Nano Energy 89 (2021) 106399

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Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

Flexible organic solar cells: Materials, large-area fabrication techniques and

potential applications
Chunhui Liu, Chengyi Xiao *, Chengcheng Xie, Weiwei Li *
Beijing Advanced Innovation Center for Soft Matter Science and Engineering & State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, China

A R T I C L E I N F O A B S T R A C T

Keywords: Organic solar cells (OSCs) that converted sunlight into electricity have obtained numerous progress in the past
Flexible organic solar cells two decades. With the efforts of developing new conjugated materials, the power conversion efficiencies (PCEs)
Transparent electrodes of OSCs have realized over 18%, which are comparable with other types of solar cells. These great achievements
Conjugated materials
enable OSCs to arrive at the key period toward industrial application. Flexibility is the main characteristic of
Large-area fabrication
Potential applications
OSCs, which endows OSCs to be applied into special fields. In this review, we will provide an overview about the
research progress of flexible OSCs (F-OSCs), from the aspect of materials (including flexible electrodes, interfacial
layers and photoactive layers), large-area fabrication techniques and potential applications. These advancements
enable F-OSCs to achieve PCEs over 15% with high stability, and we will also discuss the problems in F-OSCs. We
hope that with this review, more studies from the academia and industrial community will be involved into F-
OSCs, especially focusing on new materials toward application in the future.

1. Introduction
Flexible electronics as emerging fields will be the key technologies
that are related to our daily life in the future [1,2]. Electronics devices
with flexibility, such as electronic skin with different sensors [3,4],
flexible organic light-emitting diodes [5], field-effect transistors [6,7]
and photovoltaics [8], have the advantage of light-weight, easy fabri­
cation via printing technology, tight attached to the surface with
different shapes, etc. Integration of the electronic elements is the key to
realize the function. For example, if researchers want to setup an elec­
tronic skin for tissue cardiac sensors, the power systems by using flexible
organic solar cells (F-OSCs) and the sensor by using organic electro­
chemical transistors need to be integrated in order to generate the
self-powered sensor systems [9]. Here, F-OSCs are the first devices to
drive other flexible facilities and will be discussed in this review.
OSCs use organic semiconductors as photoactive layer to convert
sunlight into free carriers (hole/electron), and generate electricity via a
simple configuration of cathode/anode with transporting layers. OSCs
were reported as early as 1959, when researchers used a single layer of
single crystal anthracene as photoactive layer [10]. The efficiency was
fairly low due to the low dielectric constant of organic material,
resulting in bounded excitons (hole/electron) that cannot separate into
free charges. This situation was completely changed when C. W. Tang
introduced the donor/acceptor concept into the photoactive layer in
1986, so that the excitons had the extra energy to be separated [11]. In
1992, Heeger et al. found the photoinduced charge transfer between a
donor polymer to a fullerene derivative [12], and then the same group
created the bulk-heterojunction (BHJ) concept in 1995 [13], in which
the donor polymer and fullerene derivative were physically mixed to
generate the interface between donor and acceptor. Until now, BHJ is
still the main structure in OSCs, in which the photogenerated excitons
are separated into free charges in the interface of donor/acceptor and
then transport into the electrode [14].
If looking into the history of OSCs, we can find that most of efforts
focus on searching for new organic semiconductors in order to realize
high performance from the aspect of absorption spectra, energy levels,
crystallinity, charge carrier mobility, etc [15–21]. For example, the
donor polymers went from poly(phenylene vinylene) derivatives [22]
with low carrier mobilities to poly(3-hexylthiophene) [23] with high
crystallinity and high mobility and nowadays “donor-acceptor” conju­
gated polymers with distinct electron-donating and
electron-withdrawing building blocks [18,24,25]. Electron acceptors
also experience the same period, from fullerene derivatives to
non-fullerene materials, especially fused-ring electron acceptor that was

* Corresponding authors.
E-mail addresses: xiaocy@mail.buct.edu.cn (C. Xiao), liweiwei@iccas.ac.cn (W. Li).

https://doi.org/10.1016/j.nanoen.2021.106399
Received 18 June 2021; Received in revised form 22 July 2021; Accepted 31 July 2021
Available online 4 August 2021
2211-2855/© 2021 Elsevier Ltd. All rights reserved.
C. Liu et al.
invented by Zhan et al. in 2015 [26]. These efforts enabled the power
conversion efficiencies (PCEs) of OSCs to boost to over 18% [27–29],
and hence OSCs show the high competitiveness with other types of solar
cells.
Obviously, after numerous efforts in several decades, OSCs have
arrived at the key period toward application. OSCs can use flexible
substrates, inorganic or organic electrode and the organic photoactive
layers, so that they can use the printing techniques in industry to
fabricate flexible devices [46–48]. This is the special characteristic
compared to other solar cells. Many efforts have also focused on making
F-OSCs, such as searching new materials for the different layers of solar
cells, inventing large-area fabrication techniques and looking for the
application scenes. Researchers show that F-OSCs can also generate
similar PCEs as rigid OSCs (Fig. 1), and they can be installed in a large
area as a solar park [49]. These promising advancements are definitely
exciting and inspire researchers to further develop the technologies for
F-OSCs toward industrial application.
Therefore, in this review, we focus on F-OSCs, from the aspect of
materials, large-area fabrication techniques and the potential applica­
tion (Fig. 2). Particularly, we try to find out the requirement and the
possible selection (from materials and fabrication techniques) to meet
the industrial application. We hope that with this review, new ideas can
be inspired in this area toward final application.
2. Key materials for F-OSCs
2.1. Flexible substrates for F-OSCs
The substrates of F-OSCs strongly affect the final flexibility and other
properties due to the occupation of the most thickness of the whole
devices. Materials that are used as the substrate in F-OSCs should have
the following characteristics: transparency, photo-stability, chemical
stability to avoid the penetration of oxygen or solvents into photoactive
layers, relatively high thermal transition temperature and low coeffi­
cient of thermal expansion. Many flexible substrates have been used in
flexible electronics, including polymers, such as polyethylene tere­
phthalate (PET), polyethylene naphthalate (PEN) [56], Polyimide (PI),
Parylene [9], and inorganic materials, such as ultrathin glass [57], cel­
lophane substrate [58,59], etc. The main properties of flexible polymeric
substrates are summarized in Table 1.
Nowadays, PET and PEN films with excellent transparency and sol­
vent resistance have been widely used as flexible substrates in F-OSCs
[46,60]. For instance, Kim et al. used ITO/PET substrate to fabricate
Fig. 1. Summary of the progress of PCE improvement for rigid and flexible
OSCs. The black dots reproduce the best research-cell efficiency chart reported
by NREL [30] and previous reports [27–29]. for single-junction rigid OSCs. The
red dots are the best PCEs for single-junction F-OSCs [31–45].
2
Nano Energy 89 (2021) 106399
F-OSCs by using an alternating conjugated polymer PBDB-T as electron
donor, providing a PCE of 7.2% [61]. This was much lower compared to
the ITO/glass based rigid OSCs with PCEs over 10%. They found that
during thermal annealing of photoactive layers under 160 ◦ C, many
cracks were generated during annealing process, which might attribute
to the deformation between ITO and PET. Generally, the melting tem­
perature (Tm) of PET ranges in 115–258 ◦ C, and PET substrate usually
works under 150 ◦ C (Table 1) [46]. Therefore, PET substrate may not be
a good candidate for F-OSCs due to the thermal instability during
operations.
PI substrate with highly thermal-/optical-stability is an available
alternative to PET substrate, which can work under <400 ◦ C due to the
higher Tm (250–452 ◦ C, Table 1) [62]. However, most PI substrates are
not optically clear in the visible region, causing the decrease of
light-absorbing ability in OSC devices. Thus, colorless PI substrates ob­
tained by introducing functional units, such as trifluoromethyl groups
[63] or multi-bulky pendant groups into PIs [64], can be an optional
alternative for F-OSCs. In addition, PCEs of OSCs usually suffer from
degradation under UV light irradiation due to the possible denaturation
of chemical bonds of the photoactive layers under this condition [13,
65–68]. A transparent PI substrate that exhibited about 90% cut-off
property of wavelengths less than 350 nm but high transparency in
the visible wavelengths was applied into F-OSCs, showing long-term
(3 h) stability >90% of the initial value after a continuous operation
in ambient air [66].
Moreover, the ultrathin substrate in F-OSCs would reduce strain in
organic electronic devices, favoring to improve the foldability and me­
chanical cyclic durability of various optoelectronic devices [69–71]. For
example, non-fullerene ultra-flexible OSCs based on PI substrates were
constructed, in which the doping interface between the active layer and
the molybdenum oxide (MoOx) was found to improve the stability of
cells [72]. The ultra-flexible OSCs were transferred onto a pre-stretched
adhesive elastomer to test their mechanical stability. With 37%
compression, small-area ultra-flexible OSCs maintained 90% PCE after
1000 compression/extension cycles. The large-area module decreased
slightly from 11.4% to 11.0% after the first cycle, and remained un­
changed during the subsequent cycles with a compression of 12%. Me­
chanical simulations suggested that the reduction in substrate thickness
would reduce the strain in F-OSCs under folding with a small curvature
radius.
Other substrates, such as cellophane substrate [58], poly­
dimethylsiloxane (PDMS) [73] and parylene [74], were also used to
construct F-OSCs. Additionally, many strategies were used to nano­
pattern the polymer substrates so as to enhance the light-harvesting
ability via light trapping. For example, Nanograting-structured ultra­
thin parylene substrate was prepared through a multistage template in
which nanograting-patterned PDMS was the mold of a fluorinated
polymer andthe nanograting-patterned fluorinated polymer was the
mold of parylene substrate (Fig. 3) [74]. With a nanograting-structured
front surface having a pitch of 760 nm, a height of 100 nm and a flat
opposite surface, parylene substrate-based F-OSCs achieved an
enhanced PCE of 10.5% compared with 9.9% of traditional parylene
substrate-based F-OSCs at a low incident light angle dependence
(Fig. 3f).
2.2. Transparent electrodes for F-OSCs
Bottom transparent electrodes (TEs) and top electrodes in F-OSCs
play the key roles in collecting and transporting electrons (cathode) and
holes (anode), respectively. TEs of F-OSCs should have extra charac­
teristics of high optical transparency, smooth surface, low coefficient of
thermal expansion and high adhesion to the substrate [75,76]. A weak
adhesion between TEs and the substrate may result in an exfoliation
after the constant bending process, while the enhanced adhesion will
improve the mechanical robustness of the whole device [77]. The sheet
resistance (Rsh, Ω/sq) and light transmittance (Ttrans) are the dominant
C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 2. (a) Schematic diagram of source materials and fabrication techniques of F-OSCs. (b) The potential application fields of F-OSCs. Reproduced with permission
[9,49,50,52–55]. Copyright (2013, 2017 & 2018) WILEY-VCH Verlag GmbH & Co.KGaA, Weinheim; copyright (2015) The Authors. Published by WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim; (2021) The Authors. Published by Elsevier Inc.; (2019) Elsevier Inc.; (2018) Springer Nature Limited.

metal grids and nanowires.

