabilities due to the
after the stability tests are listed in Table 3, the molecular structures nonspherical structure of these molecules.207–210 Zhan et al.207
of acceptor materials are shown in Chart 3, and the molecular reported OSCs based on polymer donor PBDTTT-C-T and non-
structures of donor materials are shown in Charts 2 and 4. fullerene small molecule acceptor DC-IDT2T. The stability of
Changing side chains of fullerene provides an opportunity PBDTTT-C-T/DC-IDT2T and PBDTTT-C-T/PC71BM devices was
to enhance the thermal stability of OSCs.194–196 For example, measured under continuous illumination and heating (75 1C),
Jen et al.195 synthesized a triphenylamine (TPA)-substituted as shown in Fig. 21a. The PBDTTT-C-T/DC-IDT2T device showed
PC61BM as the acceptor material in OSCs. This alteration of the much better stability (maintained 85% PCE after 180 h) relative
side chain from small size to big size broke the high symmetry to the PBDTTT-C-T/PC71BM device (maintained only 50% PCE
degree of PC61BM and therefore decreased its crystallinity. As a after 180 h). After the 180 h stability test, the light beam-induced
result, no degradation in morphology and efficiency was found in current (LBIC) images of PBDTTT-C-T/DC-IDT2T films changed a
the P3HT/TPA-PC61BM blend even after 10 h of heating at 150 1C. little (Fig. 21b and c), suggesting little loss of current during the
In addition to change the side chains of fullerene, employing stability test. In contrast, the colour of LBIC images of PBDTTT-
bisadduct fullerene derivatives as acceptors in OSCs is a more C-T/PC71BM films after the 180 h stability test became darker
widely used strategy for increasing the stability.197–202 This (Fig. 21d and e), which meant significant loss of current.
strategy can simultaneously avoid the dimerization and crystal- In addition to increasing photo/thermal stability, non-fullerene
lization of fullerene-based acceptors. For example, Guldi et al.197 acceptors also show talent in increasing mechanical stability.
investigated the photostability of PDTSTzTz/PC61BM and Kim et al.211 fabricated OSCs based on polymer donor
PDTSTzTz/bisadduct PC61BM (bisPC61BM) solar cells. After con- PBDTTTPD and polymer acceptor P(NDI2HD-T). As shown in
tinuous illumination for 27 h, PDTSTzTz/PC61BM solar cells Fig. 22a, the PBDTTTPD/P(NDI2HD-T) film showed much
degraded rapidly due to the dimerization of PC61BM, which higher toughness relative to PBDTTTPD/PC61BM film due to
reduced charge carrier mobility (the PCE preserved 74% of its its lower tensile moduli (0.43 GPa vs. 1.76 GPa) and much
original value); while devices based on bisPC61BM, which higher elongation (7.16% vs. 0.12%). Besides the tension test,
was not prone to dimerization, exhibited almost no degradation the bending test also announced better mechanical stability of
(the PCE preserved 95% of its original value). The authors polymer/polymer film compared to polymer/fullerene film. As
concluded that the steric hindrance from the two substituents shown in scanning electron microscopy (SEM) images (Fig. 22b
was the most probable reason for the higher photostability and c), the apparent degradation was attributed to the crack
of bisPC61BM compared to PC61BM. Wang et al.200 employed propagation in the PBDTTTPD/PC61BM film by the mechanical
a dihydronaphthyl-based [60]fullerene bisadduct derivative deformation (Fig. 22b). In stark contrast, there was no change in
NC60BA as an acceptor to increase the thermal stability of OSCs. the morphology of the PBDTTTPD/P(NDI2HD-T) film (Fig. 22c).
The reason for better mechanical stability of polymer/polymer
solar cells compared to polymer/fullerene solar cells was con-
cluded: the polymer acceptor was intrinsically more ductile than
fullerene and could better entangle with other polymer chains
with strengthened interfaces.
Fig. 20 Optical microscopy images of (a) the P3HT/NC60BA and (b)

Fig. 19 Schematic diagram of the strategies to design acceptors. P3HT/PC61BM blends after heating at 150 1C for 20 h.200
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Fig. 21 (a) Stability curves of PBDTTT-C-T/DC-IDT2T and PBDTTT-C-T/ Fig. 22 (a) Strain–stress curves of PBDTTTPD/PC61BM and PBDTTTPD/
PC71BM devices under continuous AM 1.5G illumination for 180 h (75 1C). P(NDI2HD-T) blend films. (The inset in (a) shows photographs of the BHJ
LBIC images of (b and c) PBDTTT-C-T/DC-IDT2T and (d and e) PBDTTTC- blend film floating on water. The specimens were gripped by the poly-
T/PC71BM films (b and d) before and (c and e) after exposing to sunlight for dimethylsiloxane (PDMS)-coated Al grips and the films were prepared
180 h (75 1C).207 All the scale bars are 1 cm. Reprinted with permission from under the optimized device conditions). SEM images of surface morphologies
ref. 207. Copyright 2015, Wiley. of (b) PBDTTTPD/PC61BM and (c) PBDTTTPD/P(NDI2HD-T) blend films after
bending at r = 1.0 mm. The scale bars are 500 nm.211 Reprinted with permission
from ref. 211. Copyright 2015, Nature Publishing Group.
3.2. Device engineering of the active layer
3.2.1. Ternary blend of a donor, an acceptor and a third
component. Ternary blend OSCs consisting of a donor material, an
acceptor material and a third component have received increasing
attention in recent five years. Compared with binary blend, OSCs
with a third component usually have higher PCE.212–216 In addition
to PCE, employing a third component (such as a cross-linker, a
modified fullerene derivative, a compatibilizer, an insulating
polymer, nanoparticles and buffer layer materials) in the active
layer can also increase the thermal/mechanical/photo/air stability
of OSCs (Fig. 23). The photovoltaic properties of devices with
different third components before and after the stability tests are
listed in Table 4. The ratio of the third component described
below is the weight ratio of third component in total weight of the
Fig. 23 Schematic diagram of the strategies to add third components.
donor, acceptor and third component in OSCs. The molecular
structures of donor and acceptor materials are shown in Chart 4
and the molecular structures of third components are shown in temperature would result in a three-membered ring-functionalized
Chart 5. fullerene. The cross-linking reaction between polymer/fullerene or
Cross-linkers can be used as the third components in the fullerene/fullerene could stabilize the morphology of the active
active layer to increase the thermal stability.217–219 For example, layer by preventing the fullerenes from diffusing and forming large
Wantz et al.218 introduced a bis-azide cross-linking reagent crystallites (Fig. 24). After addition of 2% BABP, the PTB7/BABP/
(BABP) as the third component in PTB7/PC61BM solar cells. PC61BM device yielded a PCE of 4.60% after 16 h of heating at
BABP could react with PTB7 or PC61BM through two pathways: (1) 150 1C, preserving 79% of its original value. In sharp contrast, the
upon heating or irradiation, BABP decomposed into nitrogen gas PCE of the device using PTB7/PC61BM blend decayed drastically to
and a highly reactive nitrene, which could react randomly with both 16% after the stability test.
PTB7 and PC61BM; (2) upon heating at a lower temperature, BABP Fullerene derivatives also can be modified as cross-linkers
reacted with PC61BM through a 1,3-dipolar cycloaddition to give and used as third components in the active layer to increase
triazolino(40 ,50 :1,2) fullerenes, and subsequent heating at a higher the thermal stability.220–223 Hsu et al.220 employed fullerene
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Fig. 24 Optical microscopy images (scale bar: 50 mm) of a PTB7/PC61BM

