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Recent Advances

Cite this paper: Chin. J. Chem. 2023, 41, 3373—3387. DOI: 10.1002/cjoc.202300252

Recent Progress of Inorganic Hole-Transport Materials for

Perovskite Solar Cells†
Rui Wang,‡ Xiyue Dong,‡ and Yongsheng Liu*

The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Institute of Polymer Chemistry,
College of Chemistry and Renewable Energy Conversion and Storage Center (RECAST), Nankai University, Tianjin 300071, China

Keywords
Perovskite solar cells | Inorganic nanomaterials | Hole transport layers | Crystals | Molecular modification | Photovoltaic properties

Comprehensive Summary

Perovskite solar cells (PSCs) have achieved significant progress in the past decade and a certified power conversion efficiency (PCE)
of 26.0% has been achieved. The widely used organic hole transport materials (HTMs) in PSCs are typically sensitive to the moisture
environment and continuous light exposure. In contrast, the inorganic HTMs benefiting from their outstanding merits, such as excel-
lent environmental stability, are considered as alternatives and have attracted much attention in PSCs. In this review, we provide a
comprehensive summary of the fundamental properties and recent progress of inorganic HTMs in n-i-p and p-i-n structured PSCs.
Additionally, we emphasize the importance of inorganic HTMs in the development of highly efficient and stable PSCs.

*E-mail: liuys@nankai.edu.cn
‡
R.W. and X.D. contributed equally to this work.
†
Dedicated to the Special Issue of Perovskite.

Chin. J. Chem. 2023, 41, 3373—3387 © 2023 SIOC, CAS, Shanghai, & WILEY-VCH GmbH 3373
Recent Advances Wang, Dong & Liu

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Left to right: Rui Wang, Xiyue Dong, Yongsheng Liu
Rui Wang obtained her BS. degree from the Jinan University. Currently, she is a Ph.D. student at Nankai University under the supervision of Prof.
Yongsheng Liu. Her current research focuses on organic-inorganic hybrid perovskite solar cells.
Xiyue Dong obtained his MS. degree from the University of Chinese Academy of Sciences. Currently, he is a Ph.D. student at Nankai University under
the supervision of Prof. Yongsheng Liu. His current research focuses on organic semiconductor materials, organic solar cells, and perovskite solar cells.
Yongsheng Liu received his Ph.D. degree in chemistry from Nankai University in 2009. After postdoctoral training at Nankai University (2009—2011)
and University of California, Los Angeles (UCLA) (2011—2016), he joined Nankai University in 2016 as a full professor. His research interests include
organic and organic–inorganic hybrid semiconductor materials and devices, organic solar cells, perovskite solar cells, and nanomaterials for applica-
tions in energy technology. He has published over 90 peer-reviewed journal papers with more than 20000 citations. His H-index is 49. He has been se-
lected as Highly Cited Researcher (Clarivate Analytics) (2018—2022).

Contents
1. Introduction
2. Inorganic HTLs in PSCs
2.1. Nickel oxide (NiOx)
2.2. Copper thiocyanate (CuSCN)
2.2.1. The p-i-n architecture of CuSCN-based PSCs
2.2.2. The p-i-n architecture of CuSCN-based PSCs
2.3. Copper(I) iodide (CuI)
2.3.1. CuI for p-i-n structured PSCs
2.3.2. CuI for n-i-p structured PSCs
2.4. Copper oxides (CuxO)
2.4.1. CuxO for p-i-n structured PSCs
2.4.2. CuxO for n-i-p structured PSCs
2.5. Copper sulfides (CuS)
2.5.1. CuS for p-i-n structured PSCs
2.5.2. CuxS and CuS derivatives for n-i-p structured PSCs
2.6. Molybdenum oxides (MoOx)
2.6.1. MoOx for p-i-n structured PSCs
2.6.2. MoOx for n-i-p structured PSCs
3. Conclusions and Perspectives
1. Introduction
Perovskite solar cells (PSCs) have recently attracted much at-
tention because of their advantages, such as high photovoltaic
performance, easy solution fabrication, large area devices, and
low production cost.
[1-5]
In the last few years, the efficiency of
over 25% has been achieved using small molecules or polymers as
organic hole transport materials (HTMs), which is close to that of
[6]
traditional crystalline silicon cells. Generally, the device archi-
tecture of PSCs consists of several layers, such as the electrode
layer, a perovskite (PVSK) active layer, a hole-transport layer (HTL),
[7]
and an electron-transport layer (ETL). In specific, the device
structures of PSCs can be classified by n-i-p and p-i-n structures
(Figures 1a, b). The depositional order of the transport layers and
electrons distinguishes the various device architectures. For the
n-i-p device, the ETL is initially deposited on the transparent con-
ducting oxide (TCO) glass, followed by the deposition of the per-
ovskite layer and HTL using orthogonal solvent or evaporation.
The anode material is then evaporated onto the device surface. In
contrast, the p-i-n device is fabricated by depositing the HTL on
TCO glass, and then active layer, ETL, and cathode in sequence.
The HTLs play a vital role in both types of PSCs, as they should
have the following characteristics: (1) the highest occupied molec-
ular orbital (HOMO) energy level of HTL should be compatible
with the valence band maximum (VBM) of the perovskite for ef-
[8-9]
fective carrier extraction and transportation, (2) the HTL
should have good film-formation abilities via solution process, (3)
the HTL should equip with outstanding intrinsic stability, such as
[10-12]
chemical and environmental stability, (4) HTL should have
3374 high hole mobility and low preparation cost.
[7,13]
So far, HTLs used
3375 in perovskite can be mainly divided into two categories: organic
3375 HTLs (such as 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-
3377
9,9'-spirobifluorene (spiro-OMeTAD), poly(bis(4-phenyl)(2,4,6-tri-
3377
methylphenyl)amine (PTAA), and poly(3,4-ethylenedioxythio-
3377
phene):poly(styrenesulfonate) (PEDOT:PSS), and so on), and inor-
3379
ganic HTLs (such as CuxO, CuSCN, CuI, NiOx, MoOx, and so on).
3379
Depending on the PSC architectures, the selection of HTLs is in-
3380
fluenced by several factors. In the p-i-n structure, the HTLs are
3380
first deposited before depositing the perovskite layer. The HTL
3381
layer will absorb some incident light, thereby reducing the availa-
3381
ble sunlight for perovskite layers. Consequently, the primary re-
3382
3382 quirement for the HTL in the p-i-n structure is that it should be
3382 transparent to avoid hindering the light absorption of the perov-
3382 skite layer. Another crucial factor is the wettability of the HTL by
3382 the perovskite precursor solution, which greatly affects the suc-
3383 cessful preparation of high-quality perovskite films. For n-i-p
3383 structure PSCs, there are no specific requirements regarding the
absorption range of the HTLs since they are deposited on top of
the perovskite layer which does not impact the light absorption of
the perovskite in this device structure. However, the selection of
solvent for the HTMs is of utmost importance in the n-i-p struc-
ture PSCs. The solvent should not damage the pre-existing perov-
skite films, necessitating the use of orthogonal solvents. Moreover,
n-i-p type PSCs require HTMs with higher work function and lower
ionization potential compared to p-i-n type perovskite solar cells.
This is due to the former employing a low work function metal as
cathode, while the latter uses a high work function metal as an-
ode. As a result, some HTMs that are suitable for n-i-p type PSCs
may not be suitable for p-i-n type PSCs.
So far, the organic HTLs are widely applied in highly efficient
PSCs, but still have some drawbacks. For example, Spiro-OMeTAD
is commonly utilized as the HTM in high-efficiency n–i–p structure
PSCs. However, Spiro-OMeTAD film exhibits low conductivity and
requires doping when it is used as HTM in PSCs. The ionic dopants
used in this process are typically hygroscopic, and as a result, ionic
migration frequently occurs from HTM to the perovskite layer or
electrode, which adversely affects device stability. Furthermore,
the complex synthesis routes involved in producing Spiro-OMeTAD
[9-10]
hinder its application. In addition, PEDOT:PSS has been the
primary choice for a HTL in inverted PSCs because of its superior
optical transparency, adjustable conductivity, easy manufacturing
[14]
process, and excellent mechanical flexibility. However, the
acidic properties of PEDOT:PSS can cause the degradation of ad-
[15]
jacent electrode. Furthermore, the hygroscopic nature of PE-
DOT:PSS and the migration of indium ions from the transparent