Table 1
Ag grids have been widely used as the front contact in many
The main properties of flexible polymeric substrates [46].
inorganic-based photoelectric devices or flexible organic electronics,
.Substrate PET PEN PI PDMS such as silicon solar cells and OLEDs, where the metal fingers provide
Tga (◦ C) 70–110 120–155 155–270 -125 patterned paths for conducting electricity and the gaps between the
Tmb (◦ C) 115–258 269 250–452 – figures become the light windows for transmitting light. In 2007,
3
Density (g/cm ) 1.39 1.36 1.36–1.43 1.03
Inganäs and coworkers fabricated Ag grids (width = 40 µm, spacing =
Vol.Res.c (Ω.cm) 1.0 × 1019 105 1.5 × 1017 1.2 × 1014
Modulus (MPa) 2–4.1 × 103 0.1–0.5 × 103 2.5 × 103 1
600 µm) and further covered with PEDOT:PSS via spin-coating method
Work Temp. (◦ C) -50–150 – ≤400 -45–200 [86]. The Ag girds/PEDOT:PSS composite electrode showed Rsq of
CTEd (ppm/◦ C) 15–33 20 8–20 310 0.5 Ω/sq and Ttrans of 85% in a broad spectral range up to 2000 nm.
Water absorption (%) 0.4–0.6 0.3–0.4 1.3–3.0 >0.1 Further photovoltaic characteristics demonstrated that the performance
Solvent resistance Good Good Good Poor
of Ag grids/PEDOT:PSS composite electrode is comparable to ITO/PE­
Dimensional stability Good Good Fair Good
DOT:PSS. High-resolution hexagon-type grids possess the advantage of
a
Glass transition temperature, increased transmittance and mechanical stability due to deformability.
b
Melting temperature, In 2014, Gupta et al. developed a solution-processed method for the
c
Volume resistivity,
d fabrication of metallic grids (Fig. 4) [87]. In this work, the printed toner
Coefficient of thermal expansion. Copyright (2018) Ferreira Cruz SM, Rocha
acted as a sacrificial template for a metal precursor. The template is
LA, Viana JC. Published in [46] under CC BY 3.0 license. Available from:
https://doi.org/10.5772/intechopen.76161. retained in designated patterns and lifted off by common solvents. Ag
grids-based electrodes on a large-area PET substrate were fabricated by
roll-to-roll processing and employed in F-OSCs. The hexagonal Ag grids
parameters for transparent electrodes. TEs of F-OSCs have been fabri­
(150 mm width and 2 mm spacing) were highly conducting with an
cated by using various transparent materials, such as metal-/­
overall Rsq of 4 Ω/sq and a Ttrans of 82%. F-OSCs by using these grids
oxide-based inorganic materials [78–80], carbon-based inorganic
exhibited increased efficiency (1.85%) as compared to PEDOT:PSS
materials (carbon nanotube and graphene) [81,82], and transparent
(~0.6%) due to a significant reduction in series resistance.
organic conducting polymers [83]. The Comparison of performance,
Metallic nanowires, such as copper nanowires (CuNWs) and silver
properties, processability, and costs of commonly used transparent
nanowires (AgNWs), are the most important TEs for F-OSCs [79,80,88].
electrode materials in F-OSCs are listed in Table 2.
Metallic nanowires possess the advantages of high transmittance,
excellent electrical conductivity, and superior mechanical stability [89].
2.2.1. Metal-/oxide-based inorganic materials
Furthermore, metallic nanowires, are commercialized available and can
Initially, the traditional indium tin oxide (ITO) has been widely used
disperse in water or alcohol solvents.
as TE in F-OSCs due to its excellent light transmittance (>90% at
Although Cu is a very cost-effective conductor for the electronic in­
550 nm) and electrical conductivity (~10 Ω/sq). However, thermal ra­
dustry, employing low-cost CuNWs as TE remains challenging. At pre­
diation generated in the ITO sputtering progress would damage the
sent, the dispersion of CuNWs is almost realized through the steric
flexible substrates. Moreover, the conductivity of ITO thin film decreases
hindrance effect of polymers. However, the high post-treatment tem­
in mechanical deformation because of its brittle and crystalline nature so
perature of polymers makes this dispersion mechanism impractical for
as to lower the stabiliyt of F-OSCs. Therefore, many micro-/nano-sized
applications. Yu and coworkers realized the high dispersion of CuNWs
inorganic materials are used to replace ITO as TEs for F-OSCs, including

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C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 3. (a) Schematic of an ultra-flexible OPV with an ultrathin nanograting polymer substrate delaminated from the supporting substrate. AFM images of (b)
nanograting structure on a fluorinated polymer layer on the supporting glass, and nanograting structure on the (c) outer surface of parylene and (d) inner surface of
parylene to be used for device fabrication and (e) the upper surface of the planarization layer (SU-8) to be used for device fabrication. (f) Angle dependence
characteristics of ultra-flexible OPVs having ultrathin nanograting polymer substrates. Reproduced with permission [74]. Copyright (2020) WILEY-VCH Verlag
GmbH & Co.KGaA, Weinheim.

and low post-treatment temperature (80 ◦ C) by utilizing the electrostatic
dispersion mechanism [90]. The CuNWs based electrode exhibited an
Rsq ≈ 65.7 Ω/sq and a high high Ttrans ≈ 92%. Covering with an over­
coat PEDOT:PSS layer, the film roughness decreased from 9.26 to
1.81 nm. For the F-OSCs device based on CuNWs/PET, the PCE was
8.29%, slightly lower than the rigid cell based on ITO/glass (8.58%).
The decreased PCEs was ascribed to the low fill factor (FF) from low
shunt resistance since the CuNWs film exhibited lower conductivity than
ITO film (14 Ω/sq).
AgNWs are the most used metallic electrodes in F-OSCs. The features
of AgNWs can make it coating on arbitrary substrates through solution-
based processing, which facilitates large-area production. Nowadays,
the polyol reduction method has offered a favorable opportunity to
prepare AgNWs and makes their commercialization. In this method,
ethylene glycol (EG), silver nitrate (AgNO3), and poly(vinyl pyrroli­
done) (PVP) are generally used as the polyol, Ag source, and capping/
dispersing agent, respectively. However, since the low coverage,
random distribution, and low-adhesion features of AgNWs, AgNWs-
based electrodes still suffer from the trade-off between conductivity
and transmittance, surface roughness and operative stability. These

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C. Liu et al. Nano Energy 89 (2021) 106399

Table 2 afterward PI solution was coated onto the AgNWs by doctor blading
Comparison of physical properties, cost and processability of commonly used [39]. The AgNWs:PI composite electrodes were then peeled off from the
transparent electrode materials in F-OSCs. glass after annealing. The AgNWs:PI composite electrodes exhibited low
ITO Ag mesh Graphene PEDOT:PSS AgNWs surface roughness of 1.5 ± 0.5 nm and the average transmittance of
Rsh (Ω/sq) 10–50 6–50 100–3000 50–1000 4–100
AgNWs:PI is 83.2% in the wavelength region from 460 to 780 nm, which
Ttrans (%) 80–95 ~80 60–97.4 75–90 82–97 is comparable to the glass/ITO electrode. Besides, the AgNWs:PI com­
Roughness Low Fair Low Low High posite electrodes showed excellent thermal stability with Rsq only
Flexibility Bad Good Good Good Good increased 10% of the initial value after 4 h annealing in air, and high
Work function (eV) 4.7–5.0 ~4.2 Tunable ~5.1 ~4.2
adhesion with nearly unchanged Rsq (26.0 Ω/sq) to its original value
Stability Good Good Good Bad Fair
Costs of materials Low Low High Fair Low (25.8 Ω/sq) after 10 times sticking–peeling cycles 10 times by using
Costs of fabrication Low Low High Low Low Kapton tape. F-OSCs with an inverted structure (AgNWs:PI/ZnO/active
Solution processing No No Yes Yes Yes layer/MoO3/Ag) showed a PCE of 11.6%, which was slightly lower than
[84] [84] [78] [85] [80] that of the glass/ITO reference with a PCE of 12.3%. After 5000 times
bending cycles, the devices exhibited excellent stability since the PCEs
issues would lead to the decreased device performance, mechanical dropped to 88% of the initial values.
stability and sometimes local melting/deformation due to Joule heating. The insulating surface ligands of PVP that inevitably wrap the
Moreover, PVP, as an insulating polymer, would trigger high junction AgNWs during the synthetic process will cause high Rsq of bare AgNWs
resistance between neighboring nanowires, leading to enhanced contact due to the high contact resistance at AgNWs-PVP-AgNWs interfaces.
resistance and correspondingly a reduced open-circuit voltage (VOC). In Various strategies have been developed to address this issue and
recent years, the development of F-OSCs mainly concentrates on improve the conductivity of the AgNWs thin films, including mechanical
addressing these issues of AgNWs-based electrodes. pressing [95], plasmonic welding, thermal annealing [96], and capillary
To reduce the surface roughness, PEDOT:PSS has been used as an force-induced welding [97]. Chen and coworkers utilized a
interfacial layer on the top of AgNWs electrodes [91,92]. Another water-dispersed homogeneous suspension of AgNWs with poly(sodium
method to smooth the surface and enhance the adhesion is to embed the 4-styrenesulfonate) (PSSNa, Fig. 6a) as a polyelectrolyte to fabricate
AgNWs into insulating polymer substrates, such as PI, parylene-C [39, BTEs (Fig. 6b-c) [98]. Since the ionic electrostatic charge repulsion ex­
92], and PDMS [93], or biopolymers like polyethylene furandicarbox­ ists among the AgNWs, PSSNa anions with negative charge can be
ylate (PEF) [94]. Zhou and coworkers introduced PI to handle the sur­ adsorbed in the adjacent AgNWs. This effect would lead to AgNWs
face issue of AgNWs (Fig. 5), in which AgNWs were coated on the glass suspensions with stable, homogeneous dispersions and generated TEs
substrate through spin-coating and patterned via laser ablation and with grid-like patterns and high smoothness. The flexible electrodes

Fig. 4. Fabrication of solution-processed large area Ag patterned electrodes [87]. (a) Schematic demonstration of the fabrication procedure. The tilted SEM (scanning
electron microscope) image of the cross-sectional view of (b) a toner pattern on the PET substrate and (c) after developing with Ag. The inset shows the zoom-in view
of the cross-section of Ag printed on PET. (d) The SEM image and overlapped EDS of printed Ag. Copyright (2014) The Royal Society of Chemistry.

Fig. 5. Schematic of the preparation of flexible AgNWs:PI electrode [39]. Reproduced with permission. Copyright (2019) The Royal Society of Chemistry.