BHJ solar cell: (a) before thermal annealing and (b) after thermal annealing
at 150 1C for 16 h without a cross-linker. Numerous micrometer-sized
PC61BM crystals were observed. (c) Image of the same blend with the
addition of BABP after thermal annealing at 150 1C for 16 h, indicating the

absence of microcrystals.218 Reprinted with permission from ref. 218.
Copyright 2014, Wiley. Fig. 25 SEM cross-sectional images of the glass/ITO/PEDOT:PSS/blends
before and after heating at 150 1C for 25 h. (a) P3HT/PC61BM blend and
(b) P3HT/PCBS/PC61BM blend. The thickness of the photoactive layers is
derivative [6,6]-phenyl-C61-butyric acid styryl ester (PCBS) in approximately 250 nm.220 Reprinted with permission from ref. 220. Copy-
P3HT/PC61BM blend as the third component. Cross-linking right 2011, Wiley.
could happen between PCBS molecules by rapid polymerization
(polyaddition of styrene moieties), thus suppressing the severe
immigration of PC61BM. As shown in SEM cross-sectional Employing compatibilizers as third components in the active
images (Fig. 25), P3HT/PC61BM blend suffered severe phase layer is an effective strategy to simultaneously increase the
segregation after heating at 150 1C for 25 h. In contrast, the thermal and mechanical stabilities of OSCs.231–235 For example,
P3HT/PCBS/PC61BM blend maintained well-defined nano- Kim et al.233 employed a compatibilizer P3HT-g-P2VP in P3HT/
morphologies, which demonstrated that polymerization in o-xylenyl C60 bis-adduct (OXCBA) blend as the third component.
the blends was capable of freezing the initially formed The addition of P3HT-g-P2VP effectively modified the sharp
morphologies. As a result, the PCE of P3HT/PCBS/PC61BM solar interface between P3HT and OXCBA and decreased the surface
cells preserved 95% of its original value after the stability test, energy of D/A interfaces. As a result, the P3HT/OXCBA device
while the PCE of reference P3HT/PC61BM solar cells decreased with 3% P3HT-g-P2VP exhibited a PCE of 4.7% even after 72 h of
from 4.1% to 0.7%. In addition to fullerene-based cross-linkers, heating at 150 1C, which showed much better thermal stability
fullerene derivatives also can be modified and used as the third than that of the control device. In addition, the solar cells with
components in the active layer to control the crystallization 3% P3HT-g-P2VP exhibited higher fracture energy and lower
process of fullerene acceptors.224–229 McCulloch et al.226 con- tensile modulus, showing enhanced mechanical stability than
cluded that the addition of modified fullerene dimer (PCB)2C2 that of the control device. Using an insulating polymer as the
to the PCDTBT/PC61BM active layer could lead to enhanced third component in the active layer is another strategy to
thermal stability. The dimer could suppress the nucleation of simultaneously increase the thermal and mechanical stabilities
PC61BM, which was an effective route to suppress the excessive of OSCs. Stingelin et al.236 demonstrated that up to 50 wt% of the
aggregation and crystallization of fullerene. As a result, the PCE insulating polymer (high-density polyethylene (HDPE) or isotactic
of PCDTBT/(PCB)2C2/PC61BM solar cells preserved 90% of its polystyrene (PS)) could be used as third components in P3HT/
original value after the stability test. In contrast, the PCE of PC61BM solar cells. The addition of an insulating polymer could
PCDTBT/PC61BM solar cells preserved 75% of its original value. On increase the thermal stability and mechanical stability by impeding
the other hand, Müller et al.228 used C60 as the third component in diffusion of the lower molecular weight species (fullerene acceptor)
TQ1/PC61BM blend. C60 was able to efficiently help the formation of and increasing the toughness of the active layer.
large numbers of small fullerene crystal nuclei which could block In addition to thermal stability and mechanical stability, air
the growth of crystal nucleus to harmful micrometer-sized fullerene stability237–239 and photo/air stability240,241 can also be increased
crystals. Therefore, solar cells based on C60-nucleated active layers by employing third components in the active layer. For example,
displayed significantly enhanced thermal stability. In addition to Jo et al.237 added fullerene-end-capped poly(ethylene glycol)
thermal stability, fullerene derivatives also can be modified and (PEG-C60) in the P3HT/PC61BM blend. As shown in X-ray photo-
used as third components in the active layer to increase the electron spectroscopy (XPS) depth profiles (Fig. 26a and b), near
mechanical stability. For example, Lipomi et al.230 employed the interface between Al and the active layer, the intensity of the
PC71BM in P3HT/PC61BM blend as the third component to increase oxygen (O) signal was weaker than that of the S signal (Fig. 26a),
the mechanical stability of OSCs. They proposed that the mixing of whereas in the sample with PEG-C60 added, the intensity of the
PC61BM and PC71BM could change the aggregate states of P3HT O signal was stronger than that of the S signal (Fig. 26b).
and decrease the crystallinity of P3HT, which would increase the Considering that the O signal arose from PEG and PC61BM while
stretchability of the active layer and thus increase the mechanical the S signal arises only from P3HT, the results of XPS depth
stability of OSCs. As a result, the tensile moduli of active layers were profiles demonstrated that PEG-C60 molecules migrated to the top
decreased from 4.37 to 1.53 GPa after the addition of PC71BM as the surface of the P3HT/PC61BM active layer and induced segregation
third component. of PC61BM near the top surface (Fig. 26c). Since the PEG-C60 layer
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Fig. 27 Photophysics processes of (1) absorption; (2) emission; (3) system