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Inorganic Hole-Transport Materials for Perovskite Solar Cells
electrode into PEDOT:PSS can be harmful to PSCs. The relatively
high HOMO of PEDOT:PSS also restricts the improvement of the
[16]
open-circuit voltage (VOC) of PSCs. PTAA has been extensively
studied as a potential HTM candidate in PSCs due to its chemical
stability against solvents like DMF and DMSO, making it particu-
[14]
larly suitable for inverted PSCs. However, preparing a high-
quality perovskite film on top of the hydrophobic PTAA surface is
[7,14]
challenging. Hence, DMF solvent needs to be spin-coated onto
the PTAA layers before the perovskite film deposition to enhance
infiltration. In contrast, inorganic p-type semiconductors, such as
nickel oxide (NiOx), copper(I) thiocyanate (CuSCN) and copper(I)
iodide (CuI), have the advantages, such as matched energy levels
(Figure 1c), superior DMF infiltration, high hole mobility and con-
ductivity in pristine form, relatively large bandgap, and high
[17]
chemical stability. These unique properties make inorganic
p-type materials become promising HTM candidates for PSCs. We
note that several reviews on PSCs using inorganic HTMs have been
[11,18]
reported. This review mainly focuses on recent progress of
several promising inorganic HTMs including NiOx-based HTMs,
Cu-based HTMs and MoO3-based HTM in PSCs.
Figure 1 Device architectures of PSCs: (a) n–i–p and (b) p–i–n.[19] (c) The
valence band maximum (VBM) and conduction band minimum (CBM)
relative to the vacuum of common inorganic transport layers.
2. Inorganic HTLs in PSCs
2.1. Nickel oxide (NiOx)
One of the extensively investigated inorganic HTMs for in-
verted PSCs is NiOx. In comparison with PTAA or PEDOT:PSS, NiOx-
based HTLs offer several advantages, such as a wide bandgap
(> 3.6 eV) with high optical transmittance, energetically favorable
energy level alignment (deep VBM around ‒5.4 eV) with most
[20]
perovskite absorbers. The wide band gap of NiOx ensures min-
imal absorption of visible light, allowing for efficient transmission
of photons to the perovskite absorber layer. The matched energy
levels facilitate efficient charge extraction and reduce energy loss
at the interface between the perovskite and the HTM. Another
advantage of NiOx is its stable chemical properties, which contrib-
ute to the long-term stability of PSCs. NiOx layers can be rapidly
prepared by various approaches, such as the combustion meth-
[21] [22] [23]
od, spin coating method, and electrochemical deposition.
Benefiting from the above merits, NiOx can be considered as the
promising HTM for the application of PSCs. Table 1 shows the
photovoltaic properties and device structures of the PSCs using
NiOx as HTLs prepared by different deposition processes.
However, stoichiometric NiOx displays a relatively low intrinsic
[24-25]
conductivity, which limits their device applications. The un-
doped NiOx typically exhibits p-type characteristics due to the
numerous nickel vacancies with considerable ionization energy,
[26]
resulting in reduced total density of the hole. Besides, the
mismatch between the Fermi level (WF) of NiOx and the VBM of
[27]
perovskite will weaken the built-in field of PSCs. As a result, the
hole will accumulate at the interface between perovskite and HTL,
[28-29]
preventing efficient charge extraction. Moreover, the exist-
3+
ence of high-oxidative-state Ni species (like Ni ) on the HTL sur-
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Chin. J. Chem.
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face is also detrimental to the device stability. Due to its oxidizable
3+ ‒
characteristic, the Ni could easily react with the I present in the
perovskite layer, leading to the deterioration of perovskite film
morphology and the formation of numerous trap defects at the
[30]
interface between HTL and perovskite layer. Numerous ap-
[31]
proaches, such as UV-ozone and oxygen-plasma treatments,
[32]
interfacial modifications, and extrinsic doping, were used to
reduce the defects and improve the conductivity and hole mobili-
[33]
ties of NiOx.
The UV-ozone and oxygen-plasma treatments are considered
as the convenient methods to adjust the conductivity and Fermi
[53]
energy level of the NiOx layer. Ma et al. proposed that
UV-ozone treatment can form nickel oxyhydroxide (NiOOH) on the
NiOx film surface, generating a large surface dipole and increasing
WF of HTL. Besides, the plasma treated NiOx film shows a reduced
tendency in the near-Fermi edge density of Ni 3d states, which
could suppress the charge carrier recombination at the interface
[34]
between the perovskite layer and HTL. Shen et al. systematical-
ly studied the properties of UV-ozone exposure NiOx film, and
they found that the UV-ozone treated NiOx film exhibits suitable
surface wettability and enhanced electrical conductivity, leading
to improved efficient PSCs with PCE of 19.67%. However, the com-
mon UV-ozone treatment will decrease film transmittance and
increase the density of sub-gap states in NiOx film. Recently, Liu et
[35]
al. proposed a novel surface redox engineering (SRE) prepara-
tion method by delivering the vacuum-deposited NiOx films to go
through an Ar-plasma-initiated oxidation process and a Brønsted
acid-mediated reaction, which could eliminate the de-wetting
problem of perovskite precursor and enhanced electronic proper-
ties at buried interfaces of perovskite, leading to a more stable
perovskite surface morphology with high surface energy. Conse-
quently, outstanding PCEs of 23.4% and 18.6% were achieved for
rigid and submodule PSCs, respectively. The process of SRE and
the corresponding device performance are shown in Figure 2a.
The SRE provides a reliable way for the surface regulation of vac-
uum-processed NiOx films for wet-processed perovskite, which
could promote the industrialization of perovskite solar modules.
Extrinsic doping has been regarded as a facile method to ad-
just the WF and conductivity of NiOx film. The dopants can be
typically divided into the following categories: p-type dopants,
n-type dopants (Cu and Zn), rare-earth metal ion dopants (Y and
La), and alkali earth metal dopants (Li, Mg, Ca, Sr, and Mg). He et
[36]
al. have reported an excellent HTL of copper doped nickel oxide
(Cu:NiOx) film. The prepared Cu:NiOx film has higher carrier con-
centration and enhanced mobilities compared with pure NiOx film,
+ 2+
which can be attributed to the substitution of Cu for Ni in
Cu:NiOx film. The Zn dopant can be easily incorporated into the
NiOx matrix lattice because Zn and Ni have a similar atomic radi-
[37]
us. According to the spin-decomposed density of states (DOS)
calculated results, Zn-doped NiOx exhibits additional electronic
states near the Fermi level, which could improve the electronic
conductivity of Zn:NiOx film. Thus, the PSCs based on the NiOx HTL
with 5% Zn doping showed an improved efficiency of 19.6% with
[38]
negligible hysteresis. Zhao et al. investigated the effect of yt-
3+
trium (Y ) doping on the device performance. Typically, the Y can
easily produce additional electron configurations benefiting from
its singly occupied 4d orbital. They found that the charge extrac-
tion and transportation abilities of PSCs were improved owing to
3+
the enhanced hole mobility of Y -doped NiOx film. The monova-
lent alkali metal doping can significantly improve the conductivity
[40]
of NiOx film without transmittance changes. Yang et al. adopted
alkali earth metal dopants to tailor the semiconductor properties
of NiOx. The alkali metal treated NiOx films display deeper VBM
leading to the aligned energy levels with the perovskite layer.
Besides, the Sr-doped NiOx HTL exhibits better aligned band
structures at the NiOx/MAPbI3 interface, which is beneficial to
hole extraction and reduces the loss of photocarrier accumulation
at the interface of MAPbI3 and HTL. As a result, the PSC based on
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Table 1 The photovoltaic parameters of the PSCs based on NiOx films
Deposition method Device configuration VOC/V JSC/(mA·cm‒2) FF/% PCE/% Ref.
Electrochemical deposition FTO/NiOx/MAPbI3/PC61BM/BCP/Ag 1.11 23.39 75.59 19.67 34
Electron beam evaporation FTO/EBE-NiOx/FAPbI3/PC61BM/BCP/Ag 1.16 24.80 81.0 23.4 35
Spin-coating ITO/Cu:NiOx/MAPbI3/C60/BCP/Ag 1.12 22.23 80.90 20.15 36
Spin-coating FTO/Zn:NiOx/MAPbI3/PC61BM/BCP/Ag 1.10 22.80 78.00 19.60 37
Spin-coating FTO/Y:NiOx/MAPbI3/PC61BM/BCP/Ag 1.00 23.82 68.00 16.31 38
Spin-coating ITO/Li:NiOx/MAPbI3/PC61BM/BCP/Ag 1.12 21.79 73.60 18.00 39
Spin-coating FTO/Mg:NiOx/MAPbI3/PC61BM/BCP/Ag 1.10 22.44 74.40 18.29 40
Spin-coating FTO/Ca:NiOx/MAPbI3/PC61BM/BCP/Ag 1.13 22.30 74.80 18.75 40
Spin-coating FTO/Sr:NiOx/MAPbI3/PC61BM/BCP/Ag 1.14 22.66 75.60 19.49 40
Spin-coating FTO/Ba:NiOx/MAPbI3/PC61BM/BCP/Ag 1.10 22.24 73.70 17.94 40
Spin-coating ITO/NiOx IL/Cs0.05FA0.81MA0.14PbI2.55Br0.45/PC61BM/BCP/Au 1.13 23.75 84.21 22.62 41
Spin-coating FTO/NiOx/DEA/MAPbI3‒xClx/PC61BM/PN4N/Ag 0.95 20.90 80.00 15.90 29
Spin-coating ITO/F2HCNQ/NiOx/Cs0.05FA0.81MA0.14PbI2.55Br0.45/PC61BM/BCP/Ag 1.14 23.44 82.8 22.13 42
Spray-pyrolysis technique FTO/NiOx/TMSBr/FAPbI3/PC61BM/PN4N/Ag 1.18 22.93 81.33 22.06 43
RF-sputtering ITO/NiOx/2PACz/FAPbI3/PC61BM/BCP/Ag 1.14 23.19 80.60 21.31 44
RF-sputtering ITO/NiOx/MeO-2PACz/Cs0.05FA0.81MA0.14PbI2.55Br0.45/C60/BCP/Ag 1.11 22.30 80.40 19.90 45
Spin-coating PET/ITO/NiOx/MB/FA0.8Cs0.2PbI1.95Br1.05/C60/BCP/Ag 1.22 16.50 80.60 16.20 46
Spin-coating PET/ITO/NiOx/PTAA/Al2O3/PEI/FA0.95Cs0.05PbI3/PC61BM/PCB/Ag 1.13 23.49 81.40 23.49 47
Spin-coating FTO/NiOx/PTAA/FA1‒xMAxPb(I3‒yBry)/PC61BM/Au 1.06 21.54 74.80 17.10 48
Spin-coating ITO/NiOx/PVSK/PC61BM/BCP/Ag 1.15 24.90 83.46 23.91 49
Spin-coating FTO/NiOx/Urea/PVSK/BzMIMBr/C60/BCP/Cu 1.15 24.04 85.40 23.61 50
Spin-coating FTO/NiOx/PTAA/Al2O3/Cs0.05FA0.81MA0.14PbI2.55Br0.45/PC61BM/BCP/Ag 1.16 23.5 81.4 22.21 51
Spin-coating FTO/NiOx/Me-4PACz/DPPP/FA0.95Cs0.05PbI3/C60/BCP/Ag 1.16 25.7 81.6 24.50 52