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C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 6. (a) Chemical structures of

NaBH4 and PSSNa. Surface SEM images
of (b) the films prepared from the pris­
tine AgNW suspension (1 mg ml-1) and
(c) the AgNW suspension (4 mg ml-1)
with PSSNa [98] (10 mg ml-1), scale
bars, 500 nm. The bottom figures are
the cross-section SEM images of the
FlexAgNWs. (d) Schematic showing the
removal of PVP ligand from AgNW film
by NaBH4 [99] and subsequent decora­
tion with a DT layer to enable direct
Ag-Ag contact and complete protection
by a dense hydrophobic DT layer.
Reproduced with permission. Copyright
(2019) Springer Nature Publishing
Group; (2018) American Chemical
Society.

have an Rsq of around 10 Ω/sq and Ttrans of around 92%. single-junction main features are also summarized.
and tandem F-OSCs devices based on this electrode achieved PCEs of
13.1% and 16.5%, respectively. Another way to reduce junction contact 2.2.2. Inorganic carbon nanomaterials
resistance is the complete removal of residual PVP ligands. Duan and Carbon nanomaterials, such as carbon nanotubes and graphene [43,
coworkers reported a strong reducing agent sodium borohydride 109], have been widely studied in the past years in terms of their
(NaBH4, Fig. 6a) to completely remove surface PVP ligands, and controllable preparation and comprehensive applications in many areas
replaced the long-chain ill-defined surface ligands PVP with short-chain [82,110–114]. Due to their inherent small-size effect and conjugation
densely packed ligands (DT) (Fig. 6d) [99]. AgNWs thin films were effects of delocalized π-electrons, carbon nanomaterials have the ad­
found to possess an atomically clean Ag-Ag interface to ensure direct vantages of outstanding transparency in a wide wavelength range, good
welding of AgNW-AgNW junction at room temperature, so that the electrical properties, mechanical flexibility and feasibility of
conductivity of AgNWs based electrode was greatly increased. The final solution-processing at room temperature. These features make them
Rsq and Ttrans values were 35.0 Ω/sq and 92.6%, respectively. very promising candidates as TE in F-OSCs.
Generally, a high length/diameter ratio of AgNWs is required to Graphene, which is a 2D array of sp2-hybridized carbon atoms with a
achieve high conductivity while maintaining enough transparency. To long-range ordered hexagonal lattice structure, has received much
address the roughness issue and further enhance the conductivity, one attention as a promising flexible TE owing to its superior optical, elec­
needs to remove the PVP capping ligands to weld the AgNW-AgNW trical, and physical properties together with mechanical robustness and
junctions [98,99]. Moreover, the percolation theory should also be chemical/thermal stability. Park and coworkers adopted a commonly
taken into consideration to balance the conductivity and transparency of accessible “polar solvent” approach to improving the affinity between a
AgNWs-based conductive films [98]. For reference, Table 3 lists some graphene surface and interface layers, which enabled the ZnO layer to
typical transparent electrodes-based F-OSCs. Their performance and completely cover a graphene electrode [115]. F-OSCs based on PTB7-Th:
PC71BM obtained a high PCE of 7.53% on the flexible PET substrates.
Then, they integrated ZnO-NPs on the hydrophobic surface of graphene
Table 3 to enhance the applicability of graphene [116]. The ZnO-NPs were
Summary of Rsq and Ttrans of representative AgNWs composite electrodes and the demonstrated to be used into annealing-free OSCs through the investi­
corresponding PCEs of F-OSCs. gation of morphological, chemical, electrical, and optical properties. In
Device architecture Rsq (Ω/sq) Ttrans (%) PCE (%) Ref. 2018, this group incorporated a polymer additive with high viscosity
AgNWs:PI 25.8 83.2 11.6 [39]
into the all-polymer photoactive layer by using chemical vapor deposi­
PET/AgNWs/parylene-C 41.6 94.7 6.12 [100] tion (CVD)-graphene as bottom TEs [117]. The graphene
AgNWs/PEF 45 90 6.7 [94] electrode-based F-OSCs provided a PCE of 5.6% and maintained 90% of
AgNWs/NOA63 18.5 84.5 5.1 [101] the initial PCE after 100 bending cycles with a bending radius of
AgNWs/ZnO 28 80 12.02 [102]
3.0 mm.
Em-Ag:AgNWs:AZO-SG 18 95 15.21 [42]
PFN/AgNWs 19.3 94.4 6.17 [103]
PSSNa-AgNWs 10 ~92 16.55 [98] 2.2.3. Organic conductive polymers
AgNWs/PEDOT:PSS 5.4 94 15.12 [104] Conductive polymers, such as polyaniline (PAN), polypyrrole (PPy),
AgNWs:EG 13.7 89 6.18 [105] and polythiophene (Scheme 1), have been developed as flexible TEs for
AgNWs:GO/PH1000 20 82.1 13.44 [106]
PET/Ag-mesh/pH1000:AgNWs 6 86 12.07 [107]
many years. The distinguished characters of conductive polymers are
AgNWs/MXene 26 83.32 8.30 [108] their easily adjustable work functions and bandgaps via chemical

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C. Liu et al. Nano Energy 89 (2021) 106399

Scheme 1. Chemical structures of conductive polymers, including PEDOT:PSS, PAN, PPy, and polythiophene.

modification and doping, resulting in different transparency and con­
ductivity of the polymers [81,118–120]. Among them,poly(3,
4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a
typical conductive polymer, has been well studied as flexible TEs due to
its advantages of easy solution process, flexibility, outstanding con­
ductivity and good optical transparency [121,122].
The key issue of the study on high-performance PEDOT:PSS elec­
trode is to enhance the conductivity of PEDOT:PSS. Tuning the mass
ratio of PEDOT and PSS components was the initial strategy to improve
the conductivity of PEDOT:PSS [123]. Another strategy is the addition of
secondary dopants. The dopants, including polar organic compounds,
salt, zwitterion, carboxylic or inorganic acids, and cosolvent were
initially used to enhance the conductivity of PEDOT:PSS. In 2002, Zhang
et al. firstly investigated the possibility of conductive polymers PEDOT:
PSS as the anode in OSCs [124]. The Rsq of normal PEDOT:PSS is
~1.5 × 105 Ω/sq, which is far larger than Rsq of the ITO electrode
(20 Ω/sq). By further doping with glycerol and sorbitol, the sheet
resistance reduced to ~1.3 × 103 and ~1.0 × 103 Ω/sq, respectively.
The PCEs of OSCs based on MEH-PPV:PCBM dramatically increased
from 1.4% (ITO) to 3.4% (glycerol doped PEDOT:PSS) and 5.4%
(ITO/PEDOT:PSS).
Strong acids, like H2SO4 and HNO3, were primely used as the second
dopant to treat PEDOT:PSS toward enhanced conductivity. For instance,
Kim et al. presented a facile “pick-and-place” method to transfer the
highly conductive PEDOT:PSS films treated with H2SO4 onto arbitrary
surfaces (Fig. 7), including glass slide, silicon wafer, Cu foil, Kapton
tape, and typical large-area PET or PEN substrate [125]. The highly
conductive PEDOT:PSS film was prepared by immersing the pre-cast
film in concentrated H2SO4 and following rinsing it with deionized
water, further picked up with PDMS, and then placed on substrates. High
conductivity of > 4000 S/cm, excellent Rsq of 46 Ω/sq, and Ttrans of 90%
at 550 nm were achieved on the PEN substrate. When using the
H2SO4-treated PEDOT:PSS layer (WF = 5.1 eV) as both a transparent
anode and hole transporting layer (HTL), F-OSCs based on PTB7-Th:
PC71BM active layer and PEN as substrate yielded a PCE of 7.7%, which
was comparative to the value of 7.6% based on the rigid ITO/glass
device.
Nonetheless, since the 98 wt% H2SO4 is highly-viscous, it is difficult
to completely wash it from PEDOT:PSS matrix by deionized water. The
corrosive acid may destroy plastic substrates or reduce the device sta­
bility, and also may devitalize the charge transport oxide layer like ZnO.
Thus, mild and eco-friendly acids are needed to improve the conduc­
tivity of PEDOT:PSS in the F-OSC device. In 2015, Fan et al.[126]
introduced methanesulfonic acid (CH4SO3) to modify the PEDOT:PSS
film. The optimized PEDOT:PSS films on the PET substrate exhibited a
conductivity of 2480 S/cm.

Fig. 7. Schematic illustration of the procedure for the transfer printing of H2SO4-treated PEDOT:PSS film from a donor quartz substrate to a target substrate [125].
Reproduced with permission. Copyright (2015) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

7
C. Liu et al.
In 2018, Ge and coworkers demonstrated an efficient PEDOT:PSS
films treated by CH4SO3 at room temperature [127]. Due to the removal
of insulating PSS from PEDOT:PSS matrix and a better phase separation,
the PEDOT:PSS films treated with the gentle acid were verified to have
high optical and electrical characteristics (Ttrans ≥ 90% at a wavelength
ranging 450–900 nm and σ = 2860 S cm-1) and smooth surfaces
(roughness of 2.14 nm). All-solution-processed F-OSCs by using PBDB-T:
IT-M active layer were realized, providing a high PCE of 10.12% and
maintaining excellent bending flexibility with 1000 cycles. Recently, the
same group demonstrated the possibility of doping PEDOT:PSS with
eco-friendly acids, such as citric acid, malic acid and tartaric acid (Fig. 8)
[77]. Owing to the inherent polyhydroxy nature, the eco-friendly acid
treatment not only increased the interfacial adhesion of PEDOT:PSS to
the PET substrate, but also enhanced the interfacial abrasive resistance.
Among them, the film treated with citric acid at 58 wt% achieves the
highest conductivity (1960 S/cm) and the lowest Rsq of ~93 Ω/sq.
Non-fullerene F-OSCs based on the treated PEDOT:PSS as bottom TE and
PBDB-T-2F:Y6 as the photoactive layer were fabricated on a typical PET
substrate, exhibiting the highest PCE of 14.17%, slightly lower than the
rigid cells (15.41%). Moreover, the flexible device still retained over
90% or 80% of the initial PCEs after 1000 cycles of continuous bending
test or persistent folding, respectively.
2.3. Interfacial materials for F-OSCs
Interfacial layers, including electron transport layers (ETLs) and
HTLs, were used to alleviate interfacial energy barriers between pho­
toactive layers and electrodes in the OSCs. For F-OSCs, appropriate
interfacial layers can improve adhesion between the photoactive layers
and the electrodes, following enhance the mechanical durability and
Fig. 8. (a) Molecular structures of citric acid, tartaric acid, and malic acid, respectively [77]. (b) Transmittance spectrum, (c) Rsq and figure of merit (FoM) of the
PEDOT:PSS films with the three eco-friendly acids treatments at different concentrations. Reproduced with permission. Copyright (2020) Elsevier.
8
Nano Energy 89 (2021) 106399
operational stability of devices [128,129]. Interfacial materials in
F-OSCs should have the following features: (1) good ohmic contact with
both the active layer and the electrodes; (2) suitable electron affinity and
ionization potential values to enhance the selectivity of charges; (3)
enough mobility and high conductivity to ensure thick films; (4) high
adhesive capacity and bendable/stretchable stability; (5) thermal and
chemical stability. The materials of ETLs and HTLs used in F-OSCs are
discussed below.
2.3.1. ETL materials
As stated above, the selection of appropriate materials to form high-
quality ETLs to optimize the electron collection and transport is
particularly important to achieve high PCEs in F-OSCs. In F-OSCs, the
commonly used low-WF ETL materials contain ZnO, SnO2, titanium sub-
oxide (TiOx), fullerene derivatives (PCBB-3N-3I) [118],
organic-inorganic hybrid electrolyte [130], electrolyte PDINO, PDINN,
or SiNcTI-Br [131–133], conjugated polyelectrolyte PFN-Br or
PF3N–2TNDI [98], cationic biopolymer poly(ethyleneimine) (PEI)
[134], etc (Scheme 2).
ZnO, with a rather wide bandgap (3.4 eV), is the most commonly
used ETL material due to its advantages of convenient processing, suit­
able energy levels and transparency in the visible light region. Tradi­
tionally, ZnO film is prepared by the sol-gel method [135]. The
annealing temperature is the key factor to affect the quality of sol-gel
ZnO. As an alternative, the ZnO layer can also be prepared via a water
method, in which the suspension of ZnO is obtained by hydrolysis and
condensation of zinc acetate dihydrate at low temperature and then it is
spin-coated onto the substrate [136]. ZnO prepared by hydration does
not require additional thermal annealing treatment. However, the dis­
advantages of this method are the poor uniformity and conductivity of
C. Liu et al. Nano Energy 89 (2021) 106399