intercrossing; (4) triplet state; (5a) fluorescence; (5b) triplet quenching; and
(6a/6b) exciton recombination via trap states.241 Reprinted with permission
from ref. 241. Copyright 2015, American Chemical Society.
Fig. 26 XPS depth profile of the P3HT/PC61BM films (a) without and
(b) with 2.5 wt% PEG-C60. (c) Cross-sectional SEM image of a P3HT/
PC61BM film with 2.5 wt% PEG-C60.237 Reprinted with permission from
could protect the active layer from oxygen penetration, the air
stability of OSCs was improved. Stratakis et al.241 employed Al
nanoparticles (NPs) in PCDTBT/PC71BM blend as the third
component. Energy from the polymer triplet excitons excited
singlet oxygen, which reacted with the polymer chains to form
exciton trap states. The Al NPs embedded into the blend acted
as quenchers of the triplet excitons, and in this way, the photo-
oxidation process could be impeded (Fig. 27). This quenching Fig. 28 Schematic diagram of the strategies of processing methods.
was possibly due to the overlap of the excitonic levels with
the plasmon resonance of the embedded Al NPs. As a result, the
PCE of PCDTBT/Al NPs/PC71BM OSCs preserved 50% of images (Fig. 29b and c), P3HT nanofibrils showed dense net-
its original value after irradiation in air (45 h). In contrast, works which were much less permeable to oxygen, and hence
the PCE of PCDTBT/PC71BM OSCs preserved 35% of its the photochemical degradation of P3HT by photo-oxidation in
original value. air could be delayed considerably as compared with P3HT in
3.2.2. Processing methods. Optimization of processing the control device. After exposing the photoactive layer to
methods of the active layer can increase the air stability, sunlight for 10 h in air, the PCE of nanofibril-based P3HT/
photostability and thermal stability of OSCs. As shown in PC61BM solar cells preserved 56% of its original value. In
Fig. 28, strategies can be employed in all processing steps contrast, the PCE of control P3HT/PC61BM solar cells decreased
including solution preparation, film forming and post treat- from 3.0% to 0.5% after the stability test. Yang et al.245 fabri-
ment to increase the stability. The photovoltaic properties of cated P3HT/PC61BM OSCs using 1,8-octanedithiol (OT) and
devices using different processing methods before and after the chlorobenzene (CB) as processing solvent, respectively. The
stability tests are listed in Table 5, and the molecular structures PCEs of these two devices were similar, but photo/air degrada-
of donor and acceptor materials are also shown in Chart 4. tion in OT processed films was much more severe than CB
Solution preparation is the first step in the fabrication of the processed films. The PCE of CB processed OSCs preserved 35%
active layer, and some strategies can be employed in this step to of its original value after irradiation in air (0.5 h). In contrast,
increase the photo/air stability and thermal stability.242–246 For the PCE of OT processed OSCs decreased to 0%. The films
example, Park et al.242 investigated the photo/air stability of made from OT started with a higher concentration of defects,
OSCs with different D/A ratios of 1 : 0.6 and 1 : 1 (P3HT/PC61BM making them more susceptible to photo/air degradation. The
by weight), respectively. As a result, the OSCs with the 1 : 1 increased energetic disorder suppressed the carrier hopping,
P3HT/PC61BM showed better photo/air stability due to the which enhanced the charge recombination. In addition to
lower donor content in OSCs which could reduce the photo- photo/air stability, the change of solvent is also a good strategy
chemical degradation from the formation of oxidized species in for achieving better thermal stability. Moulé et al.246 showed
the donor polymer. Jeong et al.244 fabricated nanofibril-based that the choice of processing solvent had a significant effect on
OSCs by subjecting P3HT/PC61BM solution to cyclical cooling the thermal stability of OSCs. Since o-dichlorobenzene (ODCB)
and heating processes (Fig. 29a). As shown in SEM and TEM had a higher BP compared to CB, the presence of trapped
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cells with modest illumination preserved 85% of its original

value after the stability test. In contrast, the PCE of the control
device preserved only 64% of its original value. Tsai et al.251
employed the post treatment of low temperature drying to
increase the thermal stability of P3HT/PC61BM solar cells.
The low drying temperature (5 1C) could enhance the nuclea-
tion of P3HT crystallites as well as minimize separation of the
P3HT and PC61BM phases. The enhanced P3HT crystal network
served as an immobile frame upon heating. As a result, the PCE
of P3HT/PC61BM solar cells upon low temperature drying
preserved 50% of its original value after the stability test