Figure 2 (a) Schematic illustration showing the process of SRE (left side).[35] The J-V and I-V curves of champion rigid devices and champion modules,
respectively (right side).[35] (b) Synthesis routes of NiOx and NiOx-IL nanoparticles.[41] (c) Raman spectra of the pure IL, control Ni(OH)2, and Ni(OH)2-IL.[41]
(d) The charge density difference between NiO and IL (or NO3‒).[41]

the Sr-doped NiOx HTL achieved a champion PCE of 19.49%. Re-
cently, ionic liquid (IL) additives, such as 1-butyl-3-methylimidazo-
lium tetrafluoroborate ([BMIm]BF4IL), have also been applied to
[41]
assist the NiOx film formation process (NiOx-IL). The prepara-
tion method of NiOx-IL is shown in Figure 2b. Different from the
traditional preparation method, the [BMIm]BF4IL directly drops
into the Ni(NO3)2 precursor before reacting with NaOH to create
+
numerous [BMIm] , which could effectively hinder the existence
3−
of the impurity ligand of NiO in NiOx-IL, demonstrated by the
Raman spectra (Figure 2c). Significantly, to suppress the redox
reaction between the NiOx film and the perovskite film, it is highly
necessary to remove the impurity ions and slow down the deteri-
oration of device performance. Additionally, the charge density
difference of NiOx-IL becomes more positive with an adsorption
3+
loss of 0.43 e (Figure 2d), leading to the increased content of Ni
and enhanced conductivity of modified NiOx film.
Introducing the tailored molecules to the interface between
the perovskite layer and HTL is a simple strategy to reduce the
defects of the perovskite surface, inhibit the redox reaction at the
interface, modify the optoelectronic properties of NiOx film, and
[17,51,54-55] [29]
adjust the morphology of perovskite. Yang et al. re-
ported efficient PSCs based on the modified NiOx by diethanola-
mine (DEA) with hydroxy and amine functional groups. The DEA
could strongly interact with both NiOx and perovskite by Ni‧‧‧N,
and Pb‧‧‧O interactions, resulting in improved perovskite film
[42]
quality. Ha et al. explored the changes in energy levels and
conductivity of modified NiOx by several organic molecular do-
pants with different electron affinity (EA). They found that the
2,5,7,7,8,8-tetracyanoquino-dimethane (F2HCNQ) molecule with
a high EA can decrease the VBM of HTLs, resulting in the en-
hanced VOC of PSCs. Moreover, the interface contact and the per-
ovskite crystalline quality are also improved, resulting in an effi-