Scheme 2. Chemical structures of small molecules and polymers as ETLs.

ZnO film.
To achieve low-temperature processed ZnO, a modifying ZnO strat­
egy (like doping method) to tune the energy levels is required for its
application in F-OSCs. For instance, Xie and coworkers decrease the
annealing temperature low to 150 ℃ through a 1,6,7,12-tetraphenoxy
substituted perylene bisimide dye (PBI-SO3H, Fig. 9a) for the photo­
sensitization of ZnO [137]. The introduction of benzenesulfonic acid
functional groups to the dye molecules significantly enhances the uni­
formity of the PBI-SO3H:ZnO hybrid films through the formation of ionic
bonds (Fig. 9b-c). When PM6:Y6 blend was used as the photoactive
layer, the PCE of F-OSCs based on the PBI-SO3H:ZnO hybrid ETL was
13.5% as compared with 15.4% of the rigid device. In addition, the OSC
devices based on dye-doped ZnO ETL exhibited excellent thickness
tolerance ranging from 30 to 90 nm.
Many organic materials can be used as ETL in OSCs. Among them,
fullerene derivatives have high electron mobility and energy levels to
match with the active layer. Li and coworkers developed a fullerene self-
doping electrolyte material (named PCBB-3N-3I, Scheme 2) as the ETL
of F-OSCs based on the PET/Ag-mesh/PH1000 electrode [139].
Compared with ZnO as ETL, this material reduced the dependence of
photovoltaic characteristics on thickness, increased the ohmic contact
between the interface layer and the active layer, and had better flexi­
bility in F-OSCs. Through n-type self-doping, the conductivity of
PCBB-3N-3I film had been significantly improved. Finally, the F-OSC
with a PCE of 10.04% was obtained. Importantly, the PCBB-3N-3I ETL
also showed thickness-insensitive bending durability in F-OSCs with a
thick film of ≈60–70 nm.
Conjugated polyfluorene derivative, PFN, has been successfully
applied in state-of-the-art inverted OSCs as ETL. Seo et al. used the
alcohol-/water-soluble conjugated polymer PFN to replace ZnO as ETL
in F-OSCs [103]. With the AgNWs:PFN composite electrode, the F-OSC
provided a PCE of 6.17% and retained 96% of its efficiency at a bending
r of 5 mm. Wu and coworkers used PTB7:PC71BM blend to study the
interface between the active layer and the electrode by using PFN as ETL
[140]. F-OSCs fabricated with PTB7:PC71BM as photoactive layer
exhibited a high PCE of 8.7% on ITO/PET substrate. However, the de­
vice could only work efficiently with an extremely thin PFN film
(<10 nm) due to the low electron mobility.
2.3.2. HTL materials
HTL materials should have a relatively high WF, optical trans­
parency, and excellent solution processability. Among the HTL

Fig. 9. (a) Chemical structures of PBI-SO3H and PBI-COOH. (b) Schematic presentation of ionic bonding assisted molecular dispersion of PBI-SO3H in the ZnO matrix
[137]. (c) The process of ZnO:PBI-COOH thin-film formation leading to the incorporation of PBI-COOH into the ZnO lattice [138]. Reproduced with permission.
Copyright (2019 & 2020) American Chemical Society.

9
C. Liu et al.
materials, PEDOT:PSS and transition metal oxides, such as nickel oxide
(NiOx), tungsten oxide (WOx), molybdenum oxide (MoOx) and vana­
dium oxide (VOx) are commonly employed in OSCs. PEDOT: PSS is the
most widely used HTL for F-OSCs, which has excellent thermal stability
and good flexibility so as to enhance the stability of F-OSCs [141].
However, the sulfonic acid group contained in PEDOT:PSS makes it
acidic and hygroscopic, which will reduce the stability between the
organic active layer and the electrode, and eventually lead to the
degradation of device performance. Huang et al. proposed adding basic
dopamine into PEDOT:PSS to neutralize its acidity, and
photo-crosslinking to reduce its hygroscopicity [142]. This method can
improve the stability between the electrode and the active layer, but the
performance of the device will decline.
In addition to the polymers as HTL materials, transition metal oxides
are also used as HTL materials. Nickel nitrate and glycine were used as
precursors to synthesize NiOx as the HTL of solution-treated optoelec­
tronic devices by low-temperature spray coating [143]. NiOx prepared at
low temperature can maintain excellent nanocrystalline properties and
avoid incompatibility with the flexible substrate after normal
high-temperature annealing treatment. The NiOx obtained by this
method has excellent optical and electrical properties and a smooth
surface, and its thickness (10 nm) is much lower than that of PEDOT:PSS
(45 nm) when used as HTL. When TQ1:PC71BM was used as a photo­
active layer, the PCE of the device with NiOx as HTL was 6.42%.
2.4. Photoactive materials for F-OSCs
Photoactive layers are the central of OSCs, which directly absorb
photons from light and convert them into electricity. In F-OSCs,
considering the interlayer stresses that contribute to delamination, the
semiconducting photoactive layers should have a lower modulus to
Scheme 3. Chemical structures of conjugated polymers as the electron donor in the photoactive layers for F-OSCs.
10
Nano Energy 89 (2021) 106399
minimize the interfacial stresses in the tensile modes of deformation,
such as stretching and bending. For wearable applications, the photo­
active layers should have higher extensibility since human skin exhibits
extensibility of ca. 30% [144–146]. Adhesion between the photoactive
layer and the adjacent layers would increase the stability of the overall
device as it distributes strain and mitigates cracking in twisting and
shear modes of deformation. In total, besides the high PCEs, the pho­
toactive materials should have low modulus, large extensibility, high
adhesion, and either low or high toughness.
In general, F-OSCs use bulk heterojunction (BHJ) photoactive layers
with polymer donors and small molecule acceptors. Because of the high
crystallinity and relatively high charge mobility of poly(3-
hexylthiphene) (P3HT) and PC61BM, they were first fabricated into
BHJOSCs in 2002 with a relatively low PCE of 2.8% and rapidly
improved to 6.5% in 2009 [147]. To solve the shortcoming of the narrow
light absorption region of P3HT, in 2009, Yu and coworkers invented a
new series of PBDTTT semiconducting polymers [148,149], which
possess a broad spectrum between 500 and 750 nm and a relatively low
bandgap (Scheme 3) [150–152]. Since then, most of the F-OSCs were
fabricated by using these series of polymers. Wu and coworkers used
PTB7:PC71BM blend to study the interface between the active layer and
the electrode by incorporating an alcohol–water-soluble conjugated
polymer, PFN as the interfacial layer [140]. F-OSCs fabricated with
PTB7:PC71BM photoactive layer exhibited a high PCE of 8.7% based on
ITO/PET substrate.
Non-fullerene small-molecule acceptors were developed as alterna­
tive to fullerene derivatives, since fullerene acceptors may suffer from
poor stability, expensive cost, and crucial purification process (Scheme
4) [153–155]. In the early days, non-fullerene small-molecule acceptors
provided low PCEs of <5%. In 2015, Zhan et al. reported the
non-fullerene acceptor ITIC, which showed a superior PCE of 6.8%
C. Liu et al.
Scheme 4. Chemical structures of fullerene and non-fullerene acceptors used in F-OSCs.
[156]. Accompanied by the development of non-fullerene acceptors, the
PCE of F-OSCs rapidly increased from ~10% to >15% [25]. Li et al.
invented an imprinted light-trapping sol-gel-derived ZnO nanostructure
in PBDB-T:ITIC and PM6:IT-4F based F-OSCs [102]. Owing to the syn­
ergetic interplay between broadband light trapping and suppressed
charge recombination loss, the single-junction F-OSC with AgNWs/PET
electrode was proven to have PCEs of 10.91% and 12.02% for the
PBDB-T:ITIC blends and PM6:IT-4F blends, respectively. Recently, Ge
et al. reported non-fullerene F-OSCs based on the treated PEDOT:PSS as
TE and PBDB-T-2 F:Y6 as photoactive layer, providing the highest PCE
of 14.17%, slightly lower than the rigid cells (15.41%) [77]. Li and
coworkers increased the PCE of F-OSCs based on PBDB-T-2F:Y6 active
layer to 15.21%, which is the highest performance of F-OSCs up to data
[42]. The enhancement was attributed to the application of
embedded-Ag/AgNWs/AZO composite electrodes with a low Rsq of
≈18 Ω/sq, highest Ttrans of ≈95% at 550 nm, and RMS of 2.17 nm.
Notably, the deviation of PCE for F-OSC and the ITO/glass rigid cell is
<4%, indicating the superior characteristics of the composite electrode.
To avoid the embrittling effects of small molecular acceptors, all-
polymer OSCs by using an n-type semiconducting polymer as
acceptor, have been intensively studied recently. All-polymer OSCs have
advantages such as low-cost fabrication, good thermal stability and
robust mechanical properties. However, the performance of the all-
polymer solar cells composed of n-type conjugated polymers, such as
N2200 (Scheme 4), has shown a much lower PCE of <11% compared
with that of the corresponding small molecule/polymer devices
[157–160]. In recent years, researchers focused on introducing the fused
ring non-fullerene acceptors into the n-conjugated polymers [159] and
thus enhanced the PCEs to over 13% [161,162].
Kim et al. demonstrated all-polymer OSCs by using P(NDI2HD-T) as
polymer acceptor to dramatically enhance strength and flexibility
compared with polymer:PCBM devices, with 60- and 470-fold im­
provements in elongation at break and toughness, respectively [163]. In
stark contrast, they proved that all-polymer OSCs could endure
11
Nano Energy 89 (2021) 106399
extremely small bending radii low to 1.0 mm with no significant change
in the electrical and morphological properties. Yang et al. improved the
stretch ability of all-polymer OSCs by a newly developed, high-viscosity
polymeric additive, poly(dimethylsiloxane-co-methyl phenethylsilox­
ane) (PDPS), into the TQ-F:N2200 matrix [117]. The toughness values of
TQ-F:N2200 blends were increased to 9.67 MJ m-3 along with an elon­
gation at a break of 50.92% by adding 10 wt% PDPS. The F-OSC based
on PET substrate achieved a high PCE of 5.60% in graphene electrode
based flexible devices and remained 90% of its PCE after 100 bending
cycles at a bending radius of 3 mm. Wang and coworkers developed a
series of narrow band-gap polymer acceptors PF2-DTC, PF2-DTSi, and
PF2-DTGe with different bridging atoms (i.e., C, Si, and Ge) [164]. All of
the polymer acceptors-based blends exhibited superior integrated
toughness values of 7.33–14.35 MJ m-3, which is 9–18-fold higher
compared to the PM6:IDIC16 as photoactive layer (0.82 MJ m-3), thus
making them available for a roll-to-roll (R2R) process. Eventually, the
all-polymer F-OSCs based on PF2-DTSi polymer acceptor exhibited a
retained PCE of >90% of its initial PCE (6.37%) after bending and
relaxing 1200 times at r = 4 mm.
Generally, high rigidity and crystallinity are required to guarantee
adequate charge transport for conjugated polymers in OSCs, but
meanwhile limit their mechanical properties [165,166]. Therefore,
there is always an inherent trade-off between the mechanical and elec­
tronic properties of conjugated polymers. In a recent perspective, Ding
et al. summarized the relationships between microstructure and elec­
trical/mechanical properties of conjugated polymer films [167]. They
emphasized that the regulation of microstructures by controlling solu­
tion aggregation, film-formation dynamics, and tie chain effects would
balance the competition of charge transporting and flexibility. This
should be paid special attentions when designing new conjugated ma­
terials for efficient and stable F-OSCs.
C. Liu et al. Nano Energy 89 (2021) 106399