(long period of 1368 h). In contrast, the PCE of the control
device preserved only 16% of its original value. McNeill
et al.252 used alcohol treatment to improve the photo/air
stability of high-efficiency poly[[2,6 0 -4,8-di(5-ethylhexylthienyl)-
benzo[1,2-b;3,3-b]dithiophene]3-fluoro-2[(2-ethylhexyl)carbonyl]-
thieno[3,4-b]thiophenediyl] (PTB7-TH)/PC71BM solar cells. The
Fig. 29 (a) Schematic illustration of the formation method of nanofibril- introduction of alcohol treatment after the spin coating of the
based photoactive film using a P3HT/PC61BM solution subjected to cyclical active layer induced the fast deposition of the active layer, and
cooling and heating. The P3HT nanorods formed after the cyclical cooling prompted removal of residual DIO from the active layer.
and heating process quickly developed into single-crystal P3HT nanofibrils
Removal of the residual DIO inhibited ingress of oxygen into
through self-seeded growth during the coating process. (b) SEM and (c) TEM
images show the nanofibril-based photoactive film with a bicontinuous
the active layer, leading to enhanced photo/air stability compared
interpenetrating network of well-dispersed P3HT nanofibrils and PC61BM to that of the control device.
molecules.244 Reprinted with permission from ref. 244. Copyright 2014,
American Chemical Society. 3.3. Employing inverted geometry
For OSCs with conventional geometry, a low WF cathode, which
is easily attacked by oxygen and water, is always located at the
solvent (residual ODCB) in the OSCs would increase the diffu- exposed surface (no ITO protection) of the active layer. To
sive mobility of PC61BM within the polymer matrix, and pro- overcome the bad air stability of conventional OSCs, inverted
mote the growth of larger PC61BM crystals. Thus, OSCs geometry that the positions of the anode and the cathode are
processed by CB exhibited better thermal stability than that changed was developed. The photovoltaic properties of devices
of ODCB processed OSCs. with conventional and inverted geometries before and after the
The second fabrication step of the active layer is film stability tests are listed in Table 6, and the molecular structures
formation. Cabral et al.247 fabricated PCDTBT/PC61BM blend films of donor and acceptor materials are also shown in Chart 4.
by wire bar coating, instead of spin coating. Both wire bar coating Employing inverted geometry is an efficient strategy to
and spin coating solar cells yielded similar initial performance. significantly increase the air stability of OSCs.254–273 For example,
However, the wire bar coated solar cells exhibited improved device Choulis et al.260 fabricated inverted OSCs based on ITO/zinc oxide
thermal stability than spin coated solar cells (measured over 1000 h (ZnO)/P3HT/PC61BM/PEDOT:PSS/silver (Ag). Compared with the
of heating at 80 1C). The increased thermal stability of wire bar conventional OSCs based on ITO/PEDOT:PSS/P3HT/PC61BM/ZnO/
coated solar cells stemmed from enhanced PC61BM segregation Al, the inverted OSCs exhibited much better air stability. The
towards the top interface during deposition, which was likely due to PCE of inverted P3HT/PC61BM solar cells preserved 95% of its
the longer film drying timescale. original value after storage in air for 1 h. In contrast, the PCE of
Post treatment is the last step in the fabrication of the active the conventional OSCs preserved only 20% of its original value.
layer, and thermal stability as well as photo/air stability can be Also based on the P3HT/PC61BM active layer, Yang et al.261
increased by some strategies employed in this step.248–253 For compared the air stability of inverted geometry and conventional
example, Durrant et al.249 employed modest illumination on geometry. The structures of inverted and conventional OSCs
the active layer to induce the oligomerization of PC61BM. The were ITO/titanium oxide (TiOx) /P3HT/PC61BM/molybdenum oxide
oligomerization of PC61BM (dimer) could suppress the nuclea- (MoO3)/Ag and ITO/PEDOT:PSS/P3HT/PC61BM/Ca/Ag, respectively.
tion of PC61BM, and thus significantly suppressed the excessive As a result, the conventional P3HT/PC61BM solar cell lost 100%
aggregation and crystallization of PC61BM. As shown in Fig. 30, efficiency after aging for 48 h, while the solar cell based on inverted
illumination was employed to PS/PC61BM, PCDTBT/PC61BM, geometry lost only 5% efficiency. In addition to P3HT/PC61BM solar
PTB7/PC61BM, P3HT/PC61BM and DPP-TT-T/PC61BM blends, cells, employing inverted geometry also enhances air stability in
respectively. After continuous heating, a lot of fullerene crystals high-efficiency low band-gap donor/PCBM solar cells and small
appeared on the samples without modest illumination, but on molecule OSCs. Chang et al.263 fabricated inverted and conven-
the samples with modest illumination, no obvious fullerene tional OSCs based on PTB7/PC71BM which was one of the most
crystals appeared. As a result, the PCE of PCDTBT/PC61BM solar widely used active layers. After being stored in air for 48 h, the PCE
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Fig. 30 Optical microscopy images showing annealed morphologies of polymer/PC61BM blend films on silicon oxide (SiOx) substrates with (bottom
row) and without (top row) prior light exposure. (a and b) PS/PC61BM (1 : 1); (c and d) PCDTBT/PC61BM (1 : 2); (e and f) PTB7/PC61BM (1 : 2); (g and h) P3HT/
PC61BM (1 : 2); (i and j) DPP-TT-T/PC61BM (1 : 2). Films at the bottom panel were exposed to fluorescent light (10 mW cm2) for 165 min prior to annealing.
PS, PCDTBT, and PTB7 blend films were annealed at 140 1C for 60 min, and P3HT and DPP-TT-T blend films were annealed at 140 1C for 6 min. Film
thicknesses vary from 70 to 120 nm and are identical for each dark and light polymer film pair.249 Reprinted with permission from ref. 249. Copyright
2014, American Chemical Society.
of inverted PTB7/PC71BM solar cells preserved 95% of its original The microscopy images of ITO/MoOx/PCDTBT/PC71BM/TiOx/
value, while the PCE of the conventional OSCs preserved only Al, ITO/TiOx/PCDTBT/PC71BM/MoOx/Al, TiOx/Al and MoOx/Al
30% of its original value. Brabec et al.265 synthesized a new star- after aging of 100 h are shown in Fig. 32. It was found that the
shaped small molecule donor N(Ph-2T-DCN-Et)3, and compared formation of the bubble-like features, which reduced the
the air stability of inverted and conventional OSCs based on charge collection at the Al electrode, was linked to the presence
N(Ph-2T-DCN-Et)3:PC71BM. As a result, the PCE of inverted OSCs of hydroxyl groups in the TiOx layer (electron buffer layer). In
preserved 70% of its original value after storage in air for 360 h. contrast, the inverted OSCs with MoOx did not exhibit bubble-
In contrast, the PCE of the conventional OSCs preserved only 5% like features, attributed to the much better air stability than
of its original value. These studies changed the positions of the that of the conventional OSCs.
anode and the cathode and substituted the low WF electrode
with a high WF electrode on the top surface of the active layer.
This inverted geometry is more stable than conventional geometry 3.4. Optimizing buffer layers
due to less reactivity of the top electrode with oxygen and water. 3.4.1. Hole transport layers. PEDOT:PSS is the most widely
In-depth research for the much better air stability of used hole transport layer, while it is seriously unstable with air or
inverted geometry compared to conventional geometry was also mechanical stress. In addition, PEDOT:PSS suffers from its
carried out. Akimoto et al.266 investigated the charge dynamics strong acidity (pH = 1–2), which will etch the ITO electrode
of SubPc/C60 planar solar cells with conventional and inverted increasing the movability of In. Employing modified PEDOT:PSS,
geometries during the degradation in ambient air. As shown in metal oxide, graphene oxide (GO) and organic/polymer materials
Fig. 31, the features of transient photocurrent of the conventional to replace PEDOT:PSS can significantly increase the stability
device were ascribed to the aggravation of trap (deteriorated (Fig. 33).274–276 The photovoltaic properties of devices with
bathocuproine (BCP)) mediated recombination with increasing
aging time. In contrast, for inverted structure, the trap mediated
recombination was significantly suppressed, indicated by the
absence of the transient peak after turn-on and pulse intensity
dependent turn-off traces in the transient photocurrent. The active
layer and the BCP layer were well protected from penetration of
oxygen and water by the air stable MoO3 layer. As a result, for
the conventional devices, it only took 44 h for the PCE to
decay to 16% of its initial value. In contrast, the PCE of the
inverted devices preserved 89% of its original value after Fig. 31 The absolute transient photocurrent of conventional (a) and
storage in air for 96 h. Yoo et al.267 carried out a separate inverted devices (b) with different aging times.266 Reprinted with permission
experiment to investigate the air degradation of OSCs. from ref. 266. Copyright 2015, American Chemical Society.
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Fig. 33 Schematic diagram of the strategies to optimize the hole trans-

Fig. 32 Microscopy images of (a) conventional and (b) inverted OSCs after port layers.
aging of 100 h; (c) TiOx/Al and (d) MoOx/Al deposited on glass substrates.267
only 5% of its original value. So et al.287 employed NiOx as the
hole transport layer in pDTG-TPD/PC71BM solar cells. Similar
different hole transport layers before and after the stability tests to MoOx, NiOx also showed low hydroscopicity and good
are listed in Table 7. The molecular structures of hole transport inoxidizability as the nature of metal oxides. Therefore, the
layers are shown in Chart 6, and the molecular structures of NiOx based devices degraded much slower than the PEDOT:PSS
donor and acceptor materials are also shown in Chart 4. based devices. In addition to metal oxides, metal sulfides293 and
Modification of the PEDOT:PSS layer with the addition of polyoxometalates (POMs)294,295 can also be used to substitute the
various components (such as polymer additives, solvent additives, PEDOT:PSS layer to increase air stability.
metal oxides and nanoparticles) is an effective strategy to increase GO is also introduced as the hole transport layer for better
the air stability.277–283 For example, Kim et al.282 added PS NPs in air stability.296–300 Ouyang et al.298 used GO to substitute
the PEDOT:PSS layer to form a three-dimensionally continuous PEDOT:PSS as the hole transport layer of P3HT/PC61BM solar
minor phase via the formation of a monolayer self-assembled from cells. GO exhibited stable structure (less diffused ability) and
60 nm PS NPs. After the addition of PS, the conductivity of the low hydroscopicity, which were beneficial to achieving good air
PEDOT:PSS layer was maintained indicating that a continuous stability. As a result, the PCE of P3HT/PC61BM solar cells with
PEDOT:PSS film was successfully formed with PS NPs. As a result, the GO layer preserved 75% of its original value after the
the P3HT/OXCBA solar cells with the PEDOT:PSS layer lost 45% stability test. In contrast, the PCE of P3HT/PC61BM solar cells
efficiency after aging for 120 h, while the solar cells based on the with the PEDOT:PSS layer preserved only 5% of its original
PEDOT:PSS layer with PS NPs lost only 14% efficiency. Zhang value. In addition to inorganic materials, organic materials also
et al.283 developed a hole transport layer by in situ formation of can be used to substitute the PEDOT:PSS layer for increasing air
MoO3 in PEDOT:PSS solution (MoO3–PEDOT:PSS). As shown in the stability.301,302 Lee et al.301 introduced an organic small molecule
LBIC images (Fig. 34), the device with the MoO3–PEDOT:PSS layer 4-phenothiazin-10-yl-anisole (APS) as the hole transport layer of
exhibited much better air stability than the device with the P3HT/PC61BM solar cells. APS was highly air stable compared
PEDOT:PSS layer, due to the less hydroscopicity of MoO3. After
storage in air for 240 h, the PCE of TQ1/PC71BM solar cells with
the MoO3–PEDOT:PSS layer preserved 80% of its original value.
In contrast, the reference solar cells with the PEDOT:PSS layer
almost died.
In addition to the modification of the PEDOT:PSS layer,
employing other materials to replace the PEDOT:PSS layer is another
effective strategy to increase the air stability. Metal oxides such
as MoOx,284–286 nickel oxide (NiOx),287,288 vanadium pentoxide
(V2O5),289 tungsten oxide (WOx),290 copper oxide (CuO)291 and
ferriferrous oxide (Fe3O4)292 are promising candidates. Heeger
et al.285 fabricated PCDTBT/PC71BM solar cells with MoOx as the
hole transport layer. Compared to PEDOT:PSS, MoOx exhibited
superior long-term air stability, due to its less hydroscopicity and
better inoxidizability. As a result, the PCE of PCDTBT/PC71BM
Fig. 34 LBIC images of the devices exposed to ambient air: (a and d)
solar cells with the MoO3 layer preserved 50% of its original 0 day, (b and e) 4 days, and (c and f) 8 days. The hole transport layer was
value after storage in air for 860 h. In contrast, the PCE of PEDOT:PSS (a to c) or MoO3–PEDOT:PSS (d to f).283 Reprinted with
PCDTBT/PC71BM solar cells with the PEDOT:PSS layer preserved permission from ref. 283. Copyright 2013, Wiley.
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with PEDOT:PSS, due to its neutral PH and low hydroscopicity. The

