Solar Energy 218 (2021) 621–638

Contents lists available at ScienceDirect

Solar Energy
journal homepage: www.elsevier.com/locate/solener

Review

Recent progress in emerging 2D layered materials for organic solar cells

Yong Zhao a, Liangmin Yu b, Mingliang Sun a, c, *
a
School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China
b
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao 266100, China
c
Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology,
Guangzhou 510640, China

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

Keywords: Currently, organic solar cells (OSCs) are one of the most cutting-edge photovoltaic technologies due to their
Organic solar cells light-weight, semitransparent, and flexible advantages, which meet the needs of commercial applications. In
2D materials order to fully develop the application potential of this novel class of photovoltaic cells, organic molecular design
Electrodes
and device construction have all been playing significant roles. Research shows that two-dimensional (2D)
Charge transport materials
Additives
layered materials with unique physical structure and excellent photoelectric properties can effectively optimize
the device performance of OSCs. Although the exploration of various emerging 2D materials for use in OSCs has
made considerable progress, there remain some crucial bottlenecks to be solved. In this review, the progress that
has been made in the application of these 2D materials for OSCs in recent years is presented, including MXenes,
black phosphorus (BP), and transition metal dichalcogenides (TMDs), etc. The merits and demerits of 2D ma­
terials in OSCs application are summarized in detail. Ultimately, it outlines the commercial development di­
rection of OSCs in the near future, and the significance of 2D materials in stable, low-cost, large-area, and flexible
devices.

1. Introduction
Due to the current global energy shortage and the accompanying
environmental crisis, it is urgent to seek low-cost, clean, and renewable
energy as alternatives (Cui et al., 2019; Li et al., 2019; Sun et al., 2020;
Xing et al., 2020). The conversion of solar energy via solar cell devices is
considered to be one of the most fascinating and promising green energy
technologies. Recently, perovskite solar cells (PSCs) (Cui, D. et al.,
2020), quantum dot solar cells (QDSCs) (Wang et al., 2018), dye sensi­
tive solar cells (DSSCs) (Chen, L. et al., 2019), and other photovoltaic
technologies have all been intensively investigated. Among above solar
cells, OSCs are currently sitting in the spotlight thanks to their advan­
tages in chemical structural diversity, solution-processability and flexi­
bility. These strengths ensure that OSCs can manufacture low-cost and
large-area devices on flexible substrates (Fan et al., 2019; Yan et al.,
2019; Zhang et al., 2019). With the progress of materials (such as fused-
ring electron acceptors) (Lin et al., 2015; Lu, S. et al., 2020; Yuan et al.,
2019) and devices, the power conversion efficiency (PCE) of OSCs has
exceeded 18% so far (Cui, Y. et al., 2020; Liu et al., 2020).
Despite the unprecedented development, still a lot remains to be
done. The significant challenges include environmental stability (water,
oxygen, and irradiation), scalability, and stability of device structure,
which severely limit the potential for commercialization (Brus et al.,
2019; Naveed et al., 2019; Yu, P. et al., 2019). It is well acknowledged
that hole transport layer (HTL) and electron transport layer (ETL) of
OSCs have long-term instability and high cost (Ayari et al., 2007; Li, J.
et al., 2020; Ruscello et al., 2019; Schulz et al., 2014). As such, the
investigation of active layer, electrode, and interlayer is one of the
strategies to improve the performance and stability of device. Various
materials have been in comprehensive researched as modifiable or

Abbreviations: OSCs, Organic solar cells; PSCs, Perovskite solar cells; QDSCs, Quantum dot solar cells; DSSCs, Dye sensitive solar cells; PCE, Power conversion
efficiency; JSC, Short-circuit current density; VOC, Open circuit voltage; FF, Fill factor; EQE, External quantum efficiency; SCLC, Space charge limited current; μe,
Electron mobility; μh, Hole mobility; BP, Black phosphorus; BPQDs, Black phosphorus quantum dots; PQDs, Perovskite quantum dots; GR, Grapheme; TMDs,
Transitional metal dichalcogenides; GO, Graphene oxide; R-GO, Reduced graphene oxide; MOFs, Metal organic frameworks; AgNW, Silver nanowire; ITO, Indium-
doped tin oxide; FTO, Fluorine-doped tin oxide; PI, Polyimide; HTL, Hole transport layer; ETL, Electron transport layer; HEL, Hole extraction layer; EEL, Electron
extraction layer; 2D, Two-dimensional; TCEs, Transparent conductive electrodes; CVD, Chemical vapor deposition; FOM, Figure of merit.
* Corresponding author.
E-mail address: mlsun@ouc.edu.cn (M. Sun).

https://doi.org/10.1016/j.solener.2021.02.066
Received 21 December 2020; Received in revised form 25 February 2021; Accepted 26 February 2021
Available online 23 March 2021
0038-092X/© 2021 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
Y. Zhao et al. Solar Energy 218 (2021) 621–638

alternative materials for different components of OSCs. According to the community since the advent of GR in 2004. After that, TMDs (Shi­
literature, the work function of 2D materials is tunable through func­ vayogimath et al., 2019), BP (Eswaraiah et al., 2016; Sang et al., 2019),
tionalization or specific treatment methods. What is more, 2D materials MXenes (Lu, C. et al., 2020; Zang et al., 2020) and other 2D materials
can be fabricated easily via solution-processable techniques (Pan et al., were discovered one after another, opening a universe of applications
2019; Zhao et al., 2018). Owing to superb optoelectronic, stable me­ for 2D materials in optoelectronic devices (Table 1) (Li, F. et al., 2020).
chanical and physical properties, as well as unique morphology and Some 2D layered materials can be made into monolayer or few-layers
structure, 2D layered materials is proven to be promising candidates for nanosheets with controllable size and morphology by facile exfolia­
boosting the performance of OSCs (Batmunkh et al., 2018; Díez-Pascual tion. Therefore, 2D layered materials can be used as essential auxiliary
et al., 2018). Nowadays, with the rapid development of tandem (Ling­ factors to promote the development of OSCs devices. The recent explo­
xian Meng et al., 2018; Liu, G. et al., 2019), flexible transparent (Chen ration of emerging 2D layered materials in different components of OSCs
et al., 2020), and ternary OSCs (Jin et al., 2019), 2D layered materials will be discussed in the following sections (Fig. 1).
will definitely have more application space. Therefore, it is of great
significance to summarize the latest progresses that has been made in 3.1. Electrode
this hot field.
Herein, we briefly introduced the common structures and compo­ ITO and Fluorine-doped tin oxide (FTO) are often used as the highly
nents of OSCs. Subsequently, this review comprehensively summarized transparent and conductive electrode of OSCs. Nevertheless, the ITO is
the recent advances in applying emerging 2D materials such as BP, expensive and not resistant to high and low pH (Bonaccorso et al., 2010;
MXenes, TMDs, graphene (GR) and its derivatives to improving the Choi et al., 2011). What is more, its rigid nature makes it easily breaking
performance of OSCs by optimizing device structure. Ultimately, we or cracking on flexible substrates (Bonaccorso et al., 2010; Stotter et al.,
outlined the challenges and requirements for the future commerciali­ 2005). Such issues mean that commercial OSCs require better electrode
zation of 2D materials based efficient and low-cost OSCs. replacements with high transparency, excellent conductivity, flexibility
and stability (Table 2).
2. Overview of OSCs device structure Graphene is regarded as a potential material that could act as
transparent conductive electrodes (TCEs) for flexible optoelectronic
For decades, the growing interest in OSCs has resulted in the gradual devices due to its superb mechanical and photoelectric properties (Wan
completion of device structure, namely, conventional and inverted. In et al., 2011). It was used as TCE by Klaus Müllen et al. in 2008 (Wang
general, the device structure includes a conductive substrate, HTL, et al., 2008). Simultaneously, Peumans et al. (Wu et al., 2008) reported
active layer, ETL, and electrode. Promising component materials should the solution-processed GR as transparent electrode in OSCs. It has been
exhibit the following properties: i) suitable energy alignment to others, proved that GR and its derivatives could be used as TCEs to replace
ii) durability, iii) low-cost, iv) high carrier mobility, and v) transparency traditional ITO. Previously, the development of GR electrodes in OSCs
(Yao et al., 2019). has been systematically summarized (Mahmoudi et al., 2018).
Interface engineering is a critical factor in achieving high photo­ Lately, Park group published that flexible OSCs with polyimide (PI)-
voltaic performances for large-area, flexible, and printable OSCs. Rigid integrated GR as electrode reached 15% efficiency (Koo et al., 2020). In
indium-doped tin oxide (ITO) glass often is used as a conductive sub­ order to avoid the influence of high-temperature annealing processes on
strate, which does not meet the commercial needs of flexible substrates. the plastic substrate, this article introduced a superior thermal stable,
However, the performance of flexible OSCs still falls behind that of their mechanical durable, and flexible electrode prepared via integration of PI
rigid counterparts (Meng et al., 2019; Yan et al., 2019). Currently, the on GR (Fig. 2a-c). PI film is a flexible material with a wide range of
direct integration of polyimide (PI) on layered GR has been realized to applications and easy processing. PI is used not only as a carrier film but
obtain a highly flexible substrate with thermal stability (Tang et al., also as a substrate of GR, thereby simplifying the electrode preparation
2019). Generally, low work function materials are used as ETL, whereas process. (Koo et al., 2020). As we all know, the associated high surface
high work function materials are used as HTL (Liu et al., 2015). There roughness can deteriorate the performance of device, whereas PI@GR is
are still some deficiencies in the electron and hole transport materials ultra-clean, smooth, and high-quality surface without polymer residue
currently used. For example, metal oxides (ZnO、MoO3) (Girotto et al., (RMS only is 0.34 nm). Single layer GR (≈ 25 μm) was prepared by low-
2011; Sun et al., 2011) are fabricated from high-cost vacuum deposition, pressure chemical vapor deposition (CVD) on Cu foil, which had higher
and the hygroscopic nature and high acidity of poly (3,4-ethyl­ transparency and conductivity than those of prepared by Hummer’s.
enedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are serious
issues, greatly affecting the device performance and stability (Lin et al.,
Table 1
2019; Yun et al., 2011). Hence, the interface layer can be doped or Overview of key parameters of emerging 2D materials.
replaced with 2D layered materials to improve stability and conduc­
2D Bandgap Carrier Thermal Ref.
tivity, which has been proved by lots of research. Simultaneously,
materials [eV] Mobility Conductance [W
inserting hole or electron extraction layer between active layers and [cm2V-1s− 1] m-1K− 1]
electrodes is the effective strategies to facilitate charge collection and
Ti3C2Tx 0 – 3.4 0.70 10 – 472 Naguib et al.,
transport (Lin et al., 2016; Wijeyasinghe et al., 2017; Yu et al., 2016). 2014; Yang et al.,
Upon light absorption by the active layer, an exciton (electron-hole pair) 2019b
is generated. In order to ensure the maximum migration and separation GR 0 2 × 105 5 × 103 Wan et al., 2011
of exciton, it is necessary to build fabulous morphology of the active BP 0.3 – 2.0 1000 10 – 36 Qiao et al., 2014;
Pang et al., 2018
layer. In addition to fine molecular design, the introduction of 2D
MoS2 1.2 – 1.8 10 – 200 34.5 – 52 Bati et al., 2019;
layered materials into the active layer is also a practical means to Wang et al.,
ameliorate morphology and maintain its durability (Van Le et al., 2017). 2012; Gu et al.,
2D layered materials are attracting increasing attention as candidate 2013
WS2 1.3 – 2.1 43 – 234 32 – 53 Lin et al., 2019
materials for OSCs owing to their distinctive properties, adjustable en­
WSe2 1.2 – 1.7 140 – 500 9.7 Lin et al., 2019;
ergy level, and solution processability. yang et al.,
2019c
3. 2D layered materials in OSCs α-In2Se3 1.5 – 2.8 —— —— Wang et al.,
2019; Li et al.,
2020a,b
2D materials have drawn enormous attention from the scientific

622
Y. Zhao et al. Solar Energy 218 (2021) 621–638

Fig. 1. Schematic diagram showing

the different classes of 2D materials
covered in this progress report. (Black
Phosphorus) Reprinted with permis­
sion from (Batmunkh et al., 2018)
Copyright 2018 Wiley. (Transitional
Metal Dichalcogenides) Reprinted
with permission from (Gu et al.,
2013) Copyright 2013 Wiley. (Gra­
phene) Reprinted with permission
from (Mahmoudi et al., 2018) Copy­
right 2018 Elsevier. (MXenes)
Reprinted with permission from
(Yang et al., 2019a) Copyright 2019
Royal Society of Chemistry.

Table 2
The 2D materials are used as electrodes in OSCs recently.
2D materials Transmittance [%] Sheet resistance [Ω] Work function [eV] Device structure Ref.