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Inorganic Hole-Transport Materials for Perovskite Solar Cells
cient PSC with a high PCE of 22.13%. In addition, PTAA is another
[47]
suitable polymer for the interface modification of NiOx film. The
PTAA modified NiOx (NiOx/PTAA) could regulate the band align-
ment between HTL and perovskite, which could promote efficient
[48]
charge extraction.
The self-assembled small-molecule is considered as another
efficient method to solve the interface issues between HTL and
perovskite films. For example, a p-chlorobenzenesulfonic acid
(CBSA)-based self-assembled layer is first reported as the bridging
[54]
agent at NiOx/perovskite interface by Chen and coworkers.
Different from traditional chlorobenzene (CB) and benzenesul-
fonic acid (BSA) molecules, CBSA with -SO3H and -Cl groups could
passivate on the surface oxygen defects of NiOx and fill the iodine
vacancy defects at the buried interface of perovskite. Additionally,
the depth dependent grazing incident X-ray diffraction (GIXRD)
measurement demonstrated that the interfacial lattice mismatch
issue between perovskite and NiOx was alleviated by introducing
2
CBSA. As shown in Figure 3a, the slope of the 2θ–sin ϕ line was
used to estimate the residual stress of perovskite films deposited
on NiOx, NiOx/CBSA, NiOx/CB, and NiOx/BSA films, respectively.
The slope of NiOx/CBSA based perovskite film shows a smaller
value of 0.013 than that of the pure NiOx film based (0.097),
demonstrating negligible residual stress in the NiOx/CBSA based
perovskite film (the relevant schematic diagram is displayed in
Figure 3b). The self-assembled monolayers, such as 2PACz ([2-(9H-
[44]
carbazol9-yl)ethyl] phosphonic acid), and MeO-2PACz ([2-(3,6-di-
[45]
methoxy-9H-carbazol-9-yl)ethyl]phosphonic acid), have also been
employed to regulate the electric properties of NiOx. The 2PACz
and MeO-2PACz could tune the energy-level alignment between
NiOx and perovskites. Moreover, the oxygen from the phosphoryl of
the 2PACz and MeO-2PACz can passivate the defects in the surface
of NiOx and buried interface of the perovskite films by forming the
Ni‧‧‧O and Pb‧‧‧P interactions, respectively (Figures 3c—e). The
suppressed interfacial non-radiative recombination contributes to
[46]
the improved photovoltaic performance. Furthermore, a certi-
fied PCE of 24.4% was achieved by using the 2PACz modified NiOx
to fabricate flexible all-perovskite tandem solar cells.
Recently, a PCE of 24.5% has been achieved for inverted PSCs
[52]
based on the NiOx HTL by Yan and coworkers. The 1,3-bis(di-
phenylphosphino)propane (DPPP) was used to tune the NiO x/
perovskite interface and improve the stability of the PSCs. The
density functional theory calculation shows that the binding en-
ergy of DPPP with perovskites in two adjacent slabs is 3.08 eV,
which is larger than that of 2.24 eV in the single slab (Figure 3c).
Similar trend was observed for the binding energy of DPPP with
both the perovskite and NiOx slabs (4.31 eV) and that in the single
NiOx slab (3.28 eV). Thus, DPPP is predicted to bridge perovskite
grain boundaries and the perovskite/NiOx interface. After light
0
soaking, no Pb peaks were observed in the XPS spectrum of
DPPP-treated perovskite film, suggesting the suppressed photo-
decomposition of perovskite at the interface. In a word, the modi-
fied layer between perovskite and NiOx not only improved the
conductivity of NiOx, but also prevented the degradation of perov-
skite films. However, the degradation mechanism at the NiOx/
perovskite heterojunction under operational conditions is still
unclear. By using the time-resolved quadrupole mass spectrome-
try (MS) technique, Qi et al. revealed the degradation mechanism
of the NiOx/FAMAPbI3 perovskite heterojunction under the opera-
tional conditions. They introduced an aprotic bromide (TMSBr)
modified layer into the NiOx/perovskite interface, effectively in-
[43]
hibiting the perovskite degradation. As shown in Figure 3f, the
TMSBr buffer layer can suppress reaction 4 efficiently. The other
side reactions (2, 3, and 5) at elevated temperatures can also be
suppressed. The understanding of the interface chemistry be-
tween perovskite and metal oxide layers in this work provides a
new idea for interface layer screening for high-performance PSCs.
2.2. Copper thiocyanate (CuSCN)
CuSCN is a successful inorganic HTL for PSCs due to its excel-
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Chin. J. Chem.
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lent hole mobilities, wide bandgap (> 3.8 eV), high hole mobility
2 −1 −1 [56]
(0.01—0.1 cm ·V ·s ) and high optical transparency. Table 2
summarizes the device performances of CuSCN-based PSCs. The
preparation technologies of the CuSCN layer have been widely
[57] [58]
reported, such as spin coating, blade coating, spray deposi-
[59] [60]
tion, and electrochemical deposition. Various preparation
technologies brought broad prospects for the application of
CuSCN-based PSCs. However, the relatively low mobility of pure
CuSCN limits their application in PSCs. Therefore, in addition to
developing soluble CuSCN derivatives, many researchers have also
investigated the interface between CuSCN HTL and perovskite film
to improve the performance of PSCs.
2.2.1. The p-i-n architecture of CuSCN-based PSCs. Huang
[61]
et al. developed a new method to prepare CuSCN HTL by di-
rectly adding the CuSCN into a perovskite precursor solution for
inverted planar PSCs. The CuSCN not only was distributed inside
the perovskite layer but also can spontaneously move to the in-
terface between the perovskite layer and the ITO electrode, lead-
ing to the aligned energy levels for efficient transferring holes and
blocking electrons. Then the optimized PSC can achieve a PCE of
[62]
18.1%. This co-depositing a hole-conductor and a perovskite
layer can simplify the preparation process of PSCs, which could
promote their practical application and reduce the production
cost. To improve interface contact and adjust energy level match-
ing between CuSCN film and the perovskite layer, Park et al. ap-
plied the KSCN as a surface modifier to enhance the photovoltaic
[63]
properties and improve the stabilities of CuSCN-based PSCs.
This work highlights the importance of the interface between
perovskite and inorganic HTL in terms of carrier extraction and
long term stability. Doping is also an important strategy to im-
prove the electronic properties of CuSCN HTMs. A strong elec-
tron-accepting molecule, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-
quinodimethane (F4TCNQ), has been used to reduce the hole
extraction barrier in the PSCs due to its very low lowest unoccu-
pied molecular orbital (LUMO = −5.2 eV) energy level. The CuSCN
HTL doped with F4TCNQ could induce the electron transfer from
CuSCN HTL to F4TCNQ layer, which affords a more balanced ener-
gy level alignment between the perovskite and HTL layers (Figure
4a). As a result, the enhanced hole extraction capability and re-
duced energy barrier between the CuSCN/perovskite interface
were achieved.
[64]
[65]
Later, Zuo et al. found that the CuSCN film prepared by
traditional diethyl sulfide (DES) solvent exhibits fast crystallization
phenomenon, leading to numerous grain boundaries and pinholes.
Therefore, they investigated a series of pyridine-based solvents
which can form intermediates with CuSCN to adjust their crystal-
lization rate. As shown in Figures 4b, c, the pyridine derivatives
(3-chloropyridine (Cl-Py), 2-methylpyridine (Me-Py), and
4-tert-butylpyridine (TBP)) were considered as the suitable sol-
vents to delay CuSCN crystallization owing to the strong coordina-
tion bond between CuSCN and pyridine derivates. As a result, the
CuSCN film prepared by Cl-Py displays a more compact and
smooth morphology, which will benefit the perovskite growth on
[65]
the HTL (Figure 4d). The chlorine-doped CuSCN (Cl2-CuSCN) was
also utilized in PSCs to increase the conductivities of HTL and
achieved a PCE over 20%, attributing to the effective passivation
[66]
of interfacial electronic defects by chlorine doping. This work
shows the broad possibility of Cl2-doped CuSCN HTL for applica-
tion in third generation solar cell technologies.
2.2.2. The p-i-n architecture of CuSCN-based PSCs. The
CuSCN has also been widely used as HTL in regular n-i-p struc-
tured PSCs. To avoid the interface corrosive of the perovskite film
caused by the polar solvent during the CuSCN film deposition
process, a cross-linking polydimethylsiloxane (PDMS) interface
layer was spin-coated on the perovskite surface before the depo-
[67]
sition of CuSCN film. The function group in PDMS film can form
strong Cu‧‧‧O and Pb‧‧‧O interactions with both perovskite and
CuSCN (Figure 5a), which could prevent the solvent corrosive
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Figure 3 (a) Residual stress distribution (2θ data as a function of sin2ϕ) of perovskite films deposited on NiOx, NiOx/CB, NiOx/CBSA, and NiOx/BSA at
different tilt angles.[54] (b) Schematic diagrams of lattice strain distribution in perovskite grains deposited on NiOx and NiOx/CBSA substrates.[54] (c) P 2p
region of XPS spectra of ITO, ITO/2PACz and ITO/2PACz/Washed samples.[44] (d—e) The schematic diagram of ITO/ MeO-2PACz/perovskite film.[45] (f)
Possible degradation mechanism of the FAMAPbI3 perovskite with NiOx contact under 1-sun illumination conditions.[4]

Table 2 The photovoltaic parameters of the PSCs based on CuSCN film prepared by different deposition processes
Deposition method Device configuration Voc/V JSC/(mA·cm‒2) FF/% PCE/% Ref.
Electrochemical deposition ITO/CuSCN/MAPbI3/C60/BCP/Ag 1.00 21.90 75.80 16.60 61
Electrochemical deposition ITO/CuSCN/MAPbI3-xClx/C60/BCP/Ag 1.04 22.80 76.10 18.10 62
Electrochemical deposition ITO/CuSCN/KSCN/MAPbI3/PC61BM/BCP/Ag 1.01 19.20 77.00 14.90 63
Electrochemical deposition ITO/CuSCN/F4TCNQ/MAPbI3/PC61BM/BCP/Ag 0.99 21.01 72.00 15.01 64
Spin coating ITO/CuSCN/MAPbI3/PC61BM/BCP/Ag 1.10 22.28 78.00 19.19 65
Spin coating ITO/Cl2-CuSCN/MAPbI3/C60/BCP/Ag 1.12 23.00 78.00 20.10 66
Spin coating ITO/SnO2/MAPbI3/PDMS/CuSCN/Au 1.02 23.90 78.30 19.04 67
Spin coating FTO/TiO2/PVSK/NiOx/CuSCN/Au 1.08 20.78 61.76 13.88 68
Spin coating FTO/TiO2/PVSK/CuSCN/rGo/Au 1.11 23.24 78.20 20.40 69
Spin coating ITO/SnO2/PVSK/CuSCN/DTB/Au 1.15 24.31 78.58 22.00 70
Spin coating FTO/C-TiO2/mTiO2/(FAPbI3)0.92(MAPbBr3)0.08/CuSCN-DEE/Au 1.04 24.16 73.00 18.34 71
Spin coating FTO/TiO2/MAPbI3/CuCuSCN:Spiro-OMeTAD/Ag 1.06 22.01 77.00 18.02 72
Blade coating ITO/SAM/PVSK/CuSCN/Ta-WOx/C 1.01 17.21 71.00 12.31 73

effect during CuSCN film solution preparation and reduce the
interface defects. As shown in Figure 5b, the time-of-flight sec-
ondary-ion mass spectroscopy (ToF-SIMS) shows that most of the
PDMS polymers exist at the interface between perovskite and
CuSCN layer, which significantly improve the stability of CuSCN-
based PSC. The enhanced stability of PSC was confirmed by di-
rectly putting the deceives with/without PDMS treatments into
water (Figure 5c), and it is found that the interlayer of PDMS can
effectively hinder the penetration or diffusion of external H 2O
molecules through the device. The NiOx/CuSCN bilayer structure
was also an effective strategy for suppressing the interfacial deg-
[68]
radation of perovskite and HTL. Recently, Wei and coworkers
proposed an antisolvent-treatment approach for the DES-pro-
cessed CuSCN to mitigate solvent residue induced degradation of
[71]
perovskite. Antisolvent-treatment is a facile and effective
method for preparing high-quality CuSCN films, which can deli-
cately adjust the perovskite film morphology. The chemical reac-
tion between CuSCN film and electrode was often observed. Spe-
cifically, the electrode elements could migrate into the CuSCN
layer and form impurity phases with high resistivities, such as
−
gold-thiocyanate (SCN ), which is detrimental to the photovoltaic
performance. Therefore, designing an inorganic–organic double
HTL by applying an ultrathin polymer layer of dithiophene-ben-
zene (DTB) to the interface between the CuSCN and Au electrode
[70]
was an effective alternative. Moreover, the double layer of
CuSCN/DTB could enhance the hole extract ability by forming the
cascaded energy levels. The pinhole-free and compact DTB film
was successfully detected on the CuSCN surface (Figure 5d), which
could reduce the defect site and recombination center of the
CuSCN surface (Figure 5e). Consequently, the PSC based on