OSCs fabricated with APS maintained a PCE of 2.8% (preserved
76% of its original value) after 2400 h of stability tests in air, while
the reference device based on PEDOT:PSS almost lost its efficiency
after 2400 h of ambient exposure.
Mechanical stability is another challenge for the PEDOT:PSS
layer, and some strategies have been introduced to optimize the
hole transport layer for better mechanical stability.303–306 For
example, Kim et al.304 added PS NPs to the PEDOT:PSS hole
transport layer of P3HT/PC61BM solar cells. The PS NPs acted as
the binders in the PEDOT:PSS domains which can increase the

fracture toughness of the hole transport layer. As a result, the
adhesion energy of the PEDOT:PSS layer was increased from
2.2 J m2 to 3.4 J m2 with the addition of PS NPs, indicating
that the addition of PS NPs to PEDOT:PSS can increase the
mechanical stability. Lipomi et al.305 discovered that the addition
of zonyl fluorosurfactant and dimethylsulfoxide (DMSO) into the
PEDOT:PSS layer can significantly improve the mechanical compli- Fig. 35 (a) Photograph of the devices comprising PEDOT:PSS films with
ance without decreasing PCE. As shown in Fig. 35, the PEDOT:PSS 5% DMSO and 10% zonyl transferred onto thin PDMS substrates and
layer with zonyl and DMSO can suffer large strain (E20%) and adhered to a glove using conductive copper tape. (b) Computational
exhibit good mechanical robust during cyclic bending. analysis of strain produced in the thin films when subjected to bending
3.4.2. Electron transport layers. Lithium fluoride (LiF) or with the radius curvature of 5 mm, approximately the radius of curvature of
the second knuckle. The peak strain occurred at the location of the second
Ca and ZnO are the most widely used electron transport layers knuckle with an equivalent strain of E20%. (c) Plot of relative resistance
in conventional geometry and inverted geometry, respectively. (R)/R0 as a function of time for the devices placed on the human hand. The
LiF or Ca is unstable in air due to their reactivity with oxygen and shaded areas refer to when strains are applied by bending of the fingers.
water. On the other hand, ZnO is unstable with air and light. In (d) R/R0 vs. time of the devices on the linear actuator cycling between 0%
order to significantly increase the stability, metal oxide, stable and 20% strains. The inset shows the average R/R0 at both positions as a
function of the number of cycles.305 Reprinted with permission from
metal, electron transport polymers and modified ZnO can be
employed instead of LiF, Ca and ZnO (Fig. 36).307,308 The
photovoltaic properties of devices with different electron trans-
port layers before and after the stability tests are listed in Table 8.
The molecular structures of electron transport layers are shown
in Chart 6, and the molecular structures of donor and acceptor
materials are also shown in Chart 4.
Employing metal oxide, stable metal and electron transport
polymers to replace LiF and Ca can increase the air stability.309–313
For example, Xu et al.309 fabricated OSCs with chromium oxide
(CrOx) as the electron transport layer. The CrOx layer was much
more air-stable than LiF, and could function as a protective layer to
Fig. 36 Schematic diagram of the strategies to optimize the electron
significantly enhance the device stability by blocking the diffusion transport layers.
of oxygen and water. As a result, the PCE of P3HT/PC61BM solar
cells with the CrOx layer preserved 69% of its original value after
storage in air for 48 h. In contrast, the reference solar cells with the be modified.314,315 Zheng et al.314 employed Zn1xMgxO (ZMO)
LiF layer almost died. Yang et al.313 used an anionic surfactant SDS as the electron transport layer of PTB7-TH/PC71BM solar cells.
to modify the cationic PTMAHT polyelectrolyte and employed the Compared with the control device with the ZnO electron trans-
PTMAHT:SDS blend as the electron transport layer of OSCs. After port layer, the ZMO-based OSCs exhibited better air stability,
storage in air for 12 h, the PCE of P3HT/PC61BM solar cells with the which could be attributed to the fact that the wide bandgap
PTMAHT:SDS layer preserved 75% of its original value, while the ZMO could serve as a good moisture/oxygen scavenger to
PCE of the reference solar cells with the Ca layer only preserved protect the device against degradation in air over a long period
30% of its original value. The results suggested that the electrostatic (1 year). Secondly, the fabrication method of ZnO film can be
complexion between PTMAHT and SDS provided an effective modified.316–318 Zhang et al.317 employed ethanedithiol (EDT)
method to achieve the moisture/water-resistant electron trans- to treat the surface of ZnO film. Solar cells with EDT ZnO
port layer, which could increase the air stability. (E-ZnO) exhibited better air stability due to the passivated
In addition to LiF and Ca used in conventional geometry, surface defects. The EDT molecule could remove various surface
ZnO used in inverted geometry can also be modified to achieve groups (–COO and –OH) and form a covalent bond with
better air stability. Firstly, the chemical composition of ZnO can ZnO film. The excellent passivation made the ZnO films less
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susceptible to oxygen and water molecules. As a result, the PCE of