Ti3C2Tx 68 – 84 26 − 5.28 MX@AgNW-PUA/PEDOT:PSS/PBDB-T:ITIC:PC71BM/PDINO/Al Tang et al., 2019

GR greater than 92 83 − 4.65 PI@GR/PEDOT:PSS/PM6:Y6/PDINO/Al Koo et al., 2020
GR 89 14 —— GR@AgNW/PEDOT:PSS/PTB7:PC71BM/Ba/Al Ricciardulli et al., 2018
N-GR 97.3 305 ± 17 − 4.03 PET/GR/ZnO-NP-AF/PTB7-Th:PC71BM/MoO3/Ag Jung et al., 2018
GO 87 18 —— PET/GO@AgNW/PEDOT:PSS/PTB7:PC71BM/LiF/Al Wang et al., 2017
GR 70 520 − 4.50 GR/PEDOT:PSS/PTB7:PC71BM/Ba/Al Ricciardulli et al., 2017
ITO-glass 79 – 83 15 − 4.80 —— Tang et al., 2019

This method can improved the quality of the interface between GR and
conductive substrate, which obtained a high optical transmittance
(92%) as well as low sheet resistance (Rs = 83 Ω/sq). It is attributed to
the fact that the GR prepared by Hummer’s method contains sp3- car­
bons and structural defects, which leads to a significant decrease in the
charge carrier mobility (Mahmoudi et al., 2018; Wang et al., 2011). PI
also enhanced thermal stability and durability by suppressing delami­
nation of GR under mechanical stress. It can be seen from flat-band
energy level diagram that PI@GR has an appropriate work function as
an electrode. The PI@GR-based OSCs with PM6:Y6 as active layer
showed a PCE of 15.2% with a short-circuit current density (JSC) of 25.8
mA/cm2, an open circuit voltage (VOC) of 0.84 V, and a fill factor (FF) of
70% (Fig. 2d-e), which was the highest efficiency reported for GR
electrode based flexible OSCs so far. The performance of PI/GR based
flexible devices is comparable to ITO based on control device, and
demonstrates outstanding mechanical durability during up to 10,000
bending cycles.
In 2011, a newly class of 2D transition metal carbides and/or nitrides
discovered by Gogotsi and W. Barsoum et al. (Naguib et al., 2011), called
“MXenes”, has attracted wide attention. At present, over 70 members of
different MAX phases have been discovered, which have shown great
promise in optoelectronic devices because of metallic conductivity, high
surface area as well as transparency in the visible range (Naguib et al.,
2014; Yu, L. et al., 2019). The general formula of MXenes is Mn+1XnTx,
where M is early transition metal, X denotes carbon or nitrogen, and T
represents the termination functional groups (–O, –OH, and –F). MXenes
are typically synthesized by selective etching of the “A” layers of MAX
phase using a hydrofluoric acid (Alhabeb et al., 2017). High electrical

623
Y. Zhao et al.
Fig. 2. (a) Schematic describing the two-step fabrication process of PI@GR. AFM topography image of (b) PI/GR and (c) PI@GR. Height profile is obtained from the
dashed line in the corresponding image. (d) J–V characteristics and (e) EQE spectra with integrated current density of OSCs. Reprinted with permission from (Koo
et al., 2020) Copyright 2020 Elsevier.
conductivity 2D MXenes have been used as additive and electrode in
PSCs (Guo et al., 2018; Yang, L. et al., 2019) and DSSCs (Chen, Y. et al.,
2019). The above research results found that MXenes materials signifi­
cantly affected the growth of perovskite grains and the conductivity of
complete solar cells devices.
In 2019, Ti3C2Tx MXene materials have been investigated as trans­
parent electrodes in flexible ternary OSCs by Chen et al. (Tang et al.,
2019). They prepared Ti3C2Tx/silver nanowire (AgNW) hybrid films as
transparent and flexible electrode by a simple and scalable solution-
processed method, achieving a high figure of merit (FOM = 162.49).
The Ti3C2Tx coating was applied via electrostatic interactions. It can be
concluded from tests such as atomic force microscopy (AFM) and
transmittance that the Ti3C2Tx/AgNW hybrid films exhibits low rough­
ness (Fig. 3b). Work function calculated by the ultraviolet photoelectron
spectroscopy (UPS) is − 5.28 eV, which matches well with corresponding
transport layer material. The transmittance of Ti3C2Tx/AgNW-PUA is
624
Solar Energy 218 (2021) 621–638
comparable to ITO and the sheet resistance value only is 26 Ω/sq when
the film thickness is 800 nm. It is reported that Ti3C2Tx/AgNW-PUA
films as TCEs of ternary flexible OSCs (Ti3C2Tx/AgNW-PUA/PEDOT:
PSS/PBDB-T:ITIC:PC71BM/PDINO/Al) obtained a PCE of 8.3% with a
JSC of 14.9 mA/cm2, an VOC of 0.88 V, and a FF of 63% (Fig. 3a), which
represented a breakthrough in flexible photovoltaic technology. Finally,
bending tests indicated that the flexible ternary OSCs capable of
retaining 84.6% of the original PCE after 1000 bending-unbending cy­
cles to a 5 mm bending radius (Fig. 3c-d), which showed that the Ti3C2Tx
material had excellent mechanical stability as an electrode.
Park group reported that annealing-free ZnO nanoparticles (ZnO-
NPs)
were integrated on the GR electrode surface and applied to the
inverted OSCs in 2018 (Jung et al., 2018). It turns out that this method
can boost the applicability of GR as TCEs in flexible OSCs, because
uniform ZnO-NPs coating can effectively improve the charge transfer
Y. Zhao et al. Solar Energy 218 (2021) 621–638

Fig. 3. (a) J − V characteristics of OSCs based on PBDB-T:ITIC:PC71BM with different conductive substrate. (b) Transmittance spectra of neat PUA, MXene-PUA,
AgNW-PUA, optimized MXene/AgNW-PUA and ITO-glass. (c) R/R0 of MXene/AgNW-PUA films as a function of bending and unbending cycles to a bending
radius of 5 mm. (d) Normalized PCE of flexible OSCs with MXene/AgNW-PUA transparent electrodes at different bending radii as a function of the number of bending
cycles. Reprinted with permission from (Tang et al.,2019) Copyright 2019 American Chemical Society.

from the active layer to electrode. The PCEs of the inverted PTB7-Th: 0.24 eV after the introduction of ZnO-NPs, which was attributed to
PC71BM-based OSCs using this TCE on the solid (ITO) and flexible (PET) successfully N-doping of GR by ZnO (Fig. 4c). After the mechanical
substrates are 8.2% and 7.4%, respectively (Fig. 4a). The corresponding bending test, the flexible inverted OSCs based on GR has a PCE of 7.4%
UPS data showed that the work function of GR was reduced by about and still retains over 80% (Fig. 4b), which is attributed to the perfect

Fig. 4. (a) J − V characteristics curves of OSCs based on PET and glass substrate (insert is the schematic of graphene-ZnO NPs). (b) Normalized PCE of PET/graphene
and PET/ITO devices (PTB7-Th:PC71BM) with bending cycles at a bending radius of 3 mm. (c) Cut-off (left) and onset (right) regions of UPS spectra from pristine
graphene, and graphene/ZnO-NP. Reprinted with permission from (Jung et al., 2018) Copyright 2018 American Chemical Society. (d) J–V characteristics of the OSCs
devices (inset is flexible AgNWs/EG-based OSCs). (e) Rs response of AgNWs and AgNWs/EG films on PEN substrate to different bending cycles. (f) Cross-sectional
SEM images of EG thin layer on the top of the AgNWs network. Reprinted with permission from (Ricciardulli et al., 2018) Copyright 2018 Wiley.

625
Y. Zhao et al. Solar Energy 218 (2021) 621–638

combination of GR with superior mechanical flexibility and annealing-
free ZnO-NPs (Jung et al., 2018).
In 2018, W. M. Blom et al. (Ricciardulli et al., 2018) reported a TCE
(AgNWs/EG) with chemical stability and excellent mechanical. The
AgNWs coupled electrochemical exfoliated grapheme (EG) obtained a
high transparency electrode with low-surface roughness (RMS = 4.6 nm)
and low sheet resistance (Rs = 13.7 Ω sq-1) (Ricciardulli et al., 2018). As
shown in Fig. 4d-f, EG can not only overcome the limitations of the
AgNWs network, but also reduce the sheet resistance and roughness of
materials. The AgNWs/EG films on PEN substrate as electrode has
excellent mechanical flexibility and maintains a very low Rs under
different bending cycles, which is significantly better than AgNWs alone.
The AgNWs/EG-based OSCs had a remarkable PCE of 6.57% (JSC = 15.5
mA/cm2, VOC = 0.73 V, FF = 58%), using PTB7:PC71BM as active layer,
comparable to the commercial ITO based counterparts. Madanipour
et al. (Fakharan et al., 2019) presented an iodine-mediated fine-tuning
method to prepare RGO/iodine based electrodes for ITO-free OSCs in
2019. They studied the effects of surface roughness and iodine (I) con­
tent on PCE, and found that low surface roughness and high I content
can reduce the device resistance. In 2017, W. M. Blom et al. (Ricciardulli
et al., 2017) and Kang et al. (Wang et al., 2017) successively reported the
application of solution-processable high-quality GR and graphene oxide
(GO)/AgNW in OSCs as electrodes, reaching PCEs with PTB7:PCB71M as
active layer of 4.23% and 7%, respectively.
2D layered materials used as electrodes in OSCs are mainly designed
to meet the commercial requirements of flexibility and semitransparent.
At present, high-efficiency OSCs with 2D materials as transparent
conductive electrodes have been demonstrated. 2D materials have better
adjustability and diversity compared with rigid ITO, have excellent
electrical conductivity. The replacement of ITO with 2D materials is
feasible in the near future. However, a more reliable and low-cost
scalable fabrication process for the uniform layer is needed to bring
2D materials to market, which is an urgent problem in the application of
2D materials in OSCs.
3.2. Interface modification layer (EEL and HEL)
Here, we regard the interface layer that assists and facilitates elec­
tron transport as electron extraction layer (EEL), which exists between
active layer or ETL and electrode (Xing et al., 2018). As an effective EEL,
the material must be of low work function and high electron mobility,
and could lower the work function of the cathode and transfer electrons
from the active layer to the cathode efficiently. Conversely, hole
extraction layer (HEL) is also defined in this way. Interface modification
is one of the important means to optimize the device structure. 2D
layered materials with fine morphology as an interface modification
layer play a significant role in promoting charge extraction and
injection.

Fig. 5. (a) Zoom-in HR–TEM image of the BP as indicated (inset shows the corresponding FFT image). (b) HR–TEM image of a BP showing layered structure. (c)
Inverted OSCs with BP incorporation under different conditions. Reprinted with permission from (Lin et al., 2016) Copyright 2016 Wiley. (d) HR–TEM image of
GMo2. (e) AFM image of GMo2 deposited on a mica substrate. (f) J–V characteristics of PTB7-Th:PC71BM OSCs based on PEDOT:PSS (black), GMo1(blue), GMo2
(cyan), and GMo3(green). Reprinted with permission from (Zheng et al., 2019) Copyright 2019 Elsevier. (g) TEM and (h) AFM images of MOF nanosheets. (i) J–V
characteristics based on PBDB-T:ITIC-Th. Reprinted with permission from (Xing et al., 2018) Copyright 2018 Elsevier. (For interpretation of the references to colour
in this figure legend, the reader is referred to the web version of this article.)