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Inorganic Hole-Transport Materials for Perovskite Solar Cells

Figure 4 (a) The comparison of energy level alignment of perovskite/CuSCN/ITO with and without F4TCNQ doping.[64] (b) Chemical structures of Cl-Py,
Me-Py, and TBP ligands.[65] (c) Photographs of the vials containing the CuSCN/DES, CuSCN/Cl-Py, CuSCN/Me-Py, and CuSCN/TBP solutions.[65] (d) AFM
surface topography images of CuSCN samples spin coated on ITO glass by various methods.[65]

Table 3 The photovoltaic parameters of the representative PSCs based on CuI

Deposition method Device configuration Voc/V JSC/(mA·cm‒2) FF/% PCE/% Ref.
Chemical vapor deposition FTO/CuI/MAPbI3/PC61BM/PEI/Ag 1.04 20.9 68.00 14.70 78
Spin coating ITO/PTAA/CuI/MAPbI3/PC61BM/PEI/Ag 1.10 23.93 78.60 20.20 79
Spin coating ITO/CuI/MAPbI3/C60/BCP/Ag 1.01 22.80 73.00 16.80 80
Spin coating ITO/NiO/CuI/MAPbI3/PC61BM/BCP/Ag 1.07 20.60 69.00 15.26 81
Spin coating TO/CuI/PEDOT:PSS/MAPbI3/PC61BM/ZnO/Al 0.92 20.50 76.00 14.30 82
Spin coating ITO/Cu(Tu)I/MAPbI3-xClx/C60/BCP/Ag 1.13 22.30 78.90 19.90 83
Vacuum evaporation FTO/TiO2/MAPbI3−xClx/CuI/Au 0.73 16.40 54.00 6.40 84
Blade coating FTO/TiO2/MAPbI3/CuI/C 0.78 16.70 57.00 7.50 85
Spin coating FTO/TiO2/MAPbI3/CuI:Spiro-OMeTAD/Ag 1.06 21.52 73.00 16.67 72
Spray-deposition FTO/TiO2/MAPbI3/CuI/Au 1.03 22.78 75.00 17.60 86

CuSCN/DTB layer achieved a remarkable PCE of 22.0%. Grätzel
et al. inserted the reduced graphene oxide (rGO) between CuSCN
‒
and Au layers to prevent the reaction between the gold and SCN
[69]
group. The PSCs exhibit excellent stability and retain over 95%
of their initial efficiency after tracking at a maximum power point
for 1000 h under full solar intensity at 60 °C. All the works show
that combined with solvent engineering and interlayer strategy,
the modified CuSCN can be considered as the outstanding HTL to
obtain the remarkable PSCs with excellent environmental and
operational stability.
2.3. Copper(I) iodide (CuI)
The γ-phase CuI behaves like a p-type semiconductor and ex-
[74-75]
hibits good chemical stability. The merits of CuI, such as its
2 −1 −1
large bandgap (3.1 eV), high hole mobility (0.2—2 cm ·V ·s ),
[56]
and good solution processability, make it a widely used HTL in
both p-i-n and n-i-p PSCs. The device performances of representa-
tive CuI-based PSCs are shown in Table 3. The various technolo-
gies used to prepare high-quality CuI film have been reported,
[15]
such as the spin coating method, chemical vapor deposition
[76] [77]
(CVD), and blade coating method.
2.3.1. CuI for p-i-n structured PSCs. For inverted PSCs, the CuI
[80]
HTL was generally prepared by spin-coating method. Huang
and coworkers reported CuI-based PSCs and achieved an impres-
sive PCE of 16.8% with enhanced air stability compared to the
[80]
PEDOT:PSS-based. However, the CuI based PSCs typically pro-
cessed a low PCE due to the severe interface trap states between
CuI and the perovskite layer. Thus, constructing the multilayer HTL
or composite HTL containing CuI as an interlayer for normal HTL is
an effective method to reduce the surface defects of the original
[82]
HTL. The strategy of double HTLs was considered as an excel-
lent method to align the energy levels between the perovskite

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Recent Advances
Figure 5 (a) Schematics of the cross-linking PDMS interlayer.[67] (b) The ToF-SIMS depth profile analysis for the PDMS-interlayered device.[67] (c) Photo-
graphs of devices without and with the PDMS interlayer dipped in water.[67] (d) Cross-sectional SEM image of CuSCN/DTB-based device.[70] (e) AFM images
of corresponding films.[70]
and ITO. Inserting the CuI HTL between acidic PEDOT:PSS and ITO
[81]
could significantly improve the device stability. Saranin et al.
prepared several NiO/CuI double HTLs by directly spin-coating CuI
solution with different concentrations onto the surface of NiOx
film and investigated the surface defect changes of the NiO x HTL.
The surface trap density of NiOx could be suppressed by the pre-
cise control of the morphology of the CuI, resulting in an im-
proved PCE from 10% to 15.26%. Another double HTL of PTAA/CuI
reported by Hou and coworkers showed that the CuI film not only
improved the wettability of PTAA but also promoted the crystalli-
zation of the perovskite film. As shown in Figures 6a, b, after
treating the PTAA with CuI, the perovskite film quality and the
crystal size were significantly improved. Based on this CuI-modi-
fied HTL, the PSCs can obtain a maximum PCE of up to 20.20%. In
addition, CuI and its derivates could also be used as p-type con-
ductor additives to passivate the bulk perovskite defects. The
possible mechanism of the trap state passivation in bulk perov-
skite by the p-type additives CuI and Cu(thiourea)I (Cu(Tu)I in Fig-
ure 6c) was revealed by Huang et al., using the temperature-de-
pendent admittance spectra (Figure 6d). They found that the
p-type additives can passivate the defects by interaction with the
under-coordinated metal cations and the halide anions at the
perovskite surface. The Cu(Tu)I has more significant effects than
traditional p-type conductor CuI in the above two aspects, which
can be attributed to Cu(Tu)I more matched VBM with perovskite,
[83]
shallowing its trap state energy level (Figure 6e). The trap state
passivation in PSCs is very significant and complicated, however,
this work can guide further research and exploration of the per-
ovskite passivation.
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2.3.2. CuI for n-i-p structured PSCs. In the regular n-i-p struc-
tured PSCs, Xin et al. prepared the CuI HTL by a facile
[86]
spray-deposition method and archived a PCE of 17.6%. Cao et
al. used the resistance evaporation method to fabricate the CuI
HTL, and they found that the I distribution in the CuI film can be
[84]
affected by the deposition rate. Spiccia et al. prepared the CuI
[85]
HTL on the top of the perovskite by a blade coating method. By
controlling the type of solvent and the blade speed, the corrosive
effect of polar solvent on the perovskite film was inhibited. Com-
pared with the Spiro-OMeTAD-based device, the J-V curves of
CuI-based PSCs showed simultaneous improved stability and effi-
ciency with negligible hysteresis due to its high and more bal-
anced mobilities.
2.4. Copper oxides (CuxO)
Stable CuxO, such as cuprous oxide (Cu2O) and cupric oxide
(CuO), are well-known p-type semiconductors with bandgaps of
2.1 and 1.3 eV, respectively. CuxO has been used as HTL in PSCs
owing to their advantages of high transparency, abundant availa-
2 −1 −1
bility, high hole mobility (100 cm ·V ·s ) and multiple prepara-
[10]
tion methods. The preparation methods of CuxO film include
[87] [88] [77,89]
electrostatic spinning, spray deposition, spin coating,
[90] [91]
electrochemical deposition, sputtering, vacuum evapora-
[92]
tion, and so on. So far, various strategies, such as developing
the appropriate synthesis technology, adding additives, and in-
troducing modifiers, have been reported to improve the film qual-
[93]
ity and conductivity of the CuxO HTL. The photovoltaic param-
eters and device structures of the PSCs based on CuxO films pre-
pared by different deposition processes are summarized in Table 4.
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Inorganic Hole-Transport Materials for Perovskite Solar Cells