3. Large-scale fabrication techniques for F-OSCs
The typical multilayer structure of OSC devices is essentially solid
films in amorphous or polycrystalline states, including the substrate, top
and bottom electrode, organic active layers, interfacial layers, and
possible encapsulation layer. They usually contain various types of
materials, such as metals, nanometal wires, oxide nanoparticles, poly­
mers or small molecules, etc. Thus, different processing methods are
required for the fabrication of different layers in F-OSC [168]. Filtering
appropriate “coating” or “printing” methods for different layers and
integrating them into the R2R system is the core issue for the con­
struction of large-scale F-OSCs. For lab-scale fabrication of small-sized
cells, the spin-coating method (Fig. 10) is generally used to fabricate
the photoactive layers. However, the spin-coating method may not be
suitable for large-volume and high-throughput production [169].
Alternatively, the relatively long and flexible substrates make it easy to
realize mass production based on the “R2R” (Fig. 10) process.
Considering the resulting morphologies of the films [170,171], the
printing and coating methods in the R2R process can be divided into (1)
0-dimensional (0D) coating techniques, like knife-coating, spray
coating, brush coating, which have no pattern ability and are only
suitable for preparing smooth films over the entire under-layer surface;
(2) 1-dimensional (1D) coating technique, such as slot-die coating,
which allows for the coating of the striped film of materials; (3) 2-dimen­
sional (2D) coating technique, covering screen printing, inkjet printing,
which can deposit films with designed patterns; (4) 3-dimensional (3D)

Fig. 10. Comparison between preparation and characterization of normal polymer solar cells on glass (left) and those prepared in this work using R2R methods
(right). Reproduced with permission [169]. Copyright (2010) American Chemical Society.

12
C. Liu et al.
techniques can fabricate multilayer films in the single coating step.
Other techniques, like gravure coating, pad printing, flexographic
printing can also fabricate 1D or 2D films. The methods are differing
from ink viscosity, operation complexity, running velocity, etc., and are
hence suitable for different layers of the F-OSC devices after optimizing
the parameters. In this section, we will provide a detailed discussion
about the large-scale fabrication technique for F-OSCs.
3.1. Large-scale techniques for inorganic films/grids electrodes
The inorganic films- or grids-based electrodes in F-OSCs, including
the top electrode and bottom electrode, onsisting of metal/oxide films,
metal grids, and blends of two or three materials. The typical structure of
F-OSC devices demands at least one transparent electrode (generally
bottom transparent electrode). Hence, the difficulty of fabrication large-
area electrodes lies in the balance of transparency and conductivity.
For ITO electrodes, 0D coating techniques can meet their demands.
The large-area ITO electrode is very suitable to be prepared by a roll-to-
roll direct current magnetron sputtering system deposition as it is
feasible to strictly control the thickness of the films (Fig. 11). In this
method, the quality of the ITO film is subjected to growth conditions,
such as R2R speeds, discharge power, O2/Ar flow ratio [172].
Differently, the metal grid electrode requires a patterning process to
achieve enough transparency, and hence a 2D coating technique is
needed. Screen printing, which enables 2D controlling of the printed
layer and different patterns through screens designing, is the common
printing method for fabricating metal electrodes with no loss of the
coating materials. For example, a pattern of grid electrode could be
obtained from UV-curable Ag paste (Ebecryl 15 from Cytec), water-
Fig. 11. (a) Schematic representation of the large-area magnetron sputtering coating system. (b) ITO deposited flexible PET films (7 cm rolled, 40 cm width, 10 m
long for each process parameter). Reproduced with permission [172]. Copyright (2018) Elsevier.
13
Nano Energy 89 (2021) 106399
based Ag paste, and heat-curable Ag paste (PV410, Dupont) through
screen printing and hardened procedure [173–175]. Likewise, the per­
formance of the Ag grids is significantly influenced by different silver
paste solvents [174], printing speed, designed grid patterns [176].
However, the method is usually suitable for inks with high viscosity and
low volatilization, thus resulting in the formation of large wet film
thickness. Therefore, although the screen-printed grids could be
honeycomb-structured to enhance transparency [176], the method may
be viable for a relatively opaque electrode (generally the top electrode).
For example, Krebs et al. used the screen-printed Ag grids as top anode
electrodes in a whole R2R processed F-OSCs [175].
3.2. Large-scale techniques for nanowires-type materials
The nanowires-type materials generally refer to AgNWs TEs due to
their great potential to achieve high-performance F-OSCs. Conductive
AgNWs inks generally contain three components: conductive AgNWs,
organic binder/additive (like PVP), and solvent. Several printing tech­
niques with a 2D printing ability, such as screen printing [178], inkjet
printing [179], and gravure printing [180], are preferred to pattern
AgNWs networks.
Pei and co-workers reported the water-based screen-printed AgNWs,
in which the distilled water was selected as solvent (Fig. 12a-c), a
mixture of (hydroxypropyl)methylcellulose, fluorosurfactant (Zonyl FC-
300), an antifoaming agent (Defoamer MO-2170 from BASF) was
employed as the organic binder/additives due to its satisfactory rheo­
logical behavior [178]. The AgNWs inks have different viscosity at the
same shear rate with various solid contents. Continuous and dense
AgNWs lines on PET with various line widths of ≈50, 100, 150, 200, and
C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 12. (a) Cross-sectional illustration

of the screen-printing process [178]. (b)
SEM image of the edge of the
screen-printed AgNW line after
post-treatment. (c) SEM image showing
the dense AgNW network structure in
the screen-printed AgNW line. (d) Inkjet
printing of silver nanowire lines on a
coated PET substrate which has been
aligned with index pins on the printer’s
heated platen [179]. (e) Printed lines of
different lengths. (f) SEM image of a
relatively thin silver nanowire network.
(g) Schematic of the high-speed roll-­
based process used to print nanowire
conductive hybrid films (inset (i) with
metal rollers engraved with gravure
cells (ii) and (iii)) [180]. HRSEM images
of the gravure-printed hybrid
IZO/AgNW films which were annealed
at (h) 125 ◦ C, (b) 175 ◦ C, Scale bars are
1 µm in length. Reproduced with
permission [178–180]. Copyright
(2009) The Royal Society of Chemistry;
(2010) Elsevier.

250 µm (which were obtained from a stencil having the same line prepared from a mixture of AgNWs dispersed in ethanol and IZO sol-gel
openings) were printed through the screen printing method. All straight precursors by Subramanian and coworkers (Fig. 12g-i) [180]. The
lines of AgNWs showed a correlation factor of >0.995, indicating IZO/AgNWs hybrid films were fabricated by high-speed gravure-print­
excellent uniformity of the printed lines at various line widths. However, ing (1.0 m/s) and exhibited low Rsq of 9.3 Ω/sq, Ttrans (91% at 550 nm),
this method needs a complex post-treatment to remove the additives and as well as robust mechanical properties. The encapsulating IZO matrix
fuse the AgNWs junctions, aiming to recover the conductivity of AgNW dramatically improved the adhesion of the composite electrode, fol­
networks. lowed a low roughness of 5 nm, and had thermal stability up to 350 ◦ C.
2D type direct inkjet printing, without any mask for printing a spe­
cific pattern, has the benefit of high resolution (about 300–1200 dpi)
3.3. Large-scale techniques for micro-/nano-sized materials
[171]. This method is a digital-controlled technique and the pattern can
be replaced conveniently by computer aided design. Thus, the inkjet
The micro-/nano-sized materials, like ZnO, TiO2, MoOx, which act as
printing method could print each layer of F-OSCs due to its availability
the interfacial layer in F-OSCs, usually disperse in a sol-gel to obtain
of patterning dots, lines, films, etc. However, there are very strict re­
solution-processed ability. The thickness of interface layers would affect
quirements for the inks, such as low viscosity (4–30 cP) and high surface
the performance of the overall F-OSCs. Thus, 0D controlled spray
tension (typically >35 mN m-1), to avoid nozzle congestion and achieve
coating (Fig. 13a), in which the ink is forced through a nozzle and then
good wettability with the substrate. Coleman and coworkers demon­
forms a fine aerosol, is very appropriate to fabricate the oxide nano­
strated that the optimized isopropyl alcohol-diethylene glycol
particles films with smooth surface owing to easy control of thickness.
dispersion-based AgNWs inks could be used to inkjet print AgNWs with
Noh et al. reported the fabrication of ZnO ETLs by the direct spray of
well-defined patterns (Fig. 12d-f) [179]. The addition of diethylene
precursor (a 0.75 M zinc acetate solution in 96% 2-methoxy ethanol and
glycol into diluted isopropyl alcohol suspension improved the solution
4% ethanolamine) on the hot substrate (Fig. 13) [181]. The excellent
viscosity. After a concentration optimizing process, the ink was capable
crystal quality of ZnO film was fabricated at 350 ◦ C, exhibiting a
to process the inkjet printing without the production of any satellite
reduced WF of 4.2–4.4 eV. However, the post-treatment temperatures
droplets. The resulting AgNWs based conductive grids, with widths of
on a hot substrate were controlled at 150, 250 and 350 ◦ C, which is not
1–10 mm, thicknesses of 0.5–2 µm, Rsq of 8 Ω/sq, and conductivity was
suitable for flexible substrates.
105 S/m, were obtained under a post-treated temperature of <110 ◦ C.
Inkjet printing has been proven to be an up-scalable R2R-compatible
Gravure printing that has the characteristics of producing high-
technique for the processing of functional materials [182]. Ganesan
resolution prints and smooth layers could act as a 1D or 2D coating
et al. prepared ZnO films by inkjet printing by using the purchased ZnO
technique. Inks used in this method generally have low viscosities to
ink (2.7% weight percentage in 2-propanol) with a pre-filtering and
form good films even at high coating speeds (about 1–10 m/s). Other­
diluting procedure [183]. Through optimizing the inkjet process, the
wise, different patterns were obtained by total replacement of the
thickness of the ZnO film was restricted to ~35 nm. However, due to the
coating roller, thus making this a very expensive technique for volume
relatively higher roughness (8 nm) of the inkjet-printed ZnO film (the
production. To enhance the adhesion between AgNW networks and the
roughness of the spin-coated ZnO film was 2.05 nm), the inkjet-printed
substrate, composite inks of IZO (indium zinc oxide)/AgNWs were
devices have a PCE of 21% less than the spin-coated devices.