626
Y. Zhao et al.
Black phosphorus (BP) is a novel class of 2D semiconducting mate­
rial. At present, liquid-phase exfoliated BP nanoflakes (NFs) and quan­
tum dots (QDs) exhibit excellent performance in electronic, energy
storage, sensors, solar cells, and photonic devices etc. (Qiao et al., 2014;
Ren et al., 2017). The merits of high carrier mobility (≈1000 cm2 V− 1
s− 1), tunable direct band gap, and the intrinsic anisotropy arising from
the puckered structure makes it possible for BP to be used in OSCs
(Batmunkh et al., 2016). Whereas, its poor stability and high-density
charge traps largely limit further application and engineering opera­
tions in photovoltaic devices. The role of BP (QDs) in solar cells and
other photovoltaic devices has been summarized in detail (Bati et al.,
2019; Batmunkh et al., 2018; Lin et al., 2017; Pang et al., 2018).
In 2016, Lau et al. (Lin et al., 2016) firstly reported that solution
exfoliated layered BP can be served as an effective charge extraction
layers between active layer and charge transport layer in OSCs. The
optimum thickness of BP flakes prepared by ultrasonic-exfoliation
method was about 10 nm and the thickness of single atomic layer was
about 0.52 nm (Fig. 5a-b), which could construct cascaded band struc­
ture to boost charge transport and enhance the PCE of OSCs. BPNFs
sandwich between ZnO and PTB7:PC71BM in an inverted OSCs. BPNFs
was decorated on PEDOT:PSS or ZnO by spin-coating, and the thickness
of charge extraction layer was controlled by coated times. The UPS
spectra showed that different spin coating times could change the
valence band (VB) maximum of BP. The PCE of the optimized BP-
incorporated OSCs (PTB7:PC71BM) can be improved to 8.18% in
average with the relative enhancement of 11%. The optimal OSCs
reached a PCE of 8.25% at three times coating, with FF of 61%, VOC of
0.72 V, and JSC of 18.8 mA/cm2 (Fig. 5c). It was reported that the
improvement of device performance was attributed to the cascaded
energy level caused by BP. After two months, the stability of OSCs
introduced with BPNFs as a charge extraction layer has also been
improved, and PCE still remained at the initial 94%. These results
indicate that the emerging 2D material BP can be used in high perfor­
mance and stability OSCs as charge extraction layer.
At present, van der Waals heterostructures cannot be mass-produced,
which limit its wider application (Liu et al., 2016; Novoselov et al.,
2016). In 2019, Wang et al. (Zheng et al., 2019) successfully fabricated
GR/MoS2 heterostructures (G-MoS2) by liquid-exfoliated method and
hydrothermal reaction, which can be proved from the HRTEM image
(Fig. 5d-e). The work function of newly G-MoS2 heterostructures con­
taining oxygen-incorporated MoS2 was adjustable (Lopez-Sanchez et al.,
2013), which could remarkably enhance hole extraction efficiency be­
tween the electrode and active layer. From the impedance spectrum of
the device, it was found that G-MoS2 hybrid film obtained a series
resistance of 45 Ω and device resistance of 470 Ω. It turns out that the
GR-MoS2 heterostructure with high vertical conductivity as HEL boosts
charges transport at the interface, and consequently reduces carrier
recombination. They employ G-MoS2 hybrid thin film as the HEL to
improve hole transport in OSCs (ITO/G-MoS2/PEDOT:PSS/ P3HT:
PC71BM/Ca/Ag). G-MoS2-based device showed a maximum PCE of 9.5%
(JSC = 17.2 mA/cm2, VOC = 0.77 V, FF = 72%) (Fig. 5f), whilst retaining
more than 93% of the initial efficiency over a storage period of 1000 h.
The results represent the enormous potential of 2D heterostructures as
hole extraction materials for photovoltaic devices.
Metal organic frameworks (MOFs) nanoflakes are widely used in
various fields such as chemical separation and purification, optoelec­
tronics and sensing, etc., yet the exfoliation of 2D MOF nanoflakes is a
challenge (Peng et al., 2014; Rodenas et al., 2015). Huang et al. (Xing
et al., 2018) reported that a newly tellurophene-based 2D MOF (Te-
MOF) to fabricate single or multiple layer nanoflakes by exfoliating. The
stacked structure with a thickness of 2.7 nm and 1.3 nm thick single
nanoflakes were observed by AFM (Fig. 5g-i). The Te-MOF hybrid
dispersion solution is directly spin-coated onto ZnO as an EEL.
Compared to the polyethylenimine ethoxylate-based, the devices exhibit
enhanced PCE because of the tunable work function and high charge
carrier mobility characteristics. They introduced 2D-MOF to PBDB-T:
627
Solar Energy 218 (2021) 621–638
ITIC-Th-based OSCs, and obtained a PCE of 10.39% (JSC = 17.1 mA/
cm2, VOC = 0.86 V, FF = 71%). This work is one of the few attempts to
apply 2D MOF in OSCs (Fig. 5i).
3.3. HTL and ETL
As we all know, the work function of 2D material is tunable by
specific treatment methods (Table 3) (Ma et al., 2017). In 2019, Ouyang
et al. (Yu, Z. et al., 2019) obtained Ti3C2Tx films with various work
functions by changing the duration of special treatments. As can be seen
from the AFM image, a mono-layered Ti3C2Tx is about 2 nm thick. Ac­
cording to UPS spectra, the work function of Ti3C2Tx can be adjusted in
the range from 4.08 eV to 4.95 eV by UV-ozone (U-MXene) or N2H4 (UH-
MXene) treatment (Fig. 6c). Then they applied Ti3C2Tx with appropriate
work functions to PBDB-T:ITIC-based OSCs as HTL or ETL, and the OSCs
with Ti3C2Tx as ETL and HTL could show a PCE of 9.06% and 9.02%,
respectively. Different special treatments conditions of Ti3C2Tx can
affect the VOC of the device, so UVO and N2H4 treatment can change the
work function (Fig. 6a). When the UVO-treated Ti3C2Tx is used as the
ETL, the device structure is ITO/U-MXene/PBDB-T:ITIC/Ca/Al. The JSC
of 15.98 mA/cm2, the VOC of 0.89 V, and the FF of 64% were obtained,
similar to the commercial PEDOT:PSS-based hole transport material
(Fig. 6b). This is the first application of MXenes in OSCs. Thus, MXenes
have more promising applications in organic photovoltaic field.
PEDOT:PSS is the outstanding and commonly HTL material. Yet, it
easily corrodes ITO substrate or reacts with active layer, and its hygro­
scopicity is also detrimental to the stability of devices (Wang et al.,
2019). In 2020, to ameliorate the poor conductivity of PEDOT:PSS, Yu
et al. (Hou and Yu, 2020) doped solution-processable 2D layered Ti3C2Tx
into PEDOT:PSS to prepare organic–inorganic hybrid material, and
applied it in OSCs as HTL. The introduction of highly conductive Ti3C2Tx
nanosheets constructed additional interconnected transfer channels for
holes to enhance the efficient migration of carriers. In the other hand,
the electrostatic interaction between the functional groups of Ti3C2Tx
and PEDOT:PSS led to a conformational transition of polymer, which in
turn enhanced interchain charge transport (Fig. 6f). Hence, the incor­
poration of 2D Ti3C2Tx nanosheets obviously enhanced the conductivity
of PEDOT:PSS/Ti3C2Tx layer. In particular, the conductivity is 0.068 S/
cm when adding 0.20% Ti3C2Tx, which is much higher than that of
PEDOT:PSS (2.1 × 10-3 S/cm) alone (Fig. 6d). As expected, a PCE of 11%
was obtained for the PBDB-T:ITIC-based OSCs with PEDOT:PSS/
Ti3C2Tx, which was improved by 13.5% compared to control device
without Ti3C2Tx (9.7%). When using the PM6:Y6 blend as the active
layer, the PCE reached to 14.55%, and JSC was significantly improved.
Finally, the results showed that PEDOT:PSS/Ti3C2Tx-based devices also
had better long-term stability than control device without Ti3C2Tx added
(Fig. 6e).
Graphene and its derivatives are also widely used as the transport
material in solar cells (Liu et al., 2015). Of late, Li group (Pan et al.,
2019) added N-doped GR to PDINO to prepare a solution-processable
material (PDINO-G) as ETL in OSCs (Fig. 7a). In this work, they used
PDINO as the dispersant for GR to solve the issue that N-doped GR
prepared by CVD method had no solution processability. The results of
XPS and Raman showed that the source of N-doping was nitroxide
radical of N-oxide in PDINO. They optimized device performance by
adding different contents of GR to PDINO. From the electron spin
resonance (ESR) spectroscopy (Fig. 7c-d), it is concluded that the
nitroxide radical in the N-oxide intermolecularly transfer electrons to
graphene and N-doped GR. UPS data found that doping GR reduced the
highest occupied molecular orbital (HOMO) energy level of PDINO
(Zhou et al., 2012). As mentioned above, an ideal ETL material must be
of low work function and high electron mobility, and could lower the
work function of the cathode and transfer electrons from the active layer
to the cathode efficiently. Therefore, N doping can lower the work
function of GR, along with accelerating the charge transfer. Transient
photocurrent and transient photovoltage measurement data showed that
Y. Zhao et al. Solar Energy 218 (2021) 621–638

Table 3
The 2D materials are used as charge transport layers in OSCs recently.
2D material Function JSC [mA/cm2] VOC [V] FF [%] PCE [%] Device structure Ref.

BP E/HEL 18.78 0.72 61 8.25 ITO/ZnO/BP/PTB7:PC71BM/MoO3/Ag Lin et al., 2016

GR/MoS2 HEL 17.20 0.77 72 9.50 ITO/G-MoS2/PEDOT:PSS/P3HT:PC71BM/Ca/Ag Zheng et al., 2019
Te-MOF EEL 17.10 0.86 71 10.39 ITO/ZnO/MOF-PEIE/PTBD-T:ITIC-Th/MoO3/Ag Xing et al., 2018
Ti3C2Tx E/HTL 17.36 0.87 60 9.06 ITO/UH-MXene/PBDB-T:ITIC/MoO3/Al Yu et al., 2019
GR or GO E/HTL 25.65 0.85 76 16.52 ITO/PEDOT:PSS-GO/PM6:Y6/PDINO-G/Al Pan et al., 2019
GO HTL 18.07 0.92 73 13.13 ITO/ZnO/PBDB-T:IT-M/L-GO:NiOx/Ag Cheng et al., 2018
RGO ETL 18.61 0.78 65 9.49 ITO/IT-RGO/ZnO:IT-RGO/PTB7-Th:PC71BM/MoO3/Ag Zheng et al., 2017
GR HTL 13.63 0.48 68 4.52 TO/G-PEDOT:PSS/P3HT:PC61BM/Al Hilal and Han, 2019
RGO HTL 13.43 0.70 58 5.50 ITO/n-rGO/PTB7:PC71BM/PFN/FM Romero-Borja et al., 2018
F-RGO HTL 16.89 0.78 65 8.60 ITO/F-rGO/PTB7-Th:PC71BM/PFN/Al Cheng et al., 2017
GO HTL 8.14 0.80 42 2.73 ITO/GO/PCDTBT:PC71BM/Al Rafique et al., 2016
MoS2 HTL 9.02 0.67 62 3.14 ITO/PEDOT:PSS-FMoS2/P3HT:PC61BM/LiF/Al Ramasamy et al., 2019
MoS2 ETL 18.40 0.80 69 10.10 ITO/ZnO:MoS2/PTB7-Th:PC71BM/MoO3/Ag Huang et al., 2018
WS2 HTL 26.00 0.84 78 17.00 ITO/WS2/PM6:Y6:PC71BM/PFN-Br/Al Lin et al., 2019
Ti3C2Tx HTL 17.08 0.91 71 11.02 ITO/PEDOT:PSS@Ti3C2Tx/PBDB-T:ITIC/PFN-Br/Al Hou and Yu, 2020
α-In2Se3 HTL 16.69 0.88 65 9.58 ITO/α-In2Se3/PBDB-T:ITIC/Ca/Al Wang et al., 2019
WSe2 HTL 16.60 0.78 66 8.50 ITO/PEDOT:PSS-WSe2/PTB7:PC71BM/Al Koo et al., 2018
α-In2Se3 HTL 15.47 0.84 74 15.90 ITO/PEDOT:PSS@α-In2Se3/PM6:Y6/PDINO/Al Wang et al., 2020

Fig. 6. (a) Voc varies with the treatment duration. (b) J–V characteristics of PBDB-T:ITIC-based OSCs. (c) UPS spectra of bare ITO, PEDOT:PSS, and MXene thin films
untreated and treated with N2H4. Reprinted with permission from (Z. Yu et al., 2019) Copyright 2019 Royal Society of Chemistry. (d) The conductivities of the
PEDOT:PSS and PEDOT:PSS/Ti3C2TX films on bare glass (AFM image of single-layered Ti3C2TX flakes). (e) Stability of devices with different HTLs based on PBDB-T:
ITIC in a N2 glove box. (f) Schematic illustration of morphological and structural modifications in PEDOT:PSS with the incorporation of Ti3C2TX. Reprinted with
permission from (C. Hou et al., 2019) Copyright 2019 Royal Society of Chemistry.

the effective N-doping in PDINO-G resulted in enhancement of carrier
extraction efficiency. At the same time, the charge extraction time of the
device based on PDINO-G and PEDOT:PSS-GO is 0.34 μs, shorter than
the control device. The efficient charge extraction and longer carrier
lifetime remarkable improved the JSC (19.1 mA/cm2) and FF (74.9%) of
OSCs after the incorporation of GR. The PTQ10:IDIC-2F-based OSCs
with PDINO-G and PEDOT:PSS-GO as interface material showed the best
PCE of 13.01%, which was significantly improved in comparison with
that of the devices without GR modification in the PDINO (12.23%). As
shown in Fig. 7a, the results indicated that the device performance of
OSCs was greatly improved when GR was added to PNINO as ETL.
Notably, the single junction bulk heterojunction OSCs (PM6:Y6) with
PDINO-G as ETL demonstrated a high PCE of 16.52% (JSC = 25.65 mA/
cm2, VOC = 0.85 V, and FF = 76%).
For OSCs, the inverted device is more stable than the conventional.
C. H. Choy et al. published a self-assembled quasi-3D material as an
efficient HTL for inverted OSCs in 2018 (Cheng et al., 2018). It can be
divided into L-GO and H-GO according to the degree of oxidation. The
results showed that the dispersion of GO could be controlled by
changing the degree of oxidation to solve the shrinkage of self-
assembled material caused by highly oxidized GO. The XPS and FTIR
spectrum confirm the successful synthesis of GO, and Fig. 8a shows the
corresponding characteristic peaks of L-GO and H-GO. In this study, they
developed self-assembled quasi-3D nanocomposite and introduced
controllable hydrogen bonds between NiOx nanoparticles (NPs) and GO
nanosheets. GO is used as a support for NiOx NPs, and it also enhances
the conductivity and electron blocking ability of the transport layer. It is
worth noting that the conductivity of quasi-3D low oxidized graphene

628
Y. Zhao et al. Solar Energy 218 (2021) 621–638

Fig. 7. (a) J–V characteristics of the OSCs based on PM6:Y6 (Schematic diagram of graphene with different interfacial materials). (b) Transient photocurrent of the
devices based on PTQ10:IDIC-2F ESR spectra of (c) PDINO and PDINO-G with 5% graphene under OSCs device conditions and (d) PSO and PSO-G with 5% graphene.
Reprinted with permission from (Pan et al., 2019) Copyright 2019 Royal Society of Chemistry.

Fig. 8. (a) C1s XPS FTIR spectrum of GO. (b) PCE of inverted OSCs based on GO and L-GO:NiOx with different thicknesses (inset shows the cross-section SEM). (c)
Schematic illustration of quasi-3D GO:NiOx nanocomposite. Reprinted with permission from (Cheng et al., 2018) Copyright 2018 Wiley. (d) UV–vis spectra of various
ETL. (e) PTB7-Th:PC71BM OSCs with different ETL. (f) Schematic diagram of ITR/ITA process. Reprinted with permission from (Zheng et al., 2017) Copyright 2017
American Chemical Society.