Figure 6 Top view SEM images of perovskite films on (a) PTAA and (b) PTAA/CuI.[79] (c) Crystal structure of Cu(Tu)I. Hydrogen atoms have been omitted
for clarity.[83] (d) Admittance spectra of the reference PSCs and the devices with CuI or Cu(Tu)I treatments, measured at temperature between 230 and
300 K with a step of 10 K.[83] (e) Schematic illustration of possible mechanism for the trap state passivation.[83]

Table 4 The photovoltaic parameters of the representative PSCs based on CuxO films
Deposition method Device configuration Voc/V JSC/(mA·cm‒2) FF/% PCE/% Ref.
Spin-coating sol ITO/CuxO-UV-ozone/MAPbI3/C60/BCP/Ag 0.99 23.20 74.40 17.10 94
Spray deposition ITO/CuxO/MAPbI3/C60/BCP/Al 0.70 17.22 48.00 5.83 88
ITO/CuO/PEDOT:PSS/PVSK/PC61BM/
Electrostatic spinning 4,7-diphenyl-1,10-phenanthroline (Bphen)/Ag 0.98 22.06 78.00 16.87 87
Electrochemical FTO/Cu2O/PVSK/C60/Bphen/Ag 0.88 18.03 61.00 9.64 90
Spin-coating sol ITO/Cu2O/MAPbI3/PC61BM/Al 1.07 16.52 75.51 13.35 77
Spin-coating sol ITO/CuxO/MAPbI3−xClx/C60/BCP/Ag 1.11 22.50 76.00 19.00 95
Spin-coating sol ITO/CuxO/MAPbI3/PC61BM/ZnO/Al 1.03 22.26 76.00 17.43 96
Sputtering FTO/TiO2/PVSK/Spiro-OMeTAD/CuxO-Ny/Au 1.04 19.84 75.87 15.73 91
Spin-coating NPs FTO/mp-TiO2/Cs0.05FA0.81MA0.14PbI2.55Br0.45/Cu2O/Au 1.15 22.20 74.20 18.90 97
Vacuum evaporation FTO/SnO2/PC61BM/PVSK/FBT-Th4/CuxO/Au 1.12 22.35 75.40 18.85 92
Spin-coating NPs FTO/TiO2/MAPbI3/Cu2O/Au 1.13 22.53 67.36 17.23 89

[94]
2.4.1. CuxO for p-i-n structured PSCs. Huang et al. reported
CuxO hole transport layer for the inverted PSCs by directly
spin-coating a cupric acetylacetonate precursor solution onto an
ITO substrate. It was found that the prepared CuxO film treated
with ultraviolet–ozone treatment exhibited decreased VBM due to
2+
the increased oxygen and Cu concentration, which could align
the energy levels between CuxO/perovskite interface and improve
hole extraction and transportation. The optimized devices can
[95]
obtain a high PCE of 17.1%. Huang et al. introduced PbCl2 into
perovskite precursor to reduce the intrinsic defects of perovskite,
achieving a PCE of 19.0% for CuxO-based PSCs. This novel Cl dop-
ing process plays a crucial role to adjust the morphology of per-
ovskite, leading to reduced intrinsic defects in the film and in-
creased device recombination resistance.
2.4.2. CuxO for n-i-p structured PSCs. Due to their outstanding
stability, the CuxO has also been used as HTL in inverted n-i-p
structured PSCs. Song et al. synthesized the CuxO nanoparticles at
[89]
room temperature through a wet chemical method. The corre-
sponding device maintains over 90% of its initial efficiency after
30 d when stored in ambient air without encapsulation. This work
demonstrated that the CuxO could be a promising hole-trans-
porting material for efficient and stable PSCs. To further improve
the film quality of CuxO, a surface modification strategy for CuxO
quantum dots was proposed by Xu and coworkers by utilizing a
[97]
silane coupling agent. The hydrophobic Cu2O can be formed in
situ by reacting with silane molecules to form covalent bonds on
the surface. As a result, the modified CuxO could be well dispersed
in a nonpolar solvent, which helps form a high-quality HTL layer

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Recent Advances
(Figure 7a). Three types of modified CuxO nanoparticles were
synthesized by combining CuxO with three silane coupling agents
with different terminals (groups ethylene, octadecyl, or amino)
and their hydrophobicity was explored. As shown in Figure 7b, the
CuxO film decorated by 3-aminopropyltriethoxysilane shows a
small water contact angle indicating its strong hydrophilicity,
which is difficult to disperse in a nonpolar solvent. In contrast, the
octadecyltriethoxysilane modified CuxO film exhibits enhanced
hydrophobicity with a larger water contact angle because of the
incorporation of the hydrophobic octadecyl groups, which pro-
mote the dispersion of CuxO in a nonpolar solvent. The modifica-
tion mechanisms between the silane coupling agent and CuxO are
illustrated in Figure 7c. The modified CuxO could be directly de-
posited as the top HTL on the perovskite layer to facilitate charge
extraction and separation. Fan et al. constructed the conjugated
polymer FBT-Th4/CuxO double HTL to promote hole extraction in
[92]
n-i-p PSCs achieving an enhanced PCE of 18.85%. This HTL can
block any accessible water permeation pathways into the device,
preventing the perovskite from moisture-caused damage. Unlike
LiTFSI doped spiro-OMeTAD, the FBT-Th4/CuxO obviously increas-
es the stability of PSCs.
Figure 7 (a) Schematic illustration of the deposition process of the CuxO
film.[97] (b) Contact angle measurements of the CuxO films prepared with
these silane coupling agents.[97] (c) The interface modification mechanism
of the silane coupling agents on CuxO.[97] (d) The change in the interfacial
energy band after adding MoO3.[98]
2.5. Copper sulfides (CuS)
The CuS is another classical p-type HTM with a high conduc-
‒2 [99]
tivity of 2.7 S·cm . However, the device performances are lim-
ited by the large energy barrier between the perovskite and
[99]
CuS-based HTL (VBM = ‒5.1 eV). Different strategies have been
developed to solve this issue, such as adjusting the ratio of Cu :
[100-101]
S, and preparing ternary or quaternary derivatives for
[102] [100]
CuS. The CuS films could be prepared by spin-coating,
[103] [104]
blade coating, spray deposition, and vacuum evapora-
[105]
tion methods. Table 5 introduces the photovoltaic properties
and device structures of the PSCs based on CuxS and CuS deriva-
tive films prepared by different deposition processes.
[106]
2.5.1. CuS for p-i-n structured PSCs. Huang et al. first ap-
plied CuS as HLT in an inverted PSC by a low-cost solution-pro-
cessed method. They found that the CuS can tune the surface
work function and improve the hole collection efficiency from the
perovskite. The surface roughness and transmittance of ITO sub-
strates can be maintained after depositing a CuS layer. Compared
with the perovskite devices without HTL, the devices employing
CuS HTL displayed a PCE over 16% with excellent reproducibility
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and stability.
2.5.2. CuxS and CuS derivatives for n-i-p structured PSCs. The
CuxS and CuS derivatives have also been used as HTLs in inverted
[107] [100]
n-i-p structured PSCs. Zhao et al. reported a Spiro-
OMeTAD/Cu9S5 integrated HTL by a solution-processed method
for PSCs. Due to the matched energy levels, the holes can be
quickly extracted and separated in PSC based on the Spiro-
OMeTAD/Cu9S5 integrated HTL, achieving a PCE of 17.10%. A Spi-
ro-OMeTAD/Cu1.75S double-hole layer was developed to protect
the Spiro-OMeTAD layer against damage from both the top Au
[105]
anode and moisture erosion. Moreover, the Cu1.8S also can
[101]
adjust the conductivity and hole mobility of Spiro-OMeTAD.
The PSC based on Cu1.8S-doped HTL showed a remarkable PCE of
[104]
21.64% with negligible hysteresis. Liu et al. reported a ternary
derivative, copper antimony sulfide (Cu3SbS4) nanocrystals, as the
HTL for PSCs. It is found that the Cu3SbS4 nanocrystal layer could
enhance hole extraction and inhibit the charge-carrier recombi-
nant at the interface between perovskite and electron. Dai et
[102]
al. used ZnS-passivated copper indium disulfide (CuInS2) as the
HTL, achieving an improved performance of 8.4% compared with
[108]
pure CuInS2-based. In 2021, Zhang et al. synthesized colloidal
CsCu5S3 nanocrystals as an interlayer between Spiro-OMeTAD and
bulk perovskite film by a facile colloidal chemistry method. The
prepared CsCu5S3 film can passivate the surface trap states of the
perovskite film and adjust energy alignment with the energy level
of perovskite and Spiro-OMeTAD. As a result, the device delivered
a champion PCE of 22.29%. The results indicate that CsCu5S3 is a
promising THL for stable and efficient PSCs.
2.6. Molybdenum oxides (MoOx)
The MoOx have been successfully applied as HTLs in PSCs due
to their optical transparency, adequate conductivity, and high WF
(the WF of air-exposed MoOx and vacuum-deposited MoOx are 5.5
[108]
eV and 6.7 eV, respectively). At present, the preparation tech-
[109]
nologies of MoOx mainly include vacuum evaporator, spin-
[110]
coating, and so on. However, directly preparing MoOx film on
the perovskite surface could lead to a chemical reaction and poor
contact between them, resulting in decreased device perfor-
[111-112]
mance. Incorporating with an intermediate layer between
the MoOx and perovskite layer was considered to be an efficient
strategy to inhibit interfacial degradation. As shown in Table 6, the
preparation technologies of MoOx mainly include vacuum evapo-
[109] [110]
rator and spin-coating.
2.6.1. MoOx for p-i-n structured PSCs. For the inverted PSCs,
the high energy barrier of MoOx inhibits effective hole extraction.
The utilization of solution-processed MoO3 as an HTM in the in-
verted PSCs is currently limited. Chen et al. and Shao et al. have
explored the use of a PEDOT:PSS: MoO3 composite film as the HTL
in PSCs, aiming to benefit from the high conductivity of PEDOT:PSS
[117-118]
and the ambient stability of MoO3. However, it is worth
noting that direct contact between PEDOT:PSS and ITO (Indium
Tin Oxide) still occurs, which does not completely prevent the
erosion of ITO by PEDOT:PSS. More importantly, the MoOx will
[111-112,119]
react with the perovskite, creating recombination sites.
However, these issues can be overcome using interlayers, which
could improve the energy-level alignment, and avoid interfacial
[113]
degradation. Choi et al. introduced a PEDOT:PSS layer on the
MoOx surface in p-i-n structure PSCs to obtain a desirable energy
level alignment between the MoOx and the perovskite. The device
based on the MoOx/PEDOT:PSS double-hole layers achieved a PCE
[114]
of 18.8%. Wang et al. demonstrated that introducing a thin
layer of an organic molecule (F4TCNQ) between MoOx and perov-
skite could regulate the perovskite film morphology, hence de-
creasing the trap defect at the interface. The 2,2′,2″-(1,3,5-ben-
zinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) as an interlayer
had been deposited between the MoOx and perovskite layer to
inhibit the chemical reaction and promote efficient charge extrac-
[109]
tion, leading to a PCE of 19.0%.
Chin. J. Chem. 2023, 41, 3373—3387
 Chin. J. Chem.