P3HT/PC61BM solar cells with the E-ZnO layer preserved 96% of its
original value after being stored in air for 720 h. In contrast, the
reference solar cells preserved only 68% of its original value. Thirdly,
ZnO film can be modified by various buffer layers.319–324 Qiao
et al.319 modified the ZnO layer by inserting a poly-ethylenimine
ethoxylated (PEIE) layer. After half a year of ambient exposure, the
PCE of P3HT/PC61BM solar cells with the ZnO/PEIE layer preserved
88% of its original value. In contrast, the PCE of reference OSCs with
the ZnO layer decreased from 4.0% to 2.3% after the stability test. As
shown in Fig. 37, the ZnO device exhibited higher current density
than the fresh sample at low bias, due to the oxygen-induced trapped
states which could increase the probability of trap-assisted recombi-
nation. Contrastively, the ZnO/PEIE device maintained small current
density at low bias after the stability test. The PEIE layer could
passivate the ZnO layer and suppress the oxidation of the ZnO layer
Fig. 37 Dark current density–voltage characteristics for fresh and 6
which was the reason for the increased air stability. In addition to month aged samples.319 Reprinted with permission from ref. 319. Copy-
the modification of ZnO, the substitution of ZnO by the electron right 2015, American Chemical Society.
transport polymer (such as PEI and DPP-based polymers) is another
strategy to increase the air stability.325–327
Insufficient photostability is another shortcoming of OSCs stability test. The molecular structures of donor and acceptor
with the ZnO layer.328–333 Olson et al.329 employed phosphonic materials are also shown in Chart 4.
acids (PAs) to modify the interface of the ZnO layer. The Employing stable metal and alloy,336–339 metal nanowire
chemical nature of the ZnO surface exhibited the influence on (NW)340–342 and modified metal NW343–350 as the transparent
device photostability, specifically the presence of interstitial zinc electrode is an effective strategy to increase the mechanical stability.
(Zni) defects at the surface which can absorb oxygen and induce For example, Yun et al.339 fabricated flexible PTB7-F20/PC71BM solar
the photo-oxidation reaction of the adjacent organic active layer. cells with the ZnO/AgOx TCE on the polyethylene terephthalate (PET)
PA modification of the ZnO layer could eliminate or passivate substrate. As shown in Fig. 39a, the DR/R0 of the electrodes was
these defects. As a result, the PCE of P3HT/ICBA solar cells with measured as a function of the bending radius when the electrodes
the PA-modified ZnO layer preserved 73% of its original value were exposed to high compressive stresses induced by mechanical
after illumination for 640 h, whereas the reference solar cells bending of the PET substrates. The ZnO/AgOx electrode exhibited
preserved only 38% of its original value. Wu et al.330 modified small resistance changes of 1.33% even after being bent with a
the surface of the ZnO layer with an ultrathin layer of Al. The bending radius of 2.8 mm. However, DR/R0 of the reference ITO
diode parameters suggested that the reference solar cells with electrode dramatically increased to 35% at the same bending radius,
the ZnO layer experienced a dramatic increase in their reverse as a result of the formation and propagation of microscopic cracks
saturation current upon illumination due to a decrease in the in a direction perpendicular to the compressive load (Fig. 39b). Thus,
barrier height. The device with the Al modified ZnO layer employing the ZnO/AgOx electrode instead of the reference ITO
experienced a much less change in its diode parameters before electrode could increase the mechanical stability of flexible OSCs.
and after photoaging, due to its lower surface WF and deeper Kang et al.341 used more soft Ag NWs as the transparent electrode to
valence band maximum. As a result, the PCE of P3HT/PC61BM replace ITO. After being bent 1000 times with a bending strain of
solar cells with the ZnO/Al layer preserved 82% of its original B2.0%, the Ag NW electrode showed only a slight increase in the
value after illumination for 8 h. In contrast, the reference solar DR/R0 (3.3%), whereas that of the reference ITO electrode dramati-
cell preserved 69% of its original value. cally increased (68.8%). As a result, the PCE of PTB7/PC71BM solar
cells with the Ag NW electrode preserved 98% of its original value
3.5. Using stable electrodes after 1000 bending cycles. In contrast, the reference solar cells with
ITO and Al are the most widely used transparent electrode the ITO electrode preserved only 22% of its original value. In
(TCE) and back electrode in OSCs, respectively. However, they addition to directly using Ag NWs as the electrode, modified Ag
are seriously unstable with mechanical stress, irradiation and NWs as the electrode are also used. Kim et al.345 created a flexible
air. Employing transparent materials (such as metal and alloy, electrode based on the conductive polymer (CP)–AgNW composite
metal nanowire, graphene, polymer and modified ITO) instead which was fully embedded in colorless polyimide (cPI). Fig. 40
of ITO and stable metals (such as Ag, gold (Au) and Cu) instead shows the DR/R0 in response to outward (tensile stress) or inward
of Al can significantly increase the stability (Fig. 38).334,335 The (compressive stress) bending as a function of the bending
photovoltaic properties of devices with different transparent/ radius. The (CP)-AgNW/cPI electrode exhibited good mechanical
back electrodes before and after the stability tests are listed in stability (only a small increase (o10%) in resistance when it was
Table 9, in which the DR/R0 is defined as the change in the bent to a radius of 40 mm). PTB7-TH/PC71BM solar cells based on
sheet resistance after the stability test/resistance before the this composite electrode therefore offered a very stable performance,
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Fig. 40 Effect of the bending radius on the resistance of a 20 mm thick

Fig. 38 Schematic diagram of the strategies to use stable electrodes. film.345 Reprinted with permission from ref. 345. Copyright 2015, Wiley.
electrode instead of ITO. The efficiency of the devices with the Ag

electrode remained almost unchanged for 1000 h with illumination
(preserved 96% of its original value). In contrast, the reference solar
cells with the ITO electrode preserved only 28% of its original value.
The solar cells with the Ag electrode exhibited much better photo-
stability due to the avoiding unstable ITO/PEDOT:PSS interface.
Curran et al.360 investigated the degradation mechanism of the
ITO/PEDOT:PSS interface and the Ag/PEDOT:PSS interface under
ambient conditions. As shown in Fig. 41, the rapid and contin-
Fig. 39 (a) Photographs of irreversible bending tests of flexible TCEs uous degradation of ITO based devices was a result of obvious
coated on PET substrates. (b) The percentage change in the resistance and continuous migration of In into the PEDOT:PSS layer.
of the TCEs as a function of the bending radius. Insets represent the optical
images of the TCEs after being bent with a bending radius of 2.8 mm.339
However, for the Ag/PEDOT:PSS interface, no more Ag migrated
Reprinted with permission from ref. 339. Copyright 2014, Wiley. into the PEDOT:PSS layer except the small amount of initial
oxidized Ag, since Ag was very difficult to oxidize (the electro
0
chemical potential of Ag: EAg þ =Ag ¼ 0:7996 V). Thus it was con-
with a PCE loss of not more than 5% when it was folded at a radius vinced that Ag was more stable than ITO under ambient conditions.
of 40 mm. This high mechanical flexibility originated from the Similar to the substitution of transparent electrodes, using
enlarged interfacial area between AgNWs and cPI, and good adhe- stable metals (such as Ag, Au and Cu) instead of Al as back
sion of cPI to the CP and AgNWs. Lee et al.350 fabricated a AgNW– electrodes is an effective strategy to increase the air stability.35,361–365
graphene hybrid TCE by dry-transferring a CVD-grown monolayer For example, Kim et al.362 replaced the back electrode Al with air
graphene onto a AgNW TCE. Within the first few bending cycles with stable Ag. The PTB7/PC71BM solar cells with Ag exhibited higher
a bending radius of 30 mm, the ITO TCE began to crack, resulting PCE than the reference solar cells with Al (8.0% vs. 7.1%). More
in a sharp increase in sheet resistance. In contrast, the sheet importantly, Ag based devices exhibited better air stability due to the
resistance of the AgNW–graphene–polyethylene naphthalate low reactivity of Ag with water or oxygen. As a result, the PCE of
(PEN) TCE remained unchanged after more than 10 000 bending PTB7/PC71BM solar cells with the Ag back electrode preserved 96%
cycles with the same bending radius, indicating that the AgNW– of its original value after being stored in air for 170 h. In contrast, the
graphene hybrid TCE exhibited excellent mechanical flexibility. reference solar cells with the Al back electrode preserved 75% of its
Besides stable metal based materials, graphene351,352 and original value. Emrick et al.35 employed Au as the back electrode of
PEDOT:PSS353,354 also can be used as transparent electrodes to PTB7-TH/PC71BM solar cells. Thanks to the new and effective
increase the mechanical stability. For example, Zheng et al.352 electron buffer layer which could lower down the WF of the
fabricated a graphene-based composite transparent electrode Au/active layer interface, the device exhibited a high PCE of 8.6%
to replace ITO and used in OSCs. After 1000 bending cycles, which was the highest report for OSCs with the Au back electrode.
only ca. 5% increase in the resistance of the graphene-based After being stored in air for 24 h, the Au covered OSCs showed
TCE was observed, and no cracks appeared. In contrast, the outstanding air stability (preserved 99% of its original value).
resistance of the traditional ITO TCE increased rapidly under
bending due to crack formation.
In addition to mechanical stability, photostability355,356 and air 3.6. Encapsulation
stability357–360 also can be increased by using a stable transparent Employing organic, inorganic and organic–inorganic complex
electrode. For example, Katz et al.355 used Ag as the transparent materials to encapsulate OSCs is an effective strategy to
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Fig. 42 (a) OSCs were fabricated on top of the fused silica glass substrate. The
multilayer photonic structure was deposited on top of the electrical structure
saving the silver contacts. (b) SEM cross-sectional micrograph of the ML-ST. In
this particular case instead on a glass substrate, the structure was grown on a
doped-silicon substrate to avoid charging effects during the SEM scanning.370