(L-GO):NiOx was increased due to the breaking of the vertical conduc­
tivity limitation of traditional 2D materials. Overall, the champion OSCs
device (ITO/ZnO/PBDB-T:IT-M/HTL/Ag) obtained a PCE of 12.13%
(JSC = 18.07 mA/cm2, VOC = 0.92 V, FF = 73%), which was a 15%
improvement as compared control device (Fig. 8b-c). After 164 h in
ambient environment, the PCE of conventional device rapidly dropped
to 0 while the L-GO:NiOx-based device still remained 50% of its initial
value, so the stability of L-GO:NiOx-based device was also obviously
improved.
Generally, graphene and it is derivatives such as GO, reduced

629
Y. Zhao et al.
graphene oxide (R-GO) etc. have been proved as the promising additives
with ZnO to form ETL. In 2017, Yu et al. (Zheng et al., 2017) successfully
synthesized ZnO:R-GO hybrid material by utilizing dual-nozzle spray
coating system and applied it in inverted OSCs (Fig. 8f). This novel
method could precisely control the film thickness of the ETL, and
reduced GO to in-situ thermal reduced graphene oxide (IT-RGO) while
GO is assembled on ZnO. The conductivity values of GO, R-GO, and IT-
RGO are calculated as 2.12 × 10− 4 S/m, 7.33 × 10− 4 S/m, and 7.85 ×
10− 4 S/m, respectively. It is obvious that hybrid ZnO:IT-RGO exhibit a
better conductivity than the bare ZnO, due to the incorporation of highly
conductive IT-RGO. In addition, the light absorption intensity of ZnO:
GO and ZnO:IT-RGO were slightly increased in the visible region
compared with bare ZnO (Fig. 8d). The device based on IT-RGO/ZnO:IT-
RGO show higher conductivity of 7.17 × 10− 4 S/m than reference ZnO,
which is favorable for boosting electron transport and suppressing
charge recombination. The OSCs with ZnO:IT-RGO hybrid ETL and thin
IT-RGO baseplate exhibited the highest PCE of 9.49% (JSC = 18.4 mA/
cm2, VOC = 0.78 V, and FF = 65%) in PTB7-Th:PC71BM system (Fig. 8e),
which was higher than that using pristine ZnO (PCE = 8.02%). Similarly,
Han et al. (Hilal and Han, 2019) doped the pristine GR with PEDOT:PSS
to prepared a conductive polymer composite. They used this material as
the HTL of OSCs, which improved the performance of the device.
Thermally RGO implemented in air processed OSCs as HTL were
reported by Pérez-Gutiérrez et al. in 2018. (Romero-Borja et al., 2018)
RGO layers were fabricated via spin-deposition and thermal reduction of
GO after each deposition. A PCE of 5.5% was obtained with the device
structure of ITO/HTL/PTB7:PC71BM/PFN/FM, which was as high as
that for control devices based on PEDOT:PSS (Fig. 9a). Chen et al.
(Cheng et al., 2017) prepared a RGO film functionalized with fluorine
atoms as a HTL material for OSCs. The introduction of fluorine atoms
increased work function of GO due to high electronegativity. The result
shows C = C bonds in GO oxide after reduction enhances the conduc­
tivity of F-rGO compare to pure GO. Hence, the OSCs with F-rGO ob­
tained a PCE of 8.6%, along with long-term stability, and even superior
to the control device. In 2016, Sulaiman et al. (Rafique et al., 2016)
reported the solution-processable GO with varied concentration as HTL
for bulk heterojunction OSCs. This paper mainly discussed the influence
of HTL concentration and thickness on the whole device.
Similar to GR, 2D-TMDs can be synthesized in monolayer or few
layer morphologies by a physical or chemical method (Balis et al.,
Fig. 9. (a) OSCs parameters for each content of SPFG. Reprinted with permission from (Romero-Borja et al., 2018) Copyright 2018 Elsevier. (b) Device configuration
and crystal structure of α-In2Se3. Reprinted with permission from (Wang et al., 2019) Copyright 2019 Wiley. (c) Schematic representation of doping ZnO with MoS2
nanosheets. Reprinted with permission from ( Huang et al., 2018) Copyright 2018 American Chemical Society. (d) Device configuration and schematic of PEDOT:
PSS@α-In2Se3. Reprinted with permission from (Wang et al., 2020) Copyright 2020 American Chemical Society.
630
Solar Energy 218 (2021) 621–638
2016). 2D TMDs nanosheets also have been extensively studied and
applied to a variety of photovoltaic devices thanks to their fabulous
electrical and optical properties. It is found that lone pairs of electrons
on the surfaces of TMDs, the presence of non-covalent interaction and
dangling bonds could enhance their chemical stability (Gu et al., 2013;
Voiry et al., 2013; Wang et al., 2012). Hence, 2D TMDs nanosheets are
expected to solve the issue of instable OSCs. In nonfullerene-based OSCs,
the application of liquid-exfoliated 2D TMDs as the charge transport
layers has been reported. In 2019, Kim et al. reported oleylamine-
functionalized MoS2 (F-MoS2) nanoflakes by common solution-phase
exfoliation (Ramasamy et al., 2019). Subsequently, PEDOT:PSS/F-
MoS2 was prepared and used as a high-efficiency HTL for P3HT:PC61BM-
based OSCs. The results showed that the hybrid film has good compat­
ibility with others, and the OSCs with PEDOT:PSS/F-MoS2 obtained a
PCE of 3.74%.
Xie et al. introduced four hydroxy (–OH) groups into perylene bisi­
mide (PBI) to form PBI-OH ligands, which could complex Zn (II) ions
(PBI-OH:ZnO) after deprotonation (Wen et al., 2019). The PBI-OH:ZnO
hybrid film effectively promotes electron collection and transport.
However, the compatibility of the polymer with the inorganic transport
layer is not ideal. In 2018, Wei et al. (Yi-Jiun Huang et al., 2018) pre­
pared ZnO:MoS2 hybrid material by doping MoS2 nanoflakes into ZnO
sol–gel, which was used as ETL in OSCs based on PTB7-Th:PC71BM. It
turned out that varied amounts of MoS2 would change the energy band
structure of the ZnO:MoS2 hybrid film. It is found that doping a small
content of MoS2 into ZnO could optimize the morphology of transport
layer, and improved the FF (69%) and PCE (10.1%) of device (Fig. 9c).
Simultaneously, The charge mobility calculated by the space charge
limited current (SCLC) showed that the electron mobility (μe) increased
remarkably upon increasing the MoS2 content, and the highest value
(1.86 × 10-4 cm2 V-1s− 1) appeared when 0.5 wt% MoS2 is added (Blom
and Vissenberg, 2000). The surface defects of film decreased with the
MoS2 content increased, thereby improving the charge transfer and
reducing the leakage current. (Yi-Jiun Huang et al., 2018). Concretely,
the PTB7-Th:PC71BM-based OSCs with ZnO:MoS2 obtained a PCE of
10.1%, which was 15% higher than the control device. Similarly, Wei
et al. (Xie et al., 2019) also doped MoS2 QDs into ZnO to passivate
surface defects, aimed to promote electron extraction and suppress
charge recombination.
Recently, D. Anthopoulos et al. (Lin et al., 2019) published on the use
Y. Zhao et al.
of liquid–exfoliated WS2 and MoS2 as HTL to replace PEDOT:PSS in
high-efficiency OSCs. The results showed that both WS2 and MoS2 dis­
persions had high uniformity. (Lin et al., 2019). The AFM and trans­
mission electron microscopy (TEM) characterization showed that the
exfoliated nanoflakes of MoS2 were thicker than WS2 and easily formed
more multilayer flakes when spin-coated, which resulted in ITO/WS2
mainly consists of monolayer/bilayer sheets. The water/ethanol sus­
pensions of WS2 and MoS2 nanoflakes were dark yellow colloids, and
both showed similar UV absorption spectra (Fig. 10a). Obviously, the
HTL comprising WS2 has higher uniformity than MoS2 on ITO sub­
strates, hence the difference of local morphology can result in differ­
ences in the performance of the entire device. They studied liquid-
exfoliated WS2 and MoS2 as HTL in OSCs and comprehensively char­
acterized them. Device analysis showed that using WS2 as HTL in non-
fullerene-based OSCs could improve PCE. It is turned out that
although the work function of MoS2 was similar to WS2, the unevenness
of the MoS2 layer reduced the hole transport ability, resulting in carrier
recombination (Fig. 10b) (Lin et al., 2019). In Fig. 10c-d, OSCs based on
the ternary PM6:Y6:PC71BM with WS2 as the HTL showed the highest
PCE of 17% (JSC = 26 mA/cm2, VOC = 0.84 V, and FF = 78%). After
detailed characterization and analysis, it is shown that the significantly
enhanced PCE was most likely attributed to superb photonic structure,
high charge extraction efficiency and reduced bimolecular recombina­
tion losses. Finally, this work highlighted the potential of 2D TMDs as
low-cost HTLs for high-efficiency organic photovoltaics in the future.
In 2019, the use of solution-processable 2D α-In2Se3 prepared by
liquid-exfoliated method as an HTL in OSCs was reported by Yu et al.
(Wang et al., 2019). α-In2Se3 layer can boost hole transport efficiency
due to suitable work function, remarkable optoelectronic properties,
and smooth surface morphology. A high PCE of 9.58% was obtained
with the device structure of ITO/α-In2Se3/PBDB-T:ITIC/Ca/Al (Fig. 9b),
which was comparable to PEDOT:PSS-based device (9.50%). The hole
Fig. 10. (a) Absorption spectra of the as-prepared MoS2 and WS2 suspensions (inset image demonstrates the Tyndall effect in both WS2 and MoS2 dispersions). (b)
The work function of ITO and various HTLs deposited on ITO measured via the Kelvin Probe technique and calculated via the DFT method. (c) J–V and (d) EQE
characteristics of OSCs based on PBDB-T-2F:Y6 and PBDB-T-2F:Y6:PC71BM with different HTLs. Reprinted with permission from (Lin et al., 2019) Copyright
2019 Wiley.
631
Solar Energy 218 (2021) 621–638
mobility (μh) and JSC of α-In2Se3-OSCs are 3.44 × 10-4 cm2 V− 1 s− 1 and
16.69 mA/cm2, respectively. After long-term stability test in air envi­
ronment, it showed that α-In2Se3-based device could maintain half of
initial PCE after 48 h, while the control device dramatically decreased to
only 3.71% of its initial value. They concluded that the incorporation of
α-In2Se3 HTL obviously enhanced the long-term stability of OSCs. In
2018, in order to improve the charge transfer efficiency, Park et al. (Koo
et al., 2018) blended WSe2 and PEDOT:PSS as HTL for fullerene-based
OSCs.
In 2020, Yu et al. (Wang et al., 2020) also synthesized 2D α-In2Se3
nanoflakes with outstanding conductivity. They directly blended
different amounts of α-In2Se3 into PEDOT:PSS to prepare hybrid film
with superior transmittance and matched work function. Compared with
PEDOT:PSS, PEDOT:PSS@α-In2Se3 hybrid film as HTL has better con­
ductivity and hole selective ability. The incorporation of α-In2Se3
nanoflakes as physical linkers increased the interfacial contact area
between polymer chains and constructed more carrier transport
pathway. Moreover, α-In2Se3 and isopropyl alcohol/deionized water
synergistically produced a screening effect on PEDOT and PSS, which
led to the partial removal of PSS and the benzoid-quinoid transition of
PEDOT (Fig. 9d). When the doping concentration was 0.15 wt%, the
PBDB-T:ITIC-based OSCs device with PEDOT:PSS@α-In2Se3 obtained
the highest PCE (11.22%), which was mainly attributed to faster exciton
generation and charge exaction, as well as less charge recombination.
They fabricated PM6:Y6-based devices to explore the validity of PEDOT:
PSS@α-In2Se3 material. The optimized device reached an enhanced PCE
of 15.89%, with a JSC of 25.47 mA cm− 2, an VOC of 0.84 V, and a FF of
74%. Same as 2D α-In2Se3 for HTL (Wang et al., 2019), PEDOT:PSS@α-
In2Se3 also has better operation stability than PEDOT:PSS.
Y. Zhao et al.
3.4. Additives for active layer
Currently, the ternary OSCs has attracted intensive attention in the
OSCs filed owing to wide spectral absorption range and high charge
transfer efficiency (Duan et al., 2019; Fu et al., 2019; Gao et al., 2019;
Jin et al., 2019). The research on ternary devices has also became a hot
topic in the development of OSCs (Gasparini et al., 2019). It is reported
that the introduction of 2D materials as the third additive to OSCs could
effectively enhance device performance. 2D materials can broaden ab­
sorption range of spectrum of the active layer, enhance the light ab­
sorption ability, optimize the energy level matching, as well as improve
the morphological stability of the devices during the aging period
(Zhang et al., 2016). In 2017, Kymakis et al. (Stylianakis et al., 2017)
comprehensively reviewed the progress implemented by the application
of 2D materials in the field of blend BHJ ternary OSCs for the first time. It
was proved that 2D materials had great potential to be used in OSC as
additives. Herein, we summarized the application of promising 2D
materials as additives in OSCs recently.
In 2017, Yan et al. successfully proposed the utilization of black
phosphorus quantum dots (BPQDs) as an additive in OSCs to boost the
light harvesting (Liu et al., 2017). In this work, various sizes of BPQDs
were prepared by tuning the centrifugation rates. Assuming the expan­
sion of band levels of BPQDs is same, from the photoluminescence (PL)
spectral data, it can be estimated that the valence and conduction band
of BPQDs are 5.32 eV and 3.32 eV, respectively, and Eg is approximately
2 eV. The OSCs with PTB7:PC71BM as the active layer was optimized by
changing the nanosize and the amount of BPQDs. Significant
Fig. 11. (a) J–V characteristics of the best control device and the devices with various addition levels of BPQDs. (b) UV–vis absorption of PTB7:PC71BM layer with
the introduction of BPQDs of different sizes. Reprinted with permission from (Liu et al., 2017) Copyright 2017 Wiley. (c) Schematic of a BP/PCBM-based solar cell:
atomic structure of BP in layered stacking and the chemical structure of PCBM. Reprinted with permission from (Bai et al., 2017) Copyright 2017 Royal Society
of Chemistry.
632
Solar Energy 218 (2021) 621–638
improvement of PCE was obtained when BPQDs were added up to
0.055%, which was mainly attributed to the effect of strong light ab­
sorption and scattering of the BPQDs (Liu et al., 2017; Lu et al., 2013).
Simultaneously, it could be seen from Fig. 11b that BPQDs of different
nanosize also produced different degrees of light absorption and scat­
tering effects in the active layer. As a result, when 4.5 nm BPQDs were
added to the OSCs based on PBDTTT-EFT:PC71BM, the champion device
obtained a PCE of 10.1% with JSC of 19.3 mA/cm2, VOC of 0.76 V, and FF
of 69% (Fig. 11a). Interestingly, the weight percentage of BP added to
OSCs is much lower than that of organic additives, which is mainly
thanks to the unique 2D structural properties as well as the strong broad
band light absorption and scattering in active layers.
In 2017, Zhao et al. (Bai et al., 2017) successfully prepared solution
treated BP/PC61BM inorganic–organic hybrid heterojunction for OSCs.
In this study, they doped BP on the surface of the organic semiconductor,
and used the different morphologies of PC61BM to form various heter­
ostructures as active layer through different synthesis routes (Fig. 11c).
More importantly, BP/PC61BM makes the device have wider absorption
range spectrum and more suitable energy level matching, along with the
average PCE of the solar cells reach 6.4% and 8.0% using the hybrid with
the layered stacking and the doping-weaving structure. In order to fully
evaluate the photovoltaic performanc, the long-term thermal stability of
the two BP/PC61BM heterojunctions was tested in this work. The results
showed that devices with BP/PC61BM displayed excellent thermal sta­
bilities, and the PCE exhibited a decreasing tendency and dropped to
7.55% at 150 ◦ C on annealing for 3 days.
As we all know, 2D BP nanosheets are very expensive and hard to
Y. Zhao et al. Solar Energy 218 (2021) 621–638