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Inorganic Hole-Transport Materials for Perovskite Solar Cells

Table 5 The photovoltaic parameters of the representative PSCs based on CuxS and CuS derivative films
Deposition method Device configuration Voc/V JSC/(mA·cm‒2) FF/% PCE/% Ref.
Spin-coating ITO/CuS/MAPbI3/C60/BCP/Ag 1.02 22.3 71.20 16.20 106
Spray deposition FTO/SnO2/PVSK/Cu3SbS4/Au 0.80 19.40 55.96 8.70 104
Blade coating FTO/TiO2/MAPbI3/C:CuS/Ag 0.98 18.26 63.23 11.28 103
Spin-coating NPs ITO/SnO2/MAPbI3/undoped Spiro-OMeTAD/Cu9S5/Au 1.05 22.32 73.00 17.10 100
Spin-coating FTO/C-TiO2/Cs0.05FA0.81MA0.14PbI2.55Br0.45/Spiro-OMeTAD:Cu1.9S/Au 1.14 24.12 78.70 21.64 101
Spin-coating FTO/C-TiO2/MAPbI3/Spiro-OMeTAD:Cu9S5@SiO2/Ag 1.05 23.14 74.95 18.21 107
Vacuum evaporation FTO/SnO2/MAPbI3/Spiro-OMeTAD/CuxS/Au 1.13 23.10 71.50 18.58 105
Spin-coating FTO/TiO2/MAPbI3/CuInS2/Au 0.88 16.60 45.10 6.57 102
Spin-coating FTO/TiO2/MAPbI3/CuInS2/ZnS/Au 0.94 18.60 48.70 8.38 102
Spin-coating ITO/SnO2/MAPbI3/CsCu5S3/Spiro-OMeTAD/Au 1.10 14.84 81.38 22.29 108

Table 6 The photovoltaic parameters of the representative PSCs based on MoOx films
Deposition method Device configuration Voc/V JSC/(mA·cm‒2) FF/% PCE/% Ref.
Vacuum evaporation ITO/MoOx/PEDOT:PSS/MAPbI3/C60/BCP/LiF/Al 0.97 22.60 83.00 18.20 113
Spin-coating ITO/MoOx/PEDOT:PSS/MAPbI3/C60/Bphen/Ag 0.96 20.06 67.00 12.78 110
Spin-coating ITO/MoOx/F4-TCNQ/MAPbI3/PC61BM/BCP/Ag 1.06 20.17 76.00 16.26 114
ITO/MoOx/TPBi/N4,N4,N4′,N4′-tetra(*1,1′-biphenyl]-4-yl)-*1,1′:
Vacuum evaporation 1.08 21.40 82.00 19.00 109
4′,1′-terphenyl]-4,4′-diamine (TaTm)/MAPbI3/C60/BCP/Au
Vacuum evaporation ITO/SnO2/(FAPbI3)0.85(MAPbBr3)0.15/Spiro-OMeTAD/MoO3/Ag 1.11 23.31 72.00 18.63 115
Vacuum evaporation ITO/TiO2/C60/MAPbI3/TaTm/TPBi/MoOx/Au 1.08 21.30 81.40 18.80 109
Vacuum evaporation ITO/SnO2/FAPbI3/Spiro-OMeTAD/MoO3/Ag 1.18 25.30 81.36 24.37 116

2.6.2. MoOx for n-i-p structured PSCs. Incorporating with a
thin MoOx between the HTL and top electrode as an interface
layer could improve hole extraction in n-i-p structured PSCs and
protect the perovskite film from damage caused by metal elec-
[116,120-121] [98]
trode deposition. Kahn et al. deposited a thin MoOx
layer between the Spiro-MeOTAD and the Ag electrode layers to
tune the energy-level alignment and inhibit the chemical reaction
between them, facilitating efficient hole extraction (Figure 7d).
[115]
Zhu et al. introduced the same process to achieve improved
PSCs with PCE increased from 17.02% to 18.62%. UPS results
show that the VBM of MoOx interlayer modified Spiro-MeOTAD
exhibits 0.5 eV decline in comparison with that of MAPbI 3 layer,
leading to an increased Fermi energy. It is noteworthy that adding
the MoOx layer can protect the Spiro-OMeTAD layer against dam-
age from both the top metal electrode and moisture erosion.
3. Conclusions and Perspectives
Overall, we have summarized the recent progress of PSCs
based on inorganic HTMs. Although excellent moisture and ther-
mal stability has been demonstrated, the PSCs based on inorganic
HTLs still showed relatively inferior PCEs in comparison with that
of devices based on organic HTMs. To achieve high efficiency in
inorganic HTL-based PSCs still presents certain challenges. Firstly,
it is crucial to develop a suitable interfacial layer between the
perovskites and the inorganic HTM. This layer helps in adjusting
the energy alignment and reducing surface defects in the inor-
ganic HTL. Secondly, the fabrication of compact and pinhole-free
HTLs through solution processes requires careful selection of sol-
vents. Additionally, incorporating appropriate dopants into inor-
ganic HTL can enhance its conductivity, providing an efficient
method to improve overall device performance. Thirdly, the
search for and development of novel inorganic HTMs remains a
vital research direction. Lastly, developing fabrication processes
for inorganic HTL-based PSCs that are scalable and suitable for
large-scale production is another challenge. We believe that the
continued advancement of efficient inorganic HTLs will contribute
to enhancing the efficiency and stability of PSCs.
Acknowledgement
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (Grants No.
52273182), and the National Key Research and Development Pro-
gram of China (Grant No. 2019YFA0705900).
References
[1] Zhao, Y.; Zhu, K. Organic-inorganic hybrid lead halide perovskites for
optoelectronic and electronic applications. Chem. Soc. Rev. 2016, 45,
655‒689.
[2] Kim, J. Y.; Lee, J.-W.; Jung, H. S.; Shin, H.; Park, N.-G. High-Efficiency
Perovskite Solar Cells. Chem. Rev. 2020, 120, 7867‒7918.
[3] Correa-Baena, J.-P.; Abate, A.; Saliba, M.; Tress, W.; Jesper Jacobsson,
T.; Grätzel, M.; Hagfeldt, A. The rapid evolution of highly efficient
perovskite solar cells. Energy Environ. Sci. 2017, 10, 710‒727.
[4] Stranks, S. D.; Eperon, G. E.; Grancini, G.; Menelaou, C.; Alcocer, M. J.;
Leijtens, T.; Herz, L. M.; Petrozza, A.; Snaith, H. J. Electron-hole diffu-
sion lengths exceeding 1 micrometer in an organometal trihalide
perovskite absorber. Science 2013, 342, 341‒344.
[5] Guo, S.; Liu, K.; Rao, L.; Hu, X.; Chen, Y. Preparation of Perovskite So-
lar Cells in the Air: Degradation Mechanism and Prospects on Large‐
Area Fabrication. Chin. J. Chem. 2023, 41, 599‒617.
[6] Park, J.; Kim, J.; Yun, H. S.; Paik, M. J.; Noh, E.; Mun, H. J.; Kim, M. G.;
Shin, T. J.; Seok, S. I. Controlled growth of perovskite layers with vol-
atile alkylammonium chlorides. Nature 2023, 616, 724‒730.
[7] Shao, J.-Y.; Li, D.; Shi, J.; Ma, C.; Wang, Y.; Liu, X.; Jiang, X.; Hao, M.;
Zhang, L.; Liu, C.; Jiang, Y.; Wang, Z.; Zhong, Y.-W.; Liu, S. F.; Mai, Y.;
Liu, Y.; Zhao, Y.; Ning, Z.; Wang, L.; Xu, B.; Meng, L.; Bian, Z.; Ge, Z.;
Zhan, X.; You, J.; Li, Y.; Meng, Q. Recent progress in perovskite solar
cells: material science. Sci. China Chem. 2023, 66, 10‒64.
[8] Sheibani, E.; Yang, L.; Zhang, J. Recent Advances in Organic Hole

Chin. J. Chem. 2023, 41, 3373—3387 © 2023 SIOC, CAS, Shanghai, & WILEY-VCH GmbH www.cjc.wiley-vch.de 3383
Recent Advances
Transporting Materials for Perovskite Solar Cells. Sol. RRL 2020, 4,
2000461.
[9] Elseman, A. M.; Sajid, S.; Shalan, A. E.; Mohamed, S. A.; Rashad, M.
M. Recent progress concerning inorganic hole transport layers for ef-
ficient perovskite solar cells. Appl. Phys. A 2019, 125, 476.
[10] Jing, X.; Zhang, Z.; Chen, T.; Luo, J. Review of Inorganic Hole
Transport Materials for Perovskite Solar Cells. Energy Technol. 2023,
11, 2201005.
[11] Singh, R.; Singh, P. K.; Bhattacharya, B.; Rhee, H.-W. Review of cur-
rent progress in inorganic hole-transport materials for perovskite
solar cells. Appl. Mater. Today 2019, 14, 175‒200.
[12] Liu, J.; Pathak, S. K.; Sakai, N.; Sheng, R.; Bai, S.; Wang, Z.; Snaith, H. J.
Identification and Mitigation of a Critical Interfacial Instability in
Perovskite Solar Cells Employing Copper Thiocyanate
Hole-Transporter. Adv. Mater. Interfaces 2016, 3, 1600571.
[13] Yin, X.; Song, Z.; Li, Z.; Tang, W. Toward ideal hole transport materials:
a review on recent progress in dopant-free hole transport materials
for fabricating efficient and stable perovskite solar cells. Energy En-
viron. Sci. 2020, 13, 4057‒4086.
[14] Yao, Y.; Cheng, C.; Zhang, C.; Hu, H.; Wang, K.; De Wolf, S. Organic
Hole-Transport Layers for Efficient, Stable, and Scalable Inverted
Perovskite Solar Cells. Adv. Mater. 2022, 34, 2203794.
[15] Chen, W.-Y.; Deng, L.-L.; Dai, S.-M.; Wang, X.; Tian, C.-B.; Zhan, X.-X.;
Xie, S.-Y.; Huang, R.-B.; Zheng, L.-S. Low-cost solution-processed
copper iodide as an alternative to PEDOT:PSS hole transport layer for
efficient and stable inverted planar heterojunction perovskite solar
cells. J. Mater. Chem. A 2015, 3, 19353‒19359.
[16] Elbohy, H.; Bahrami, B.; Mabrouk, S.; Reza, K. M.; Gurung, A.; Pathak,
R.; Liang, M.; Qiao, Q.; Zhu, K. Tuning Hole Transport Layer Using
Urea for High‐Performance Perovskite Solar Cells. Adv. Funct. Mater.
2019, 29, 1806740.
[17] Zhang, H.; Zhao, C.; Yao, J.; Choy, W. C. H. Dopant-free NiOx Nano-
crystals: A Low-cost and Stable Hole Transport Material for Commer-
cializing Perovskite Optoelectronics. Angew. Chem. Int. Ed. 2023, 62,
e202219307.
[18] Chen, J.; Park, N.-G. Inorganic Hole Transporting Materials for Stable
and High Efficiency Perovskite Solar Cells. J. Phys. Chem. C 2018, 122,
14039‒14063.
[19] Yin, X.; Guo, Y.; Xie, H.; Que, W.; Kong, L. B. Nickel Oxide as Efficient
Hole Transport Materials for Perovskite Solar Cells. Sol. RRL 2019, 3,
1900001.
[20] Wang, K. C.; Jeng, J. Y.; Shen, P. S.; Chang, Y. C.; Diau, E. W.; Tsai, C.
H.; Chao, T. Y.; Hsu, H. C.; Lin, P. Y.; Chen, P.; Guo, T. F.; Wen, T. C.
p-Type mesoscopic nickel oxide/organometallic perovskite hetero-
junction solar cells. Sci. Rep. 2014, 4, 4756.
[21] Jung, J. W.; Chueh, C. C.; Jen, A. K. A Low-Temperature, Solu-
tion-Processable, Cu-Doped Nickel Oxide Hole-Transporting Layer via
the Combustion Method for High-Performance Thin-Film Perovskite
Solar Cells. Adv. Mater. 2015, 27, 7874.
[22] Yin, X.; Chen, P.; Que, M.; Xing, Y.; Que, W.; Niu, C.; Shao, J. Highly
Efficient Flexible Perovskite Solar Cells Using Solution-Derived NiOx
Hole Contacts. ACS Nano 2016, 10, 3630‒3636.
[23] Zhao, L.; Su, G.; Liu, W.; Cao, L.; Wang, J.; Dong, Z.; Song, M. Optical
and electrochemical properties of Cu-doped NiO films prepared by
electrochemical deposition. Appl. Surf. Sci. 2011, 257, 3974‒3979.
[24] Kim, J. H.; Liang, P. W.; Williams, S. T.; Cho, N.; Chueh, C. C.; Glaz, M.
S.; Ginger, D. S.; Jen, A. K. High-performance and environmentally
stable planar heterojunction perovskite solar cells based on a solu-
tion-processed copper-doped nickel oxide hole-transporting layer.
Adv. Mater. 2015, 27, 695‒701.
[25] Chen, X.; Zhao, L.; Niu, Q. Electrical and Optical Properties of p-Type
Li, Cu-Codoped NiO Thin Films. J. Electron. Mater. 2012, 41, 3382‒
3386.
[26] Xu, L.; Chen, X.; Jin, J.; Liu, W.; Dong, B.; Bai, X.; Song, H.; Reiss, P. In-
verted perovskite solar cells employing doped NiO hole transport
layers: A review. Nano Energy 2019, 63, 103860.
[27] Wang, Q.; Chueh, C. C.; Zhao, T.; Cheng, J.; Eslamian, M.; Choy, W. C.
H.; Jen, A. K. Effects of Self-Assembled Monolayer Modification of
3384 www.cjc.wiley-vch.de © 2023 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Wang, Dong & Liu
16147065, 2023, 23, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cjoc.202300252 by University Of Belgrade, Wiley Online Library on [26/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Nickel Oxide Nanoparticles Layer on the Performance and Applica-
tion of Inverted Perovskite Solar Cells. ChemSusChem 2017, 10,
3794‒3803.
[28] Park, J. H.; Seo, J.; Park, S.; Shin, S. S.; Kim, Y. C.; Jeon, N. J.; Shin, H.
W.; Ahn, T. K.; Noh, J. H.; Yoon, S. C.; Hwang, C. S.; Seok, S. I. Efficient
CH3NH3PbI3 Perovskite Solar Cells Employing Nanostructured p-Type
NiO Electrode Formed by a Pulsed Laser Deposition. Adv. Mater.