Fig. 41 (a) Proposed mechanism for the degradation of the ITO/PEDOT:PSS

interface under ambient conditions. (b) Proposed mechanism of the degrada-
tion of the Ag/PEDOT:PSS interface under ambient conditions.360
Fig. 43 Structure of a complete device encapsulated with UV resin and
ZnO as the barrier layer.381 Reprinted with permission from ref. 381. Copy-
right 2013, Elsevier.
increase the air stability. The photovoltaic properties of devices
with different encapsulation materials before and after the
stability tests are listed in Table 10. The molecular structures Organic–inorganic complex materials can be used as the
of donor and acceptor materials are also shown in Chart 4. encapsulation layers of OSCs. Epoxy resin and glass is the most
Organic materials can be used for encapsulation of popular partner.375–378 Watkins et al.375 encapsulated the OSCs
OSCs.366–369 Würfel et al.366 employed epoxy resin to encapsu- by using epoxy and glass. Epoxy resin was an effective and
late OSCs. Completely flexible devices maintained 490% of widely used UV photocuring resin, and glass was cheap. After
their initial device performance after 1000 h. The good air the simple encapsulation, the air stability of OSCs was
stability of the encapsulated flexible OSCs was attributed to the obviously increased. However, the process of glass/UV resin
similar coefficient of thermal expansion of these organic mate- encapsulation usually brought additional mechanical stress to
rials, which was beneficial for good adhesion between different OSCs, and the solvent of resin would damage the active layer. In
layers. In addition to organic materials, inorganic materials order to avoid this additional mechanical stress and the
also can be used as the encapsulation layer.370–374 For example, adverse solvent effect, other organic–inorganic complex encap-
Martorell et al.370 designed a transparent multilayered MoO3/ sulation layers were employed.379–381 For example, Jang et al.381
MgF2 (ML-ST) to encapsulate the OSCs (Fig. 42). The thick developed a solution process encapsulation method: coating
inorganic multilayer could provide efficient isolation from the ZnO layer on top of the back electrode and subsequently
oxygen and water, which contributed to good air stability. As drop coating UV resin (Fig. 43). The ZnO buffer layer was used
a result, the PCE of PTB7/PC71BM solar cells with multilayered to minimize the damage from acetone in UV resin film and the
MoO3/MgF2 preserved 60% of its original value after being thermosetting properties of UV resin. As a result, the PCE of
stored in air for a long period of 3500 h. In contrast, the P3HT/PC61BM solar cells with ZnO/UV resin encapsulation
reference solar cells almost died. Park et al.372 used the reduced preserved 80% of its original value after being stored in air
GO (rGO) to encapsulate PCDTBT/PC71BM solar cells. The rGO for 636 h, while the reference solar cells almost died.
encapsulation layer could act as an efficient gas barrier with a
very low permeability of 3.65 104 g mm m2 day1. After 4. Summary and outlook
being stored in air for 24 h, the PCE of PCDTBT/PC71BM solar
cells with rGO encapsulation preserved 95% of its original This review discussed the factors that limit the stability of OSCs
value, while the reference solar cells preserved only 7% of its during their whole lives in terms of metastable morphology,
original value. diffusion of electrodes and buffer layers, oxygen and water,
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Fig. 44 Schematic diagram of the strategies to increase stability.
irradiation, heating and mechanical stress. More importantly, promotion of uniform standards of stability tests, e.g. ISOS protocols;
this review highlighted the recent developments in strategies to (c) design of a polymer donor with balanced crystallinity/amorphism
increase stability of organic solar cells (a polymer donor/fullerene and rigidity/flexibility to simultaneously increase photo/air, thermal
acceptor is used as the model system and shown in Fig. 44): and mechanical stabilities; (d) increasing the PCE of OSCs based on
(I) Strategies to increase photo- or photo/air stability: the polymer with cleavable side chains and photo/air stable units;
employing cleavable side chains and photo/air stable units on (e) using non-fullerene acceptors instead of PCBM for better photo/
the polymer; increasing polymer crystallinity and decreasing air, thermal and mechanical stabilities; (f) increasing the PCE of
fullerene crystallinity; decreasing defects/traps in the active OSCs without high BP solvent additives and thermal or solvent
layer; and decreasing oxygen permeation to the active layer. annealing; (g) employing advanced encapsulation technologies in
(II) Strategies to increase air stability: decreasing oxygen permea- OSCs. So far, OSCs have already exhibited the PCEs of exceeding
tion and water ingress into the active layer; using electrodes which 10%, and increasing the stability of OSCs will provide a great
exhibit low reactivity with oxygen and water; employing charge opportunity to realize future industrial manufacture.
transport layers with good inoxidizability, low hydroscopicity and
neutral PH; and changing the device geometry.
(III) Strategies to increase thermal stability: decreasing full- Abbreviations
erene crystallinity; increasing Tg of the polymer; employing a
cross-linkable polymer/fullerene or adding a cross-linker; 2T Bithiophene
removing residual solvents in the active layer; and forming a Z/Z0 The ratio of PCE after and before the stability
stable D/A interface and an active layer/electrode interface. test
(IV) Strategies to increase mechanical stability: increasing Ag Silver
polymer flexibility and entanglement but decreasing polymer Al Aluminium
crystallinity; forming a stable D/A interface; increasing layer/ AM Air mass
layer adhesion; and increasing the flexibility of encapsulated APS 4-Phenothiazin-10-yl-anisole
materials. Au Gold
In order to achieve high-efficiency and high-stability OSCs for BABP Bis-azide cross-linking reagent
future industrial manufacture, some research areas of device BCP Bathocuproine
stability may deserve further attention in the future: (a) in-depth BDT Benzodithiophene
investigation of the device degradation mechanisms with oxygen, BHJ Bulk heterojunction
water, irradiation, heating and mechanical stress; (b) setup and BT Benzothiadiazole
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bisPC61BM Bisadduct PC61BM PEIE Poly ethylenimine ethoxylated