prepare (Sun, Z. et al., 2015). However, Liu et al. produced BP from
inexpensive white phosphorus via a one-step solvothermal method
(Zhao et al., 2018). In this work, the 10 wt% BP prepared by the above
method was added to the PTB7-Th:PC71BM active layer, and the FF and
PCE of the OSCs reached an impressive 74.2% and 10.5%, respectively
(Fig. 12a). Compared with the binary devices without BP, PCE is
significantly improved by 20%, mainly due to the high charge mobility
of BP. Detailed characterization showed that despite the existence of
heterogeneity, BP had little effect on the phase separation and crystal­
linity of the active layer (Fig. 12b) (Bai et al., 2017; Lee et al., 2019;
Zhao et al., 2018), yet it still enhanced carrier migration.
Morphology of bulk heterojunction blend film is of great signifi­
cance. In 2019, Chen group used BP nanosheets as a morphology mod­
ifier and blended it with the active layer (PTB7-Th:IEICO-4F) (Yang, W.
et al., 2019a). The Raman spectrum presented three characteristic
peaks, confirming the successful preparation of BPNFs. The inverted
OSCs based on PTB7-Th:IEICO-4F blends incorporating with BP reached
a high FF (73%) and PCE (12.2%). They studied the morphological
thermal stability of device doped with BP by thermal treatment at 150 ◦ C
in glove box. Finally, the PCE still remained initial 73% after thermal
treatment for over 200 min, and the thermal stability was significantly
improved compared to the control device. Thus, they rationally
concluded that the embedded BP enhanced the morphological stability
of the OSCs by maintaining proper phase separation during the aging
period. Moreover, this work also embeded BP into other non-fullerene
systems for versatility testing. Applying BP to PBDB-T:ITIC system also
showed remarkable results, which demonstrated BP has been widely
used as morphology modifier in non-fullerene OSCs. Similarly, they also
used solution exfoliated few layers BP or WSe2 as third additives in
fullerene-based BHJ OSCs in 2019 (Yang, W. et al., 2019b). PL spectra
and EIS measurements revealed that BP and WSe2, as third additive,
obviously boosted the exciton dissociation and charge transfer. As a
result, the JSC of the device based on BP and WSe2 was enhanced from
16.36 mA/cm2 to 17.34 mA/cm2 (BP) and 17.54 mA/cm2 (WSe2), along
with slight improvement of VOC and FF, and stabilities were improved
for both BP and WSe2 devices. PTB7-Th:PC71BM-based OSCs with BP or
WSe2 as additive obtained PCE of 9.20% and 9.24%, respectively.
The 2D materials with different sizes would provide varied portions
of the basal plane, and it was expected that the nanoscale domains size of
the various components of the blend would significantly impact the
performance of the OSCs. Hence, the size distributions of 2D layered
materials affect the dispersion stability and morphological aggregation
of the BHJ layer, yet there is no substantive evidence on the interplay
between the size of 2D crystals and active layer. In 2019, Cho et al. (Kim
et al., 2019) used sonication method to fabricate different sizes of GO
and added it to active layer (PTB7:PC71BM). In this work, they studied
the mechanism of the effect of different 2D materials sizes on the per­
formance of the device. It is found that size-selected GO nanosheets
could boost charge transport and reduce non-geminate recombination
(Fig. 12e). The introduction of GO also improved the morphology of the
active layer greatly, and the FF of conventional and inverted devices
reached 70% and 69.4%, respectively (Fig. 12d). In 2018, Pérez-
Gutiérrez et al. (Romero-Borja et al., 2018) incorporated the function­
alized graphene (SPFG) as a third component in the active layer. They
prepared ternary active layers by blending SPFG with PTB7:PC71BM,
varying the amounts of SPFG to optimize the device. The results showed
that the optimal doping amount was 4 wt%, the enhancement in PCE for
a ternary system was 22% (PCE = 6.73%) compared to control device.
Similarly, A. Mahmoud et al. (Aïssa et al., 2018) doped GR nanoflakes
into P3HT:PC71BM as photoactive blended layers. The above experi­
mental results showed that the additive of GR enhanced light absorption
and promoted charge transfer.
2017, Bonaccorso et al. (Kakavelakis et al., 2017) found that the
performance of the device could be improved more effectively by
matching the size of 2D WSe2 crystals with that of the PC71BM domain in
active layer. As shown in schematic energy levels, WSe2 exhibited well
energy level matching and formed a cascaded band structure in ternary
OSCs (Fig. 12c). The OSCs device (ITO/PFN/PTB7:PC71BM:WSe2/

Fig. 12. (a) J–V characteristics of the OSCs based PTB7-Th:PC71BM@BP. (b) AFM height image for ternary film (inset is molecular structures of PTB7-Th, PC71BM,
and BP). Reprinted with permission from (Y. Zhao et al., 2019) Copyright 2018 Elsevier. (c) Schematic energy levels of the inverted devices. Reprinted with
permission from (Kakavelakis et al., 2017) Copyright 2017 American Chemical Society. (d) J − V characteristics of the PTB7:PC71BM inverted devices based on
photoactive layers prepared with various sized GO NSs, DIO, and NMP. (e) Hole and electron mobilities measured from SCLC devices. Reprinted with permission from
(Kim et al., 2019) Copyright 2019 American Chemical Society. (f) Energy level diagrams of hole − only and electron − only devices. Reprinted with permission from
(Ahmad et al., 2017) Copyright 2017 American Chemical Society.

633
Y. Zhao et al.
MoO3/Al) obtained PCE of 9.3%(JSC = 19.68 mA/cm2, VOC = 0.73 V, and
FF = 72%), which was 15% higher than standard binary devices (PCE =
8.1%). The improvement is mainly due to the enhanced exciton gener­
ation and dissociation at the WSe2-fullerene interface. In other work,
Srivastava et al. (Ahmad et al., 2017) incorporated the functionalized 2D
MoS2 into the ternary polymer solar cells to realize the long-range
ordering of polymer chains induced by 2D materials on charge trans­
port. The results showed that a synergic enhancement in JSC and FF of
MoS2 incorporated active layer led to an increase of about 32% in PCE
(3.7%) compared to control device. The higher electron mobility is
attributed to the highly conducting 2D network of MoS2 which provides
additional electron transport channels within the active layer (Fig. 12f).
It can be concluded from the above, both inorganic 2D materials and
organic non-fullerene acceptors have their own advantages and limita­
tions. In 2020, in order to combine advantages of both inorganic and
non-fullerene materials, Zhan et al. (Wang, Y. et al., 2020) applied
perovskite quantum dots (PQDs) in non-fullerene-based OSCs (Fig. 13).
CsPbI3 QDs was added to PTB7-Th:FOIC as the third additive, and the
JSC of OSCs devices significantly increased from 23.8 mA/cm2 to 25.0
mA/cm2. From the experimental data measured by the time-resolved
photoluminescence (TRPL), the average decay time of the blend film
with PQDs was 0.707 ns, which was shorter than the blend film without
PQDs (0.858 ns). It indicated faster charge transfer and exciton sepa­
ration, which could be partly due to the formation of a cascade energy
alignment in the PQDs hybrid blend. In addition, it was found that
nonradiative recombination voltage loss was reduced by measuring the
external quantum efficiency (EQEEL) of solar cells with CsPbI3 QDs. The
nonradiative energy loss of OSCs with CsPbI3 was only 0.295 eV, mainly
due to the strong fluorescence of QDs. Finally, the PCE of PM6:Y6-based
OSCs with CsPbI3 QDs (ITO/ZnO/PM6:Y6@PQDs/MoO3/Ag) reached
the highest 16.8%, similar to the record PCE of the perovskite QDCSs
(16.6%) (Hao et al., 2020). Perovskite materials could also be prepared
into 2D structures, so it might have broad application prospects in OSCs.
Fig. 13. (a) Energy level diagram of PTB7-Th:FOIC:PQDs. (b) TRPL spectra of PTB7-Th:FOIC blends with or without PQDs. (c) J–V and (d) EQEEL curves of PTB7-Th:
FOIC-based cells with or without PQDs (inset is HR–TEM image of PQDs). Reprinted with permission from (Wang et al., 2020) Copyright 2020 Wiley.
634
Solar Energy 218 (2021) 621–638
The incorporation of 2D materials as the third additive to the active
layer can generate improvements and synergetic effects such as the
improved crystallinity of the polymer, more effective carrier migration,
and the enhanced light trapping ability. Besides, 2D layered materials
produce energy cascade effect to promote charge transfer in the active
layer. However, introducing 2D materials in active layer complicates the
operational principle and increases the thickness, which increases the
cost of industrialization. At the same time, it is unclear to explain how
2D materials affect the crystallinity and interface morphology of the
active layer. In conclusion, the incorporation of the unique properties of
2D layered materials inside the active layer opens up a promising
pathway in the design and construction of high effective and low-cost
solar cells.
4. Conclusion and outlook
Herein, the developments of the OSCs based on different emerging
2D layered materials were summarized. We explored the role of these 2D
materials in OSCs through their own upsides by sorting out the above
work. It turns out that the incorporation of 2D materials to device shows
enormous and efficient effect on operating stability and performance of
OSCs. Moreover, 2D materials are used in different components of OSCs
due to excellent transport characteristics and high tunability in struc­
ture. 2D materials can be solution-processed like organic polymers to
prepare uniform thin films, so they can effectively modify and optimize
the interface of the device structure, which is of great significance for
reducing future commercial manufacturing costs (Table 4) (Garg et al.,
2016; Qin et al., 2014).
Despite the obvious upsides of 2D materials, there are still many
challenges to be solved in the application of OSCs. It can be seen from
the currently published articles that the nanoscale and number of layers
of 2D materials determine their optical and electronic properties, which
have different effects on photovoltaic devices. Currently, the reported
Y. Zhao et al. Solar Energy 218 (2021) 621–638

Table 4 efficient and stable large-area OSCs.