14
C. Liu et al.
Fig. 13. (a) Schematics spray pyrolysis. SEM images of (b) ZnO film-based sol-gel process and ZnO pyrolyzed at (c) 150 ◦ C, (d) 250 ◦ C, and (e) 350 ◦ C. Reproduced
with permission [181]. Copyright (2009) The Royal Society of Chemistry; (2010) Elsevier.
3.4. Large-scale techniques for organic layers
The organic materials discussed here commonly compose of PEDOT:
PSS and photoactive materials. Inks based on polymer layers guaranteed
viscosity without extra additives. Techniques with 1D control charac­
teristics are suitable for the fabrication of this type of layer to achieve
stripe-like films.
The viscosity of the polymer can be adjusted by concentrations, ad­
ditives, and solvents in a wide range, and hence most of the coating/
printing methods could be used to obtain the polymer films. When the
conductive PEDOT:PSS was used as an electrode in OSCs, the desired
coating or printing techniques need to regulate the thickness of films for
balancing the trade-off between conductivity and transmission. As for
PEDOT:PSS HTLs, the thickness is required to be thin to eliminate shunt
resistance. The device configurations also need to be considered in terms
of the wettability of the underlying layers on which the PEDOT:PSS was
printed.
The early studies usually used the printing of PEDOT:PSS on trans­
parent substrates (as an electrode) or ITO/glass electrode (as an HTL)
with a smooth surface, to construct OSCs. Screen printing, which enables
full 2D patterning of the printed layer, is a commonly used industrial
technique for fast, large-scale, and cost-effective deposition of films.
15
Nano Energy 89 (2021) 106399
Typically, it requires a highly viscous and low volatile ink. In 2004,
Aernouts et al. developed a suitable screen to print the PEDOT ink onto
the PET substrate [184]. These screen-printed PEDOT layers were used
as bottom TEs in F-OSCs with a Ttrans of 90% over the full visible spec­
trum, although they are thicker than 1 µm. Krebs and coworkers used a
manually fed screen printing technique with 165 mesh screens for the
deposition of PEDOT:PSS toward large-area F-OSCs (the process took
90 min) [185].
The low-cost, program-controlled inkjet printing technique, similar
to spray coating, is theoretically capable to print each layer for the
stacked F-OSCs. Due to the auto-registration controlled by the software
program, it can print specific patterns without masks. Generally, a low
viscosity (4–30 cP), high surface tension (>35 mN m-1), and electro­
statically charged ink are required for the operation. Gutiérrez-Fernán­
dez et al. conducted a quantitative assessment of conductivity and
mechanical properties on the inkjet-printed PEDOT:PSS dispersion by
local probe methods [186]. This result demonstrated that the
inkjet-printed PEDOT:PSS film on ITO substrate had adequate electrical
conductivity and mechanical stability. Hence, a dilution and additive
treated PEDOT:PSS ink is required to adopt the technique. Ganesan et al.
demonstrated that the PEDOT:PSS dispersion was capable of inkjet-print
onto Ag grids [187]. Ag grids and the PEDOT:PSS film were inkjet
C. Liu et al.
printed in sequence from silver nanoparticle ink and PEDOT: PSS
dispersion to fabricate the TE in OSCs. It should be noted that the surface
tensions of the silver ink, PEDOT: PSS ink (1 wt% in H2O), and glass
substrate were 28, 51, 64.9 mN/m, respectively. The smaller margin
between PEDOT:PSS and substrate resulted in an adhesion issue. To
address this issue, a plasma post-treatment was conducted to increase
the surface tension of the substrate.
However, it is still challenging to print the PEDOT:PSS on top of the
active layer with a hydrophobic surface for the fabrication of the
inverted OSCs. For example, P3HT:PCBM layer was found to have a
surface energy of 24.2 mN/m, which is far lower than the surface energy
of PEDOT:PSS film (~72 mN/m). Therefore, tuning the ink formulations
to change the aqueous nature of the PEDOT:PSS solution for better
spread ability on the hydrophobic surface is an essential issue. Isopropyl
alcohol (IPA) is the most commonly used additive for PEDOT:PSS to
reduce surface tension [189]. Krebs and coworkers dilute the PEDOT:
PSS with isopropanol (IPA) to give a viscosity of ~200 mPas in a slot-die
process (integrated into an R2R system) with speeds of 12.0 m h-1 [190].
Surfactants, such as Triton X-10024[191] and Zonyl FS-30025 [192],
were also used previously. In 2018, Pali et al. used IPA and fluo­
rosurfactant zonyl FS-300 as additives to modify the PEDOT:PSS inks
[188]. With the excellent wettability of IPA on the surface of P3HT:
PC61BM blends, the screen-printed PEDOT:PSS films with 5 wt% IPA
exhibited homogeneous features (Fig. 14). Due to their thickness
ranging from 500 to 700 nm, the PEDOT:PSS front electrode showed
60–70% transmission in the visible range (350–750 nm) and exhibited
an Rsq of 700–1100 Ω/sq.
As we previously state, the photoactive materials consist of polymer/
polymer blends or polymer/small molecule blends in a typical BHJ type
F-OSCs, in which the polymers enable the solution to have enough vis­
cosity for most coating/printing methods. For photoactive materials,
there exists a trade-off between film thickness and photoelectric prop­
erty due to the light absorption and charge transport, while it is difficult
to fabricate very thin films via the most scalable fabrication techniques.
Hence, thick-film photoactive materials with thickness insensitiveness
are required in the large-scale fabrication of F-OSCs. Also, a smooth
surface to gain ohmic contact with the electrodes and a separated phase
morphology facilitating for exciton separation is of great importance to
achieve high performance and stability. Thus, the demand for the large-
scale method should satisfy the demands.
With the 3D-printer-based slot-die coating equipment, Lee et al.
fabricated F-OSCs based on the ternary blend of PTB7-Th, PC71BM, and
Fig. 14. (a) Schematic diagrams of the screen printing process. Optical micrographs of screen printed PEDOT:PSS films on P3HT:PC61BM layer: (b) edge of the film,
(c) center of the film and (d) contact angle of P3HT:PC61BM layer. Optical micrographs of screen printed PEDOT:PSS films with the addition of 5 wt% IPA on P3HT:
PC61BM layer: (e) edge of the film, (f) center of the film and (g) contact angle of IPA on P3HT:PC61BM layer. Reproduced with permission [188]. Copyright (2018)
Springer Science+Business Media, LLC, part of Springer Nature.
16
Nano Energy 89 (2021) 106399
COi8DFIC at a scalable level [193]. The 3D slot-die platform can provide
accurate 3D direction control and auto solution-feed controlling by
computer commands. Thus, the system makes it possible to realize auto
registration and printed F-OSCs with high reproducibility. The slot-die
coated module with 30 cm2 active-area and roll-to-roll produced
F-OSC has shown 8.6% and 9.6%, while the PCE for small-area F-OSC
(0.1 cm2) is 12.4% with careful and systematic optimization of the
slot-die active-layer-deposition conditions. To remove the toxic and
hazardous organic solvents in the R2R process, aqueous solar nano­
particle (ASNP) inks were developed to obtain surfactant-free nano­
particles in alcohol [194]. Large-scale F-OSCs based on the ASNP inks
were constructed with a conventional architecture (PET/silver grid/­
PH1000/ASNP/ZnO/Al) by Almyahi et al.[195] Silver grids were
flexographically printed onto PET substrates by using an anilox roller,
and simultaneously the Al electrode was deposited by R2R sputter
coater. Other layers were fabricated by a slot-die coating method. The
ozone treatments significantly improved the wetting properties of ASNP
inks on the PEDOT:PSS films, resulting in a smoother ASNP layer. Min
and coworkers fabricated non-fullerene F-OSCS by slot-die printing
PBDB-T-SF:IT-4F blend onto PET/Ag-mesh/ZnO substrate after
balancing the flowing rate and coating speed (Fig. 15) [40]. The printed
F-OSCs exhibited a PCE of 12.01%, which is comparable to that of the
ITO/glass-based devices (12.9%). Furthermore, the printed F-OSCs
retains> 87% of its initial PCE after 500 blending cycles at radius of
6 mm.
Most researches for F-OSCs focus on lab-scale processing, such as
spin-coating, which may be very different in manufacture-level mod­
ules. The lab-to-manufacturing translation from the existing lab-scale
devices to industrial-scale modules is a critical challenge for future ap­
plications. However, the complex operation process and ink formula­
tions make it difficult to control the morphology and phase separation of
the BHJ type photoactive layers. To establish a general correlation to
guide lab-to-manufacturing translation and provide a sustainable insight
for future improvement, Chen and coworkers explored the mechanism
of morphological evolution in the BHJ layer with different coating/
printing methods, trying to establish the quantitative transformation of
shear impulse between slot-die printing and spin-coating (Fig. 16)
[196]. After excluding the influence of the solvent volatilization, a
transformation factor about 1.1 × 104, which represents the trans­
formation factor of impulse between slot-die printing and spin-coating,
was calculated and applied into the actual preparation of F-OSCs. The
reliability of the transformation was further confirmed through the
C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 15. (a) The conceptual diagram for the slot die coating with independently controlled parameters. The inset shows the schematic of meniscus formation and the
streamlines near the stagnation point in the slot-die head. (b) Digital photograph of slot-die coating setup and the achieved high-quality BHJ films with the ZnO layer.
(c) Left: the stable coating window for slot-die coating allows for defect-free films; Right: the performance of inverted PBDB-T-SF:IT-4F based OSCs depending on
flowing rate and coating speed. Reproduced with permission [40]. Copyright (2019) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

morphological measurements and molecular simulations. This me­
chanics of shear impulse initiatively provides a new perspective to
resurvey the lab-to-manufacturing translation for F-OSCs.
4. Potential applications of F-OSCs
The application of F-OSCs will be a great complement to the existing
photovoltaic techniques to expand the border of the photovoltaic
industry. Different target applications would result in distinct demands
for performance, stability, and mechanical parameters. For example, for
building-integrated photovoltaics, devices should possess requirement
on long-term stability under operation and illumination but fewer de­
mands on flexibility. Thus, one should consider a specific target appli­
cation to make the relevant parameters before designing and
constructing F-OSCs. Here, we discuss the several attempts on exploiting
the possibility of F-OSCs for emerging unique industrialization.