BP Boiling point PEDOT:PSS Poly(3,4-ethylenedioxythiophene):poly(styrene
Br Bromide sulfonate)
Ca Calcium P3HT Poly(3-hexylthiophene)
CB Chlorobenzene PCDTBT Poly(N-9 0 -hepta-decanyl-2,7-carbazole-alt-5,5-
CrOx Chromium oxide (4 0 ,7 0 -di-2-thienyl-2 0 ,1 0 ,3 0 -benzothiadiazole))
cPI Colorless polyimide PTB7-TH Poly[[2,6 0 -4,8-di(5-ethylhexylthienyl)benzo-
CP Conductive polymer [1,2-b;3,3-b]dithiophene]3-fluoro-2[(2-ethylhexyl)-
CuO Copper oxide carbonyl]thieno[3,4-b]thiophenediyl]
DIO 1,8-Diiodooctane PTB7 Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo-
DPP Diketopyrrolopyrrole [1,2-b:4,5-b 0 ]dithiophene-2,6-diyl]-

DPP2F Diketopyrrolopyrrole unit flanked by two furan [3-fluoro-2-[(2-ethylhexyl)-carbonyl]-thieno-
rings [3,4-b]thiophenediyl]]
DMSO Dimethylsulfoxide PEN Polyethylene naphthalate
DTT Dithienothiophene PET Polyethylene terephthalate
DTZ Dithienylthiazolo[5,4-d]thiazole PEG-C60 Fullerene-end-capped poly(ethylene glycol)
D/A Donor/acceptor PFs Polyfluorenes
EDT Ethanedithiol POM Polyoxometalate
Fe3O4 Ferriferrous oxide PS Polystyrene
FF Fill factor PCE Power conversion efficiency
F Fluorine rGO Reduced graphene oxide
GO Graphene oxide RRa Regiorandom
GISAXS Grazing incidence small angle X-ray scattering RR Regioregular
GIWAXS Grazing incidence wide angle X-ray scattering R Resistance
HDPE High-density polyethylene R2R Roll-to-roll
HOMO Highest occupied molecular orbital SEM Scanning electron microscope
H Hydrogen SiO2 Silicon dioxide
ICBA Indene-C60 bisadduct S Sulfur
In Indium T Thiophene
ISOS International summit on OPV stability Tg Glass transition temperature
ITO Indium tin oxide TQ1 Poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-
IQE Internal quantum efficiency diyl-alt-thiophene-2,5-diyl]
JSC Short-circuit current density TiOx Titanium oxide
LBIC Light beam-induced current TEM Transmission electron microscope
LiF Lithium fluoride TCE Transparent electrode
LUMO Lowest unoccupied molecular orbital TPA Triphenylamine
MW Molecular weight UV Ultraviolet
MoO3 Molybdenum oxide VOC Open circuit voltage
MDMO-PPV Poly[2-methoxy-5-(3 0 ,7 0 -dimethyl-octyloxy)]-1,4- V2O5 Vanadium pentoxide
phenylene vinylene WF Work function
ML-ST Transparent multilayered MoO3/MgF2 WOx Tungsten oxide
NPs Nanoparticles XPS X-ray photoelectron spectroscopy
NW Nanowire ZnO Zinc oxide
NiOx Nickel oxide Zni Interstitial zinc
NC60BA Dihydronaphthyl-based [60]fullerene bisadduct ZMO Zn1xMgxO
derivative
ODCB o-Dichlorobenzene
OSC Organic solar cell Acknowledgements
OT 1,8-Octanedithiol
We thank the NSFC (91433114, 51261130582, and 21025418) for
O Oxygen
financial support.
OXCBA o-Xylenyl C60 bis-adduct
PA Phosphonic acids
PCBS [6,6]-Phenyl-C61-butyric acid styryl ester References
PC61BM [6,6]-Phenyl-C61-butyric-acid-methyl-ester
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Chem Soc Rev

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Stability of organic solar cells: challenges

Cite this: DOI: 10.1039/c5cs00593k

1. Introduction environmentally friendly, is a good candidate. Especially, organic

Pei Cheng received his BS degree in Xiaowei Zhan obtained a PhD

Review Article Chem Soc Rev

designing and fabricating new device structures.37–42 As a result,

example, Heeger et al.56 fabricated a conventional OSC with the

Fig. 2 Simulated and measured short-circuit current. Black squares repre-

Chem Soc Rev Review Article

will change their photon absorption, energy levels and charge

damage the low WF metal electrodes as an oxidation agent.76

Review Article Chem Soc Rev

Thirdly, these reactions can change the energy levels of donors

Fig. 6 Schematic energy diagram of bulk heterojunction organic solar cells

Chem Soc Rev Review Article

temperature is still far below the decomposition temperatures of

tures on the PCDTBT/PC71BM blend films was investigated and the

Review Article Chem Soc Rev

test conditions are employed; ‘‘w’’ means ‘‘with’’; ‘‘w/o’’ means

3.1. Material design of the active layer

This journal is © The Royal Society of Chemistry 2016

Chem. Soc. Rev.

Chem. Soc. Rev.

This journal is © The Royal Society of Chemistry 2016

This journal is © The Royal Society of Chemistry 2016

Chem. Soc. Rev.

Chem. Soc. Rev.

This journal is © The Royal Society of Chemistry 2016

This journal is © The Royal Society of Chemistry 2016

Chem. Soc. Rev.

Review Article Chem Soc Rev

Chem Soc Rev Review Article

Chart 3 The molecular structures of fullerene and non-fullerene acceptor materials.

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Chem Soc Rev Review Article

Chart 6 The molecular structures of buﬀer layers.

Fig. 10 Schematic diagram of the strategies to design the molecular

Alkyl side chains facilitate the dissolution and assembly of

Review Article Chem Soc Rev

Reducing the polymer regioregularity is another eﬀective

Chem Soc Rev Review Article

Fig. 17 Illustration of diﬀerent formations of polymer aggregates based

original value. Maes et al.187 reported that the stability of OSCs

Review Article Chem Soc Rev

Fig. 20 Optical microscopy images of (a) the P3HT/NC60BA and (b)

Chem Soc Rev Review Article

Review Article Chem Soc Rev

Fig. 24 Optical microscopy images (scale bar: 50 mm) of a PTB7/PC61BM

addition of BABP after thermal annealing at 150 1C for 16 h, indicating the

Chem Soc Rev Review Article

Fig. 27 Photophysics processes of (1) absorption; (2) emission; (3) system

Review Article Chem Soc Rev

cells with modest illumination preserved 85% of its original

preserved 50% of its original value after the stability test

Chem Soc Rev Review Article

Review Article Chem Soc Rev

Fig. 33 Schematic diagram of the strategies to optimize the hole trans-

Chem Soc Rev Review Article