The best-performing OSCs employing emerging 2D materials.
Materials JSC VOC FF PCE Device structure Declaration of Competing Interest
&Function [mA/ [V] [%] [%]
cm2] The authors declare that they have no known competing financial
BP—additive 23.44 0.71 70 12.20 ITO/ZnO/PTB7-Th: interests or personal relationships that could have appeared to influence
IEICO-4F@BPNFs/ the work reported in this paper.
MoO3/Ag
Ti3C2Tx—E/HTL 17.36 0.87 60 9.06 ITO/UH-MXene/
PBDB-T:ITIC/MoO3/ Acknowledgements
Al
Ti3C2Tx—electrode 14.84 0.88 63 8.30 MX@AgNW-PUA/ The authors are deeply grateful to the National Key Research and
PEDOT:PSS/PBDB-T: Development Program of China (2019YFC0312101), Natural Science
ITIC:PC71BM/PDINO/
Al
Foundation of Shandong Province (ZR2018MEM023), the Fundamental
Te-MOF—EEL 17.10 0.86 71 10.39 ITO/ZnO/MOF-PEIE/ Research Funds for Central Universities (201822002), State Key Labo­
PTBD-T:ITIC-Th/ ratory of Marine Coatings (GZ-19-0002) and Open Fund of the State Key
MoO3/Ag Laboratory of Luminescent Materials and Devices (South China Uni­
GR—electrode 25.80 0.85 70 15.20 PI@GR/PEDOT:PSS/
versity of Technology, 2021-skllmd-11). The authors also thank Miss
PM6:Y6/PDINO/Al
GR/MoS2—HTL 17.20 0.77 72 9.50 ITO/G-MoS2/PEDOT: Xiaojie Liu for her critical reading of the manuscript.
PSS/P3HT:PC71BM/
Ca/Ag References
N-GR—ETL 25.65 0.85 76 16.52 ITO/PEDOT:PSS-GO/
PM6:Y6/PDINO-G/Al Aïssa, B., Nedil, M., Kroeger, J., Ali, A., Isaifan, R.J., Essehli, R., Mahmoud, K.A., 2018.
WS2—HTL 26.00 0.84 78 17.00 ITO/WS2/PM6:Y6: Graphene nanoplatelet doping of P3HT:PCBM photoactive layer of bulk
PC71BM/PFN-Br/Al heterojunction organic solar cells for enhancing performance. Nanotechnology 29,
PQDs—additive 27.20 0.84 73 16.60 ITO/PEDOT:PSS/ 105405.
PM6:Y6@PQDs/ Ahmad, R., Srivastava, R., Yadav, S., Chand, S., Sapra, S., 2017. Functionalized 2D-MoS2-
PDINO/Al incorporated polymer ternary solar cells: role of nanosheet-induced long-range
ordering of polymer chains on charge transport. ACS Appl. Mater. Interfaces 9,
34111–34121.
Alhabeb, M., Maleski, K., Anasori, B., Lelyukh, P., Clark, L., Sin, S., Gogotsi, Y., 2017.
preparation methods have problems such as low-yield, high-cost,
Guidelines for synthesis and processing of two-dimensional titanium carbide
complicated preparation, and uncontrollable morphology, etc., which (Ti3C2Tx MXene). Chem. Mater. 29, 7633–7644.
severely limit the further application of 2D materials. So the preparation Ares, P., Aguilar-Galindo, F., Rodriguez-San-Miguel, D., Aldave, D.A., Diaz-Tendero, S.,
Alcami, M., Martin, F., Gomez-Herrero, J., Zamora, F., 2016. Mechanical isolation of
of high-quality 2D materials with high-yield, controllable layer size, and
highly stable antimonene under ambient conditions. Adv. Mater. 28, 6332–6336.
number is one of the problem to be solved urgently. In addition, some Ayari, A., Cobas, E., Ogundadegbe, O., Fuhrer, M.S., 2007. Realization and electrical
materials are unstable in ambient conditions and could be oxidized characterization of ultrathin crystals of layered transition-metal dichalcogenides.
easily. For example, the instability of BP is a drawback that hinders its J. Appl. Phys. 101, 014507.
Bai, L., Sun, L., Wang, Y., Liu, Z., Gao, Q., Xiang, H., Xie, H., Zhao, Y., 2017. Solution-
further application in optoelectronics (Sun, J. et al., 2015; Zhang et al., processed black phosphorus/PCBM hybrid heterojunctions for solar cells. J. Mater.
2018). At present, the protection of easily oxidizable 2D materials can be Chem. A 5, 8280–8286.
achieved by preparing ternary heterostructures of type A-B-C (B is un­ Balis, N., Stratakis, E., Kymakis, E., 2016. Graphene and transition metal dichalcogenide
nanosheets as charge transport layers for solution processed solar cells. Mater. Today
stable material) (Deng et al., 2014; Liu, X. et al., 2019). Currently, the 19, 580–594.
heterostructure of the 2D material combination as transport materials Bati, A.S.R., Batmunkh, M., Shapter, J.G., 2019. Emerging 2D layered materials for
has good applications in lithium batteries, PSCs, and other optoelec­ perovskite solar cells. Adv. Energy Mater. 10, 1902253.
Batmunkh, M., Bat-Erdene, M., Shapter, J.G., 2016. Phosphorene and phosphorene-based
tronics (Liu, F. et al., 2019; Qin et al., 2014). But this kind of nano­ materials-prospects for future applications. Adv. Mater. 28, 8586–8617.
composites with complicated structure would increase the Batmunkh, M., Bat-Erdene, M., Shapter, J.G., 2018. Black phosphorus: synthesis and
manufacturing cost. More importantly, 2D materials and device com­ application for solar cells. Adv. Energy Mater. 8, 1701832.
Blom, P.W.M., Vissenberg, M.C.J.M., 2000. Charge transport in poly(p-phenylene
ponents must have certain solvent compatibility during the preparation
vinylene) light-emitting diodes. Mater. Sci. Eng. 27, 52–94.
of OSCs. This is the key to restrict the application of 2D materials in the Bonaccorso, F., Sun, Z., Hasan, T., Ferrari, A.C., 2010. Graphene photonics and
active layer, because 2D materials is hard to be incorporated into OSCs optoelectronics. Nat. Photonics 4, 611–622.
Brus, V.V., Lee, J., Luginbuhl, B., Ko, S.J., Bazan, G.C., Nguyen, T.Q., 2019. Solution-
uniformly. In the laboratory, 2D materials are usually introduced into
processed semitransparent organic photovoltaics: from molecular design to device
the device by spin coating, but a number of voids or small holes are performance. Adv. Mater. 31, 1900904.
generated, which reduces the quality of interface. It is reported that this Chen, L., Chen, W.L., Wang, X.L., Li, Y.G., Su, Z.M., Wang, E.B., 2019a. Polyoxometalates
problem can be solved by increasing the number of layers, but it sacri­ in dye-sensitized solar cells. Chem. Soc. Rev. 48, 260–284.
Chen, X., Xu, G., Zeng, G., Gu, H., Chen, H., Xu, H., Yao, H., Li, Y., Hou, J., Li, Y., 2020.
fices transparency of the device. 2D layered materials enhance light Realizing ultrahigh mechanical flexibility and >15% efficiency of flexible organic
absorption by physically scattering, but it does not help the active layer solar cells via a “welding” flexible transparent electrode. Adv. Mater. 32, 1908478.
broaden the absorption wavelength range, so broadening its own light Chen, Y., Wang, D., Lin, Y., Zou, X., Xie, T., 2019b. In suit growth of CuSe nanoparticles
on MXene (Ti3C2) nanosheets as an efficient counter electrode for quantum dot-
absorption range is also one of the key challenges. Recent research has sensitized solar cells. Electrochim. Acta 316, 248–256.
shown that 2D layered materials had a significant effect on improving Cheng, J., Zhang, H., Zhao, Y., Mao, J., Li, C., Zhang, S., Wong, K.S., Hou, J., Choy, W.C.
the efficiency of OSCs by enhancing the operational stability of equip­ H., 2018. Self-assembled quasi-3D nanocomposite: a novel p-Type hole transport
layer for high performance inverted organic solar cells. Adv. Funct. Mater. 28,
ment. Therefore, exploring the mechanism by which 2D materials 1706403.
enhance the stability of the active layer is also a critical point. Cheng, X., Long, J., Wu, R., Huang, L., Tan, L., Chen, L., Chen, Y., 2017. Fluorinated
It has been proved that although 2D layered materials have shown reduced graphene oxide as an efficient hole-transport layer for efficient and stable
polymer solar cells. ACS Omega 2, 2010–2016.
great potential in OSCs. There is still room for improvement. With the
Choi, Y.-Y., Choi, K.-H., Lee, H., Lee, H., Kang, J.-W., Kim, H.-K., 2011. Nano-sized Ag-
advent of the latest 2D materials such as blue phosphorus (Zhuang et al., inserted amorphous ZnSnO3 multilayer electrodes for cost-efficient inverted organic
2018), antimonene (Ares et al., 2016), and borophene (Mannix et al., solar cells. Sol. Energy Mat. Sol. C. 95, 1615–1623.
Cui, D., Wang, Y., Han, L., 2020a. China’s progress of perovskite solar cells in 2019. Sci.
2018), and they will also play a significant role in OSCs. It is considered
Bull. 65, 1306–1315.
that when the reliable and low-cost preparation technology of 2D ma­ Cui, Y., Wang, Y., Bergqvist, J., Yao, H., Xu, Y., Gao, B., Yang, C., Zhang, S., Inganäs, O.,
terials is mature, they can effectively promote the commercialization of Gao, F., Hou, J., 2019. Wide-gap non-fullerene acceptor enabling high-performance
organic photovoltaic cells for indoor applications. Nat. Energy 4, 768–775.