17
C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 16. Schematic illustrations and experimental design. a) Molecular structure of PTB7-Th, PC71BM, PBDB-T, and ITIC. b) Schematic diagram of morphology
evolution between spin-coating and slot-die process. T means the transformation factor. c) The PCEs of OSCs devices with different spin-coating times [196].
Copyright (2019) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

4.1. Solar trees demonstrated the possibility of large-scale solution-processable F-OSC

Researchers of Merck Chemicals represented a paradigm shift for
semitransparent (Ttrans ≈ 20%) F-OSCs modules by preparing large-area
OSC products named “solar trees” and installing them at the German
pavilion, Universal Exhibition Milan 2015 (Fig. 17a) [50]. All the layers
of the devices were fabricated by the doctor-blade coating technique
under the ambient condition at lab-scale, except for the PEDOT:PSS HTL
layer that was spin-coated onto the stacked devices. The
manufacturing-scale F-OSCs were fabricated by a typical R2R process.
The device transferred from lab-scale (0.04 cm2) to manufacturing-scale
(250 m2) without additional optimization. Eventually, hexagonal
“leaves” modules of the solar trees were obtained by connecting 6
groups in parallel, and each group has 9 serially connected cells. With
the areas growing larger, the PCEs of the devices decreased in sequence
from 8.5% (0.04 cm2) to 7.2% (1.00 cm2), 4.3% (114.5 cm2), and 4%
(250 m2). The solar trees at the Universal EXPO 2015 in Milan clearly
systems.
4.2. Green house and photosynthesis
Photosynthesis processes for plant growth generally absorb light
irradiation in the visible light region (370–740 nm) because of the
dominant status of chlorophyll a and b pigments [198]. The photo­
morphogenesis process for plants also needs lights located in specific
regions. For example, light irradiation with short-wavelength (blue)
would facilitate vegetative leaf growth and with long-wavelength (red)
would accelerate for flowering. Thus, the semi-transparent F-OSCs with
tuned spectrum can be integrated into the greenhouse to provide addi­
tional electrical energy while transmitting enough sunlight for plant
growth, or controlling the photomorphogenesis process [21]. Recently,
Ge and coworkers exploited the feasibility of using foldable-flexible
OSCs for photosynthesis in the lab scale [197]. The semi-transparent

Fig. 17. Building-integrated photovol­

taics: (a) Images of a commercial mod­
ule fabricated by BELECTRIC OPV, top
left corner; chemical structure of the
polymer PBTZT-stat-BDTT, top right
corner; and large scale deployment of
BELECTRIC OPV modules at the Uni­
versal Exhibition Milan 2015, bottom
[50]. (b) Depiction of the greenhouse
[52]. (c) Optical photograph of mung
bean leaves changing in 9 d under direct
sunlight (L), direct sunlight with
FST-OSCs roof (S), and dark (D) [197].
Reproduced with permission. Copyright
(2015) The Authors. Published by
WILEY-VCH Verlag GmbH & Co.KGaA;
Weinheim; (2020) Elsevier Inc.; (2020)
WILEY-VCH Verlag GmbH & Co.KGaA,
Weinheim.

18
C. Liu et al. Nano Energy 89 (2021) 106399

F-OSCs were fabricated with modified PEDOT:PSS as electrode and
PBDB-T-2F:Y6 as photoactive layer to ensure enough transmittance in
the visible region. The overall semi-transparent foldable-flexible OSCs
yielded PCEs of >10% and Ttrans of 21% in the visible region. F-OSCs
were then integrated as part of roofs into the simulated greenhouse. The
plants showed comparable growth rates under F-OSCs with those grown
under sunlight after monitoring for 9 days (Fig. 17c). The researchers
also prospected that additional power could be used for future
self-powered greenhouse, although they did not provide or store the
output power. Recently, semi-transparent OSCs were employed on
greenhouses to achieve net-zero energy greenhouses in warm and
moderate climates (Fig. 17b) [52].
4.3. Self-powered skin-wearable sensors
Weight and flexibility are the fundamental characteristics of organic
electronics, which totally agree with the “mechanical invisibility”
concept for skin-wearable devices. To better implement the skin-
wearable sensors, ultrathin, ultra-flexibility while lightweight OSCs as
the power source in the circuits are required. Prof. Someya from The
University of Tokyo had made significant effort on the ultrathin and
ultra-flexibility F-OSCs [34,66,201]. In 2011, they demonstrated that
ultrathin F-OSCs based on 1.4-μm-thickness PET substrate (which is
commercially available Mylar 1.4 CW02) could be fabricated in a total
<2 µm thickness while exhibiting comparative efficiency with ITO/glass
based counterparts (Fig. 18a-c) [34]. The overall ultrathin F-OSC yiel­
ded a PCE of 4.2% and an excellent specific weight value of 10 W/g.
High flexibility was measured by adhering the flexible device to a
pre-stretched elastomer. The F-OSCs could survive quasi-linear
compression to below 70% aas well as cyclic compression and stretch­
ing to 50%, over more than 20 full cycles. In 2018, they proved the
possibility of F-OSCs to be integrated into organic electrochemical
transistors (OECTs) and thus the self-powered cardiac sensors were
achieved (Fig. 18b-f) [9]. The cardiac sensors were proven to have high
transconductance (0.8 mS), high responsivity (105), high-speed re­
sponses (0.58–0.62 ms), and be compatible with the frequency ranges of
human biological signals (approximately 200 Hz). F-OSC module in the
system was demonstrated to have an enormous contribution to the
signal-to-noise ratio (S/N) as it exhibited the lowest noise currents of
0.02 μA as compare with that of source meter (0.58 μA) and commercial
battery (0.08 μA). The self-powered sensors were attached to the
fingertip and the exposed surface of a rat heart with S/N of 25.9 dB and
40.02 dB, respectively.
Near-infrared light is generally appropriate for skin-interfaced health
monitoring, such as photoplethysmogram [146]. Because near-IR is not
harmful to humans and has a long propagation distance (>4 mm) within
the tissue [202]. Thus, F-SOCs with a narrow-bandgap active layer can
be applied into near-IR organic photodetectors. Park et al. fabricated an
ultraflexible OSCs-structured near-infrared skin-conformal photo­
plethysmogram sensor based on a narrow-bandgap polymer and
PC61BM as photoactive layer [200]. The ultrathin (3-µm thick)
OSCs-structured near-IR photodetector exhibited mechanical stability at
r < 3 µm for 1000 bending cycles. Also, the fabricated sensors exhibited
outstanding cut-off response frequency over 1 kHz at − 3 dB and better
sensitivity than a normal rigid glass-based device. Therefore, Due to its
high conformability and bio-compatibility, F-OSCs emerged as the
next-generation electronics and would be much capable as a
human-compatible, wireless power source.
4.4. Photo-charging capacitors
Flexible integrated photo-charging (or named self-rechargeable)
devices composed of F-OSCs and flexible supercapacitors[203,204] or
lithium batteries [205] as energy storage units were reported. The
photo-charging system can provide an independent power supply for
next-generation wearable electronics or biomedical devices. To balance
the trade-off between performance and thickness, Liu et al. demon­
strated that the 50-µm-thick flexible photo-charging capacitor showed a
total PCE of 5.92% by integrating 3-µm-thick F-OSCs on 40 µm-thick
carbon nanotube/polymer-based supercapacitors (Fig. 19a-c) [203].
The flexible photo-charging capacitor was achieved by stacking the
F-OSCs and the supercapacitor. The systems also exhibited superior

Fig. 18. Ultraflexible OSCs toward self-powered skin-wearable sensors: (a) Scheme of the ultra-light and sub-2-μm-thick F-OSCs [34]. (b) Extreme bending flexibility
demonstrated by wrapping a solar cell around 35-μm-radius human hair. (c) Stretchable solar cells were made by attaching the ultrathin solar cell to a pre-stretched
elastomer. They are shown flat (left) and at 30% (middle) and 50% (right) quasi-linear compression. (d) Schematic of a double-grating-patterned F-OSCs integrated
with an OECT [9]. (e) Photograph of the integrated device. (f) Circuit diagram of the integrated device. (g) Experimental setup to test near-IR light time response
[200]. (h) Images of an ultrathin near-IR responsive device laminated into a pre-stretched acrylic elastomer for conformability testing. Images from left to right
represent the transition from the flat state to the wrinkled state. Reproduced with permission. Copyright (2012 & 2018) Springer Nature Limited; (2018) WILEY-VCH
Verlag GmbH & Co.KGaA, Weinheim.

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C. Liu et al. Nano Energy 89 (2021) 106399

Fig. 19. Photo-charging application: (a) Schematic illustration of the top-down integrated device [203]. (b) Working mechanism of the photo-charging process. (c)
Photographs of the as-fabricated ultra-thin device (left) and the device wrapped onto a rod (diameter: 2 mm). (d) Schematic of conversion and control circuit (CC)
that manages the flow of charge between the OSCs and a sensor load [204]. (e) flexible substrate using 3D-printed PLA and with conductive traces showing potential
integration of OSC, sensors, and CC. Reproduced with permission. Copyright (2020) WILEY-VCH Verlag GmbH & Co.KGaA. Copyright (2021) IOP Publishing.

Fig. 20. Textile-based washable F-OSCs. (a) Photograph of the washing process for the devices conforming to a dress shirt. Scale bar, 1 cm [207]. (b) Structure of the
free-standing OSCs. (c) Chemical structure of PNTz4T. (d) Schematic of the double-side-coated OPVs. (e) schematic diagrams of the optoelectronic module and OLED
structure and the picture of the operating module during the washable test with the inset image indicating the module being dipped in water after washing [208].
Reproduced with permission. Copyright (2017) Macmillan Publishers Limited, part of Springer Nature; (2018) The Royal Society of Chemistry.