635
Y. Zhao et al.
Cui, Y., Yao, H., Zhang, J., Xian, K., Zhang, T., Hong, L., Wang, Y., Xu, Y., Ma, K., An, C.,
He, C., Wei, Z., Gao, F., Hou, J., 2020b. Single-junction organic photovoltaic cells
with approaching 18% efficiency. Adv. Mater. 32, 1908205.
Díez-Pascual, A.M., Luceño Sánchez, J.A., Peña Capilla, R., García Díaz, P., 2018. Recent
developments in graphene/polymer nanocomposites for application in polymer solar
cells. Polymers 10, 217–239.
Deng, Y., Luo, Z., Conrad, N.J., Liu, H., Gong, Y., Najmaei, S., Ajayan, P.M., Lou, J.,
Xu, X., Ye, P.D., 2014. Black phosphorus monolayer MoS2 van der Waals
heterojunction p-n diode. ACS Nano 8, 8298–8299.
Duan, C., Peng, Z., Colberts, F.J.M., Pang, S., Ye, L., Awartani, O.M., Hendriks, K.H.,
Ade, H., Wienk, M.M., Janssen, R.A.J., 2019. Efficient thick-film polymer solar cells
with enhanced fill factors via increased fullerene loading. ACS Appl. Mater.
Interfaces 11, 10794–10800.
Eswaraiah, V., Zeng, Q., Long, Y., Liu, Z., 2016. Black phosphorus nanosheets: synthesis,
characterization and applications. Small 12, 3480–3502.
Fakharan, Z., Naji, L., Madanipour, K., 2019. Surface roughness regulation of reduced-
graphene oxide/iodine-based electrodes and their application in polymer solar cells.
J. Collid Interf. Sci. 540, 272–284.
Fan, B., Zeng, Z., Zhong, W., Ying, L., Zhang, D., Li, M., Peng, F., Li, N., Huang, F.,
Cao, Y., 2019. Optimizing microstructure morphology and reducing electronil Losses
in 1 cm2 polymer solar cells to achieve efficiency over 15%. ACS Energy Lett. 4,
2466–2472.
Fu, H., Li, C., Bi, P., Hao, X., Liu, F., Li, Y., Wang, Z., Sun, Y., 2019. Efficient ternary
organic solar cells enabled by the integration of nonfullerene and fullerene acceptors
with a broad composition tolerance. Adv. Funct. Mater. 29, 1807006.
Gao, J., Ming, R., An, Q., Ma, X., Zhang, M., Miao, J., Wang, J., Yang, C., Zhang, F., 2019.
Ternary organic solar cells with J71 as donor and alloyed acceptors exhibiting
13.16% efficiency. Nano Energy 63, 103888.
Garg, R., Elmas, S., Nann, T., Andersson, M.R., 2016. Deposition methods of graphene as
electrode material for organic solar cells. Adv. Energy Mater. 7, 1601393.
Gasparini, N., Salleo, A., McCulloch, I., Baran, D., 2019. The role of the third component
in ternary organic solar cells. Nat. Rev. Mater. 4, 229–242.
Girotto, C., Voroshazi, E., Cheyns, D., Heremans, P., Rand, B.P., 2011. Solution-processed
MoO3 thin films as a hole-injection layer for organic solar cells. ACS Appl. Mater.
Interfaces 3, 3244–3247.
Gu, X., Cui, W., Li, H., Wu, Z., Zeng, Z., Lee, S.-T., Zhang, H., Sun, B., 2013. A solution-
processed hole extraction layer made from ultrathin MoS2 nanosheets for efficient
organic solar cells. Adv. Energy Mater. 3, 1262–1268.
Guo, Z., Gao, L., Xu, Z., Teo, S., Zhang, C., Kamata, Y., Hayase, S., Ma, T., 2018. High
electrical conductivity 2D MXene serves as additive of perovskite for efficient solar
cells. Small 14, 1802738.
Hilal, M., Han, J.I., 2019. Enhancing the photovoltaic characteristics of organic solar
cells by introducing highly conductive graphene as a conductive platform for a
PEDOT:PSS anode interfacial layer. J. Mater. Sci-Mater. El. 30, 6187–6200.
Hou, C., Yu, H., 2020. Modifying the nanostructures of PEDOT:PSS/Ti3C2TX composite
hole transport layers for highly efficient polymer solar cells. J. Mater. Chem. C 8,
4169–4180.
Jin, Y., Zhang, Y., Liu, Y., Xue, J., Li, W., Qiao, J., Zhang, F., 2019. Limitations and
perspectives on triplet-material-based organic photovoltaic devices. Adv. Mater. 31,
1900690.
Jung, S., Lee, J., Seo, J., Kim, U., Choi, Y., Park, H., 2018. Development of annealing-free
solution-processable inverted organic solar cells with N-doped graphene electrodes
using zinc oxide nanoparticles. Nano Lett. 18, 1337–1343.
Kakavelakis, G., Del Rio Castillo, A.E., Pellegrini, V., Ansaldo, A., Tzourmpakis, P.,
Brescia, R., Prato, M., Stratakis, E., Kymakis, E., Bonaccorso, F., 2017. Size-tuning of
WSe2 flakes for high efficiency inverted organic solar cells. ACS Nano 11,
3517–3531.
Kim, J.H., Sin, D.H., Kim, H., Jo, S.B., Lee, H., Han, J.T., Cho, K., 2019. Improved charge
transport and reduced non-geminate recombination in organic solar cells by adding
size-selected graphene oxide nanosheets. ACS Appl. Mater. Interfaces 11,
20183–20191.
Koo, D., Jung, S., Oh, N.K., Choi, Y., Seo, J., Lee, J., Kim, U., Park, H., 2018. Improved
charge transport via WSe2-mediated hole transporting layer toward efficient organic
solar cells. Semicond. Sci. Tech. 33, 125020.
Koo, D., Jung, S., Seo, J., Jeong, G., Choi, Y., Lee, J., Lee, S.M., Cho, Y., Jeong, M., Lee, J.,
Oh, J., Yang, C., Park, H., 2020. Flexible organic solar cells over 15% efficiency with
polyimide-integrated graphene electrodes. Joule 4, 1021–1034.
Lee, J., Lee, S.M., Chen, S., Kumari, T., Kang, S.H., Cho, Y., Yang, C., 2019. Organic
photovoltaics with multiple donor-acceptor pairs. Adv. Mater. 31, 1804762.
Li, F., Shen, T., Wang, C., Zhang, Y., Qi, J., Zhang, H., 2020a. Recent advances in strain-
induced piezoelectric and piezoresistive effect-engineered 2D semiconductors for
adaptive electronics and optoelectronics. Nano-Micro Lett. 12, 106–150.
Li, J., Wang, N., Wang, Y., Liang, Z., Peng, Y., Yang, C., Bao, X., Xia, Y., 2020b. Efficient
inverted organic solar cells with a thin natural biomaterial L-Arginine as electron
transport layer. Sol. Energy 196, 168–176.
Li, Z., Ying, L., Zhu, P., Zhong, W., Li, N., Liu, F., Huang, F., Cao, Y., 2019. A generic
green solvent concept boosting the power conversion efficiency of all-polymer solar
cells to 11%. Energy Environ. Sci. 12, 157–163.
Lin, S., Chui, Y., Li, Y., Lau, S.P., 2017. Liquid-phase exfoliation of black phosphorus and
its applications. FlatChem 2, 15–37.
Lin, S., Liu, S., Yang, Z., Li, Y., Ng, T.W., Xu, Z., Bao, Q., Hao, J., Lee, C.-S., Surya, C.,
Yan, F., Lau, S.P., 2016. Solution-processable ultrathin black phosphorus as an
effective electron transport layer in organic photovoltaics. Adv. Funct. Mater. 26,
864–871.
Lin, Y., Adilbekova, B., Firdaus, Y., Yengel, E., Faber, H., Sajjad, M., Zheng, X., Yarali, E.,
Seitkhan, A., Bakr, O.M., El-Labban, A., Schwingenschlogl, U., Tung, V.,
636
Solar Energy 218 (2021) 621–638
McCulloch, I., Laquai, F., Anthopoulos, T.D., 2019. 17% efficient organic solar cells
based on liquid exfoliated WS2 as a replacement for PEDOT:PSS. Adv. Mater. 31,
1902965.
Lin, Y., Wang, J., Zhang, Z.G., Bai, H., Li, Y., Zhu, D., Zhan, X., 2015. An electron
acceptor challenging fullerenes for efficient polymer solar cells. Adv. Mater. 27,
1170–1174.
Meng, L., Zhang, Y., Wan, X., Li, C., Zhang, X., Wang, Y., Ke, X., Xiao, Z., Ding, L., Xia, R.,
Yip, H.-L., Cao, Y., Chen, Y., 2018. Organic and solution-processed tandem solar cells
with 17.3% efficiency. Science 361, 1094–1098.
Liu, F., Shi, R., Wang, Z., Weng, Y., Che, C.M., Chen, Y., 2019a. Direct Z-scheme hetero-
phase junction of blackred phosphorus for photocatalytic water splitting. Angew.
Chem. Int. Ed. 58, 11791–11795.
Liu, G., Jia, J., Zhang, K., Jia, X.e., Yin, Q., Zhong, W., Li, L., Huang, F., Cao, Y., 2019.
15% Efficiency tandem organic solar cell based on a novel highly efficient wide-
bandgap nonfullerene acceptor with low energy loss. Adv. Energy Mater. 9,
1803657.
Liu, Q., Jiang, Y., Jin, K., Qin, J., Xu, J., Li, W., Xiong, J., Liu, J., Xiao, Z., Sun, K.,
Yang, S., Zhang, X., Ding, L., 2020. 18% efficiency organic solar cells. Sci. Bull. 65,
272–275.
Liu, S., Lin, S., You, P., Surya, C., Lau, S.P., Yan, F., 2017. Black phosphorus quantum
dots used for boosting light harvesting in organic photovoltaics. Angew. Chem. Int.
Ed. 56, 13717–13721.
Liu, X., Balla, I., Sangwan, V.K., Usta, H., Facchetti, A., Marks, T.J., Hersam, M.C., 2019c.
Ultrahigh vacuum self-assembly of rotationally commensurate C8-BTBT/MoS2/
graphene mixed-dimensional heterostructures. Chem. Mater. 31, 1761–1766.
Liu, Y., Weiss, N.O., Duan, X., Cheng, H.-C., Huang, Y., Duan, X., 2016. Van der Waals
heterostructures and devices. Nat. Rev. Mater. 1, 16042.
Liu, Z., Lau, S.P., Yan, F., 2015. Functionalized graphene and other two-dimensional
materials for photovoltaic devices: device design and processing. Chem. Soc. Rev.
44, 5638–5679.
Lopez-Sanchez, O., Lembke, D., Kayci, M., Radenovic, A., Kis, A., 2013. Ultrasensitive
photodetectors based on monolayer MoS2. Nat. Nanotechnol. 8, 497–501.
Lu, C., Yang, L., Yan, B., Sun, L., Zhang, P., Zhang, W., Sun, Z., 2020. Nitrogen-doped
Ti3C2 MXene: mechanism investigation and electrochemical analysis. Adv. Funct.
Mater., 2000852.
Lu, L., Xu, T., Chen, W., Lee, J.M., Luo, Z., Jung, I.H., Park, H.I., Kim, S.O., Yu, L., 2013.
The role of N-doped multiwall carbon nanotubes in achieving highly efficient
polymer bulk heterojunction solar cells. Nano Lett. 13, 2365–2369.
Lu, S., Li, F., Zhang, K., Zhu, J., Cui, W., Yang, R., Yu, L., Sun, M., 2020b. Halogenation
on terminal groups of ITIC based electron acceptors as an effective strategy for
efficient polymer solar cells. Sol. Energy 195, 429–435.
Ma, Y., Shen, C., Zhang, A., Chen, L., Liu, Y., Chen, J., Liu, Q., Li, Z., Amer, M.R.,
Nilges, T., Abbas, A.N., Zhou, C., 2017. Black phosphorus field-effect transistors with
work function tunable contacts. ACS Nano 11, 7126–7133.
Mahmoudi, T., Wang, Y., Hahn, Y.-B., 2018. Graphene and its derivatives for solar cells
application. Nano Energy 47, 51–65.
Mannix, A.J., Zhang, Z., Guisinger, N.P., Yakobson, B.I., Hersam, M.C., 2018. Borophene
as a prototype for synthetic 2D materials development. Nat. Nanotechnol. 13,
444–450.
Meng, X., Zhang, L., Xie, Y., Hu, X., Xing, Z., Huang, Z., Liu, C., Tan, L., Zhou, W., Sun, Y.,
Ma, W., Chen, Y., 2019. A general approach for lab-to-manufacturing translation on
flexible organic solar cells. Adv. Mater. 31, 1903649.
Naguib, M., Kurtoglu, M., Presser, V., Lu, J., Niu, J., Heon, M., Hultman, L., Gogotsi, Y.,
Barsoum, M.W., 2011. Two-dimensional nanocrystals produced by exfoliation of
Ti3AlC2. Adv. Mater. 23, 4248–4253.
Naguib, M., Mochalin, V.N., Barsoum, M.W., Gogotsi, Y., 2014. MXenes: a new family of
two-dimensional materials. Adv. Mater. 26, 992–1005.
Naveed, H.B., Zhou, K., Ma, W., 2019. Interfacial and bulk nanostructures control loss of
charges in organic solar cells. Acc. Chem. Res. 52, 2904–2915.
Novoselov, K.S., Mishchenko, A., Carvalho, A., Castro Neto, A.H., 2016. 2D materials and
van der Waals heterostructures. Science 353, 461–472.
Pan, F., Sun, C., Li, Y., Tang, D., Zou, Y., Li, X., Bai, S., Wei, X., Lv, M., Chen, X., Li, Y.,
2019. Solution-processable n-doped graphene-containing cathode interfacial
materials for high-performance organic solar cells. Energy Environ. Sci. 12,
3400–3411.
Pang, J., Bachmatiuk, A., Yin, Y., Trzebicka, B., Zhao, L., Fu, L., Mendes, R.G.,
Gemming, T., Liu, Z., Rummeli, M.H., 2018. Applications of phosphorene and black
phosphorus in energy conversion and storage devices. Adv. Energy Mater. 8,
1702093.
Peng, Y., Li, Y., Ban, Y., Jin, H., Jiao, W., Liu, X., Yang, W., 2014. Metal-organic
framework nanosheets as building blocks for molecular sieving membranes. Science
346, 1356–1359.
Qiao, J., Kong, X., Hu, Z.X., Yang, F., Ji, W., 2014. High-mobility transport anisotropy
and linear dichroism in few-layer black phosphorus. Nat. Commun. 5, 4475.
Qin, P., Fang, G., Ke, W., Cheng, F., Zheng, Q., Wan, J., Lei, H., Zhao, X., 2014. In situ
growth of double-layer MoO3/MoS2 film from MoS2 for hole-transport layers in
organic solar cell. J. Mater. Chem. A 2, 2742–2756.
Rafique, S., Abdullah, S.M., Alhummiany, H., Abdel-wahab, M.S., Iqbal, J., Sulaiman, K.,
2016. Bulk heterojunction organic solar cells with graphene oxide hole transport
layer: effect of varied concentration on photovoltaic performance. J. Phys. Chem. C
121, 140–146.
Ramasamy, M.S., Ryu, K.Y., Lim, J.W., Bibi, A., Kwon, H., Lee, J.E., Kim, D.H., Kim, K.,
2019. Solution-processed PEDOT:PSS/MoS2 nanocomposites as efficient hole-
transporting layers for organic solar cells. Nanomaterials 9, 1328–1340.
Y. Zhao et al.
Ren, X., Li, Z., Huang, Z., Sang, D., Qiao, H., Qi, X., Li, J., Zhong, J., Zhang, H., 2017.
Environmentally robust black phosphorus nanosheets in solution: application for