20
C. Liu et al.
operational stability (> 96% efficiency retention after 100 charge/di­
scharge cycles for one week) and mechanical robustness (94.66% effi­
ciency retention after 5000 bending cycles at an r ≈ 2 mm). However,
the systems may suffer the issues of undercharging or unbalanced charge
storage of the supercapacitor arrays in practical application due to
instability of F-OSCs. Glass and coworkers further incorporated a con­
version and control circuit (CC) between F-OSCs and supercapacitors
through 3D-printing technique, demonstrating its possibility to solve the
problems (Fig. 19e-f) [204]. The application of CC achieved more energy
harvesting from the F-OSCs by storing them in the supercapacitor bank.
4.5. Washable electronic textile toward self-powered smart clothing
Self-powered smart clothes integrated with multi-functional elec­
tronic devices have attracted much attention in the Internet of Things
(IoT) [206]. For electronic wearable devices, it is essential to possess
features of environmental stability, sufficient energy efficiency, and
mechanical robustness. Textile-based wearable F-OSCs, which produce
power from the surrounding environment and even the indoor circum­
stances, are promising to smart clothes. However, achieving these re­
mains difficult because of the susceptibility of the traditional F-OSC
architecture and active layers to the surrounding moisture and oxygen.
To address this issue, thin-film encapsulation barriers were reported
[207,208]. Jinno et al. reported the single-/double-side-coated passiv­
ation layer, prepared by coating 500-μm-thick acrylic elastomers (3 M
VHB Y-4905J), was used to improve the operational stability of F-OSCs
(Fig. 20a-c) [207]. The textile-based F-OSCs showed excellent wash­
ability with only a 5.4% decrease of PCE after immersion in water for
120 min. Furthermore, due to the elastomeric state of the passivation
layer, PCEs of the F-OSCs remained at 80% of the initial value even after
52% mechanical compression for 20 cycles with 100 min of water
exposure. Jeong et al. incorporated the SiO2-polymer composite capping
layer to encapsulate the F-OSCs (Fig. 20e) [208]. The textile-based
washable F-OSCs exhibited water resistance with only 2% degradation
after washing 20 times for 10 min and mechanical stability when
operated at a low curvature radius (r = 3 mm).
5. Conclusion and perspective
In conclusion, this review provided an overview of F-OSCs, from the
aspect of materials, large-area fabrication techniques and potential ap­
plications. Materials for F-OSCs contain flexible substrates, transparent
electrodes, interfacial layers and photoactive layers. PET and PI are the
most widely used flexible substrates, in which PI has better performance
due to the excellent stability and mechanical properties. PEDOT:PSS and
AgNWs are the two promising candidates, in which AgNWs show much
higher conductivity that is suitable for large-area application. Graphene
is another candidate, but its large-quality synthesis limits its application.
For interfacial layers, several materials, from inorganic ZnO and SnO2 to
organic materials, such as PEDOT:PSS and PFN, have been applied into
F-OSCs. Photoactive layers, containing electron donor and acceptor
(fullerene or non-fullerene), have been widely applied into F-OSCs. With
the innovation of conjugated polymers and non-fullerene acceptors,
high-performance rigid OSCs were also transferred to flexible substrates,
so that the PCEs of F-OSCs could also realize PCEs over 15% in recent
years.
After many years of researches, OSCs have arrived at the crucial
moment toward industrial application. Konarka Technologies, Inc. that
was found in 2001 ever tried to realize this goal. They obtained some
investment and build large-area modules as charge facilities at the bus
station, but unfortunately, it announced bankruptcy in 2012. Nowadays,
new materials emerge, such as high-performance non-fullerene electron
acceptors and AgNWs, so that OSCs gain new opportunities. For large-
area devices, high efficiency, low cost and long lifetime are the three
key components for the application. To meet these requirements, more
efforts from the aspect of materials and large-area fabrication techniques
21
Nano Energy 89 (2021) 106399
are still needed.
Firstly, materials for F-OSCs are the most important parts. For the
flexible substrates, PI is a promising candidate due to the excellent
stability and mechanical properties, but it also meets some drawbacks,
such as high cost, transparency, solvent tolerance and large-area thin-
film fabrication techniques. Transparent electrodes also have similar
issues with PI, in which AgNWs and PEDOT:PSS are the two candidates.
PEDOT:PSS has low roughness and good mechanical properties, but its
conductivity and transparency can not meet the requirement for large-
area devices. AgNWs have relatively high conductivity, but their high
roughness and low stability should be addressed. For the interfacial
layers, it is important to realize high PCEs under thick films. Among
large amounts of materials, ZnO and low conductivity PEDOT:PSS
would be the optimal choice for ETL and HTL, but the high thermal
treatment of ZnO films and the poor wettability of PEDOT:PSS on the
photoactive layers are still needed to be tackled. Photoactive layers are
the most important part of these materials although they have been
widely studied. Large quantity with low cost is the key issue in these
conjugated materials. Nowadays, most of high-performance conjugated
materials for OSCs have high costs with complex synthetic procedures.
P3HT ever had the low cost with easy synthesis, but unfortunately,
P3HT-based solar cells showed low PCEs. Recently, some studies re­
ported that when using specially designed non-fullerene acceptors,
P3HT-based OSCs could realize PCEs over 9% [209–211], which would
be a promising candidate for F-OSCs. Another possibility is to develop
new conjugated polymers with a similar synthetic method for P3HT by
using Grignard metathesis polymerization.
Secondly, the composite and assembly of different layers in F-OSCs
should be paid special attention. For example, AgNWs on top of flexible
substrates shows large roughness, which can be significantly reduced
when using embedded AgNWs/PI substrates. In this system, the inter­
action between AgNWs and PI substrate, and the fabrication techniques
to form the composite electrodes should be considered. The electrodes
and interfacial layers with organic-inorganic composite materials are
the optimal choice to solve the problems in these materials, such as
AgNWs/PEDOT:PSS and ZnO/polymer electrolytes. The combination of
multi-materials is helpful to improve their performance and meanwhile
solve their defect during application. Additionally, the adhesion be­
tween different layers is also important for the stability of solar cells.
Therefore, some non-covalent interactions, such as H-bonding, can be
introduced into different layers.
Thirdly, although several large-area fabrication techniques have
been applied into F-OSCs, there are still very few studies to focusing on
this field. One of the important questions is the high cost of photoactive
layers so that researchers are hesitant to be involved into this field. This
would require effort from industrial partners. Before their interest
entering into this field, people from academia can have some prepara­
tion, such as, trying to find out new conjugated materials with low cost
and high quantity, and doing some relatively small area devices by using
roll-to-roll techniques.
Finally, for the potential application, although some applications,
such as IoT, indoor photovoltaics, semi-transparent windows, green­
house, etc., have been explored, the interest from markets is still low.
This would be one reason that investors are hesitant to be involved in
this field. Recently, the electric vehicle has become important in our
daily life, in which charging is one of the important issues to relate to
performance. It seems that F-OSCs are the promising candidate to be
used in this field. Let’s do some calculations: the annual total radiation
irradiance of sunlight was 160–200 W/m2 in Beijing, according to the
data from Wind and Solar Energy Resource Center, China Meteorolog­
ical Administration [212]. We assume that the average PCEs of OSC
modules are 10%, the areas of the modules are 4 m2. Thus, those mod­
ules could produce ≈ 1.54 kWP h/day in Beijing. This definitely extends
the possible range of commutes and eliminates range anxiety.
Hence, in terms of all these discussions, intense efforts have been
devoted to preparing new materials, optimizing the various large-scale
C. Liu et al.
techniques, and exploiting the application possibility in specific areas.
Even though the exchanging and communication of the three aspects are
not fluent, fruitful achievements of F-OSCs have been achieved during
the past years. Considering the current trend of non-fullerene acceptors,
the chasing on high PCEs and high flexibility of F-OSCs is speeding up.
We predict that the F-OSCs will occupy a major position in the semi­
conductor industry in the future.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This study is jointly supported by MOST of China
(2017YFA0204702, 2018YFA0208504), and the National Natural Sci­
ence Foundation of China (52073016, 51773207, 51973031, 21905018,
21905158). This work was further supported by the Fundamental
Research Funds for the Central Universities (buctrc201828, XK1802-2),
Open Project of State Key Laboratory of Supramolecular Structure and
Materials (sklssm202043) and Jiangxi Provincial Department of Science
and Technology (No. 20192ACB20009).
Conflict of Interest
The authors declare no conflict of interest.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2021.106399.
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[208] E.G. Jeong, Y. Jeon, S.H. Cho, K.C. Choi, Textile-based washable polymer solar Chengcheng Xie received his B.S. and master degree from
cells for optoelectronic modules: toward self-powered smart clothing, Energy Tianjin Polytechnic University in 2016 and 2019. He is now a
Environ. Sci. 12 (2019) 1878–1889. Ph. D. candidate at BUCT. His research focuses on transparent
[209] C. Yang, R. Yu, C. Liu, H. Li, S. Zhang, J. Hou, Achieving over 10 % efficiency in electrodes for F-OSCs.
poly(3-hexylthiophene)-based organic solar cells via solid additives,
ChemSusChem (2021), https://doi.org/10.1002/cssc.202100627.
[210] X. Xu, G. Zhang, L. Yu, R. Li, Q. Peng, P3HT-based polymer solar cells with 8.25%
efficiency enabled by a matched molecular acceptor and smart green-solvent
processing technology, Adv. Mater. 31 (2019), 1906045.
[211] B. Xiao, M. Du, X. Wang, Z. Xiao, G. Li, A. Tang, L. Ding, Y. Geng, X. Sun, E. Zhou,
Effects of oxygen atoms introduced at different positions of non-fullerene
acceptors in the performance of organic solar cells with poly(3-hexylthiophene),
ACS Appl. Mater. Interfaces 12 (2020) 1094–1102.
[212] J.J. Pan, Y. Jiang, P. Guo, Y.S. Zhang, Analysis of China’s solar energy resources
and environmental meteorological factors, Sci. Technol. Rev. 32 (2014) 15–21.
Weiwei Li received his Ph.D. from ICCAS in 2010. He then
worked as a postdoctoral researcher at the University of
Chunhui Liu received her B.S. degree from Nanjing University Alberta, Canada and Eindhoven University of Technology, the
of Information Science and Technology in 2019. She is now a Netherlands in 2010–2014. He has been a full professor at
master student at Beijing University of chemical technology ICCAS since 2014 and joined BUCT in 2019. His research in­
(BUCT). Her research focuses on high-efficiency and flexible terest is flexible OSCs, from materials to devices.
organic photovoltaics.

Chengyi Xiao is currently a lecturer of BUCT. He received his

B.S degree in the department of Applied Chemistry from
Xiangtan University (XTU) in 2011. Then, he received his Ph.D.
degree at the Institute of Chemistry, Chinese Academy of Sci­
ences (ICCAS) in 2017. In the period from 2016 to 2019, he
collaborated with Prof. Lei Zhang as a postdoctor at BUCT. His
research focuses on organic field-effect transistors and high-
efficient F-OSCs.

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