self-powered photodetector. Adv. Funct. Mater. 27, 1606834.
Ricciardulli, A.G., Yang, S., Feng, X., Blom, P.W.M., 2017. Solution-processable high-
quality graphene for organic solar cells. ACS Appl. Mater. Interfaces 9,
25412–25417.
Ricciardulli, A.G., Yang, S., Wetzelaer, G.-J.A.H., Feng, X., Blom, P.W.M., 2018. Hybrid
silver nanowire and graphene-based solution-processed transparent electrode for
organic optoelectronics. Adv. Funct. Mater. 28, 1706010.
Rodenas, T., Luz, I., Prieto, G., Seoane, B., Miro, H., Corma, A., Kapteijn, F., Llabres, I.X.
F.X., Gascon, J., 2015. Metal-organic framework nanosheets in polymer composite
materials for gas separation. Nat. Mater. 14, 48–55.
Romero-Borja, D., Maldonado, J.-L., Barbosa-García, O., Rodríguez, M., de León, A.,
Fernández, S., Pérez-Gutiérrez, E., 2018. Organic solar cells based on graphene
derivatives and eutectic alloys vacuum-free deposited as top electrodes. Carbon 134,
301–309.
Ruscello, M., Sarkar, T., Levitsky, A., Matrone, G.M., Droseros, N., Schlisske, S., Sachs, E.,
Reiser, P., Mankel, E., Kowalsky, W., Banerji, N., Stingelin, N., Frey, G.L.,
Hernandez-Sosa, G., 2019. Nanocomposite of nickel oxide nanoparticles and
polyethylene oxide as printable hole transport layer for organic solar cells. Sustain.
Energy Fuels 3, 1418–1426.
Sang, D.K., Wang, H., Guo, Z., Xie, N., Zhang, H., 2019. Recent developments in stability
and passivation techniques of phosphorene toward next-generation device
applications. Adv. Funct. Mater. 29, 1903419.
Schulz, P., Cowan, S.R., Guan, Z.-L., Garcia, A., Olson, D.C., Kahn, A., 2014. NiOX/
MoO3Bi-Layers as efficient hole extraction contacts in organic solar cells. Adv. Funct.
Mater. 24, 701–706.
Shivayogimath, A., Thomsen, J.D., Mackenzie, D.M.A., Geisler, M., Stan, R.M., Holt, A.J.,
Bianchi, M., Crovetto, A., Whelan, P.R., Carvalho, A., Neto, A.H.C., Hofmann, P.,
Stenger, N., Boggild, P., Booth, T.J., 2019. A universal approach for the synthesis of
two-dimensional binary compounds. Nat. Commun. 10, 2957.
Stotter, J., Show, Y., Wang, S., Swai, G., 2005. Comparison of the electrical, optical, and
electrochemical properties of diamond and indium tin oxide thin-film electrodes.
Chem. Mater. 17, 4880–4888.
Stylianakis, M.M., Konios, D., Petridis, C., Kakavelakis, G., Stratakis, E., Kymakis, E.,
2017. Ternary solution-processed organic solar cells incorporating 2D materials. 2D
Mater. 4, 042005.
Sun, J., Lee, H.W., Pasta, M., Yuan, H., Zheng, G., Sun, Y., Li, Y., Cui, Y., 2015a.
A phosphorene-graphene hybrid material as a high-capacity anode for sodium-ion
batteries. Nat. Nanotechnol. 10, 980–985.
Sun, R., Wu, Q., Guo, J., Wang, T., Wu, Y., Qiu, B., Luo, Z., Yang, W., Hu, Z., Guo, J.,
Shi, M., Yang, C., Huang, F., Li, Y., Min, J., 2020. A layer-by-layer architecture for
printable organic solar cells overcoming the scaling lag of module efficiency. Joule 4,
407–419.
Sun, Y., Seo, J.H., Takacs, C.J., Seifter, J., Heeger, A.J., 2011. Inverted polymer solar
cells integrated with a low-temperature-annealed sol-gel-derived ZnO film as an
electron transport layer. Adv. Mater. 23, 1679–1683.
Sun, Z., Xie, H., Tang, S., Yu, X.F., Guo, Z., Shao, J., Zhang, H., Huang, H., Wang, H.,
Chu, P.K., 2015b. Ultrasmall black phosphorus quantum dots: synthesis and use as
photothermal agents. Angew. Chem. Int. Ed. 54, 11526–11530.
Tang, H., Feng, H., Wang, H., Wan, X., Liang, J., Chen, Y., 2019. Highly conducting
MXene-Silver nanowire transparent electrodes for flexible organic solar cells. ACS
Appl. Mater. Interfaces 11, 25330–25337.
Van Le, Q., Choi, J.-Y., Kim, S.Y., 2017. Recent advances in the application of two-
dimensional materials as charge transport layers in organic and perovskite solar
cells. FlatChem 2, 54–66.
Voiry, D., Yamaguchi, H., Li, J., Silva, R., Alves, D.C., Fujita, T., Chen, M., Asefa, T.,
Shenoy, V.B., Eda, G., Chhowalla, M., 2013. Enhanced catalytic activity in strained
chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 12,
850–855.
Wan, X., Long, G., Huang, L., Chen, Y., 2011. Graphene - A promising material for
organic photovoltaic cells. Adv. Mater. 23, 5342–5358.
Wang, B.-Y., Lee, E.-S., Oh, Y.-J., Kang, H.W., 2017. A silver nanowire mesh overcoated
protection layer with graphene oxide as a transparent electrode for flexible organic
solar cells. RSC Adv. 7, 52914–52922.
Wang, J., Yu, H., Hou, C., Zhang, J., 2019. Solution-processable 2D α-In2Se3 as an
efficient hole transport layer for high-performance and stable polymer solar cells.
Solar RRL 4, 1900428.
Wang, J., Yu, H., Hou, C., Zhang, J., 2020. Solution-processable PEDOT:PSS:α-In2Se3
with enhanced conductivity as a hole transport layer for high-performance polymer
solar cells. ACS Appl. Mater. Interfaces 12, 26543–26554.
Wang, Q.H., Kalantar-Zadeh, K., Kis, A., Coleman, J.N., Strano, M.S., 2012. Electronics
and optoelectronics of two-dimensional transition metal dichalcogenides. Nat.
Nanotechnol. 7, 699–712.
Wang, W., Feng, W., Du, J., Xue, W., Zhang, L., Zhao, L., Li, Y., Zhong, X., 2018.
Cosensitized quantum dot solar cells with conversion efficiency over 12%. Adv.
Mater. 30, 1705746.
Wang, X., Zhi, L., Tsao, N., Tomovic, Z., Li, J., Mullen, K., 2008. Transparent carbon films
as electrodes in organic solar cells. Angew. Chem. Int. Ed. 47, 2990–2992.
Wang, Y., Tong, S.W., Xu, X.F., Ozyilmaz, B., Loh, K.P., 2011. Interface engineering of
layer-by-layer stacked graphene anodes for high-performance organic solar cells.
Adv. Mater. 23, 1514–1518.
Wen, X., Nowak-Krol, A., Nagler, O., Kraus, F., Zhu, N., Zheng, N., Muller, M.,
Schmidt, D., Xie, Z., Wurthner, F., 2019. Tetrahydroxy-perylene bisimide embedded
in zinc oxide thin film as electron transporting layer for high performance non-
fullerene organic solar cells. Angew. Chem. Int. Ed. 131, 13185–13189.
637
Solar Energy 218 (2021) 621–638
Wijeyasinghe, N., Regoutz, A., Eisner, F., Du, T., Tsetseris, L., Lin, Y.-H., Faber, H.,
Pattanasattayavong, P., Li, J., Yan, F., McLachlan, M.A., Payne, D.J., Heeney, M.,
Anthopoulos, T.D., 2017. Copper(I) thiocyanate (CuSCN) hole-transport layers
processed from aqueous precursor solutions and their application in thin-film
transistors and highly efficient organic and organometal halide perovskite solar cells.
Adv. Funct. Mater. 27, 1701818.
Wu, J., Becerril, H.A., Bao, Z., Liu, Z., Chen, Y., Peumans, P., 2008. Organic solar cells
with solution-processed graphene transparent electrodes. Appl. Phys. Lett. 92,
263302.
Xie, J., Wang, X., Wang, S., Ling, Z., Lian, H., Liu, N., Liao, Y., Yang, X., Qu, W., Peng, Y.,
Lan, W., Wei, B., 2019. Solution-processed ZnO/MoS2 quantum dots electron
extraction layer for high performance inverted organic photovoltaics. Organic
Electro. 75, 105381.
Xing, W., Ye, P., Lu, J., Wu, X., Chen, Y., Zhu, T., Peng, A., Huang, H., 2018.
Tellurophene-based metal-organic framework nanosheets for high-performance
organic solar cells. J. Power Sources 401, 13–19.
Xing, Z., Meng, X., Sun, R., Hu, T., Huang, Z., Min, J., Hu, X., Chen, Y., 2020. An effective
method for recovering nonradiative recombination loss in scalable organic solar
cells. Adv. Funct. Mater. 30, 2000417.
Yan, T., Song, W., Huang, J., Peng, R., Huang, L., Ge, Z., 2019. 16.67% rigid and 14.06%
flexible organic solar cells enabled by ternary heterojunction strategy. Adv. Mater.
31, 1902210.
Yang, L., Dall’Agnese, Y., Hantanasirisakul, K., Shuck, C.E., Maleski, K., Alhabeb, M.,
Chen, G., Gao, Y., Sanehira, Y., Jena, A.K., Shen, L., Dall’Agnese, C., Wang, X.-F.,
Gogotsi, Y., Miyasaka, T., 2019a. SnO2–Ti3C2 MXene electron transport layers for
perovskite solar cells. J. Mater. Chem. A 7, 5635–5642.
Yang, W., Ye, L., Yao, F., Jin, C., Ade, H., Chen, H., 2019b. Black phosphorus nanoflakes
as morphology modifier for efficient fullerene-free organic solar cells with high fill-
factor and better morphological stability. Nano Res. 12, 777–783.
Yang, W., Ye, Z., Liang, T., Ye, J., Chen, H., 2019c. Facilitate charge transfer at donor/
acceptor interface in bulk heterojunction organic photovoltaics by two-dimensional
nanoflakes. Sol. Energy Mat. Sol. C. 190, 75–82.
Yao, K., Zhong, H., Liu, Z., Xiong, M., Leng, S., Zhang, J., Xu, Y.X., Wang, W., Zhou, L.,
Huang, H., Jen, A.K., 2019. Plasmonic metal nanoparticles with core-bishell
structure for high-performance organic and perovskite solar cells. ACS Nano 13,
5397–5409.
Huang, Yi-Jiun, Chen, Hsiu-Cheng, Lin, Hsi-Kuei, Wei, K.-H., 2018. Doping ZnO electron
transport layers with MoS2 nanosheets enhances the efficiency of polymer solar cells.
ACS Appl. Mater. Interfaces 10, 20196–20204.
Yu, L., Bati, A.S.R., Grace, T.S.L., Batmunkh, M., Shapter, J.G., 2019a. Ti3C2Tx (MXene)-
silicon heterojunction for efficient photovoltaic cells. Adv. Energy Mater. 31,
1901063.
Yu, P., Zhen, Y., Dong, H., Hu, W., 2019b. Crystal engineering of organic optoelectronic
materials. Chem 5, 2814–2853.
Yu, X., Marks, T.J., Facchetti, A., 2016. Metal oxides for optoelectronic applications. Nat.
Mater. 15, 383–396.
Yu, Z., Feng, W., Lu, W., Li, B., Yao, H., Zeng, K., Ouyang, J., 2019c. MXenes with tunable
work functions and their application as electron- and hole-transport materials in
non-fullerene organic solar cells. J. Mater. Chem. A 7, 11160–11169.
Yuan, J., Zhang, Y., Zhou, L., Zhang, G., Yip, H.-L., Lau, T.-K., Lu, X., Zhu, C., Peng, H.,
Johnson, P.A., Leclerc, M., Cao, Y., Ulanski, J., Li, Y., Zou, Y., 2019. Single-junction
organic solar cell with over 15% efficiency using fused-ring acceptor with electron-
deficient core. Joule 3, 1140–1151.
Yun, J.M., Yeo, J.S., Kim, J., Jeong, H.G., Kim, D.Y., Noh, Y.J., Kim, S.S., Ku, B.C., Na, S.
I., 2011. Solution-processable reduced graphene oxide as a novel alternative to
PEDOT:PSS hole transport layers for highly efficient and stable polymer solar cells.
Adv. Mater. 23, 4923–4928.
Zang, X., Wang, J., Qin, Y., Wang, T., He, C., Shao, Q., Zhu, H., Cao, N., 2020. Enhancing
capacitance performance of Ti3C2Tx MXene as electrode materials of supercapacitor:
from controlled preparation to composite structure construction. Nano-Micro Lett.
12, 77–101.
Zhang, J.L., Han, C., Hu, Z., Wang, L., Liu, L., Wee, A.T.S., Chen, W., 2018. 2D
phosphorene: epitaxial growth and interface engineering for electronic devices. Adv.
Mater. 30, 1802207.
Zhang, S., Xie, M., Li, F., Yan, Z., Li, Y., Kan, E., WeiLiu, Chen, Z., Zeng, H., 2016.
Semiconducting group 15 monolayers: a broad range of band gaps and high carrier
mobilities. Angew. Chem. Int. Ed. 128, 1698-1701.
Zhang, Y.X., Fang, J., Li, W., Shen, Y., Chen, J.D., Li, Y., Gu, H., Pelivani, S., Zhang, M.,
Li, Y., Tang, J.X., 2019. Synergetic transparent electrode architecture for efficient
non-fullerene flexible organic solar cells with >12% Efficiency. ACS Nano 13,
4686–4694.
Zhao, Y., Chen, T.L., Xiao, L., Kolaczkowski, M.A., Zhang, L., Klivansky, L.M., Altoe, V.,
Tian, B., Guo, J., Peng, X., Tian, Y., Liu, Y., 2018. Facile integration of low-cost black
phosphorus in solution-processed organic solar cells with improved fill factor and
device efficiency. Nano Energy 53, 345–353.
Zheng, D., Huang, W., Fan, P., Zheng, Y., Huang, J., Yu, J., 2017. Preparation of reduced
graphene Oxide:ZnO hybrid cathode interlayer using in situ thermal reduction/
annealing for interconnecting nanostructure and its effect on organic solar cell. ACS
Appl. Mater. Interfaces 9, 4898–4907.
Y. Zhao et al.
Zheng, X., Zhang, H., Yang, Q., Xiong, C., Li, W., Yan, Y., Gurney, R.S., Wang, T., 2019.
Solution-processed graphene-MoS2 heterostructure for efficient hole extraction in
organic solar cells. Carbon 142, 156–163.
Zhou, Y., Fuentes-Hernandez, C., Shim, J., Meyer, J., Giordano, A.J., Li, H., Winget, P.,
Papadopoulos, T., Cheun, H., Kim, J., Fenoll, M., Dindar, A., Haske, W.,
Najafabadi, E., Khan, T.M., Sojoudi, H., Barlow, S., Graham, S., Bredas, J.L.,
638
Solar Energy 218 (2021) 621–638
Marder, S.R., Kahn, A., Kippelen, B., 2012. A universal method to produce low-work
function electrodes for organic electronics. Science 336, 327–332.
Zhuang, J., Liu, C., Gao, Q., Liu, Y., Feng, H., Xu, X., Wang, J., Zhao, J., Dou, S.X., Hu, Z.,
Du, Y., 2018. Band gap modulated by electronic superlattice in blue phosphorene.
ACS Nano 12, 5059–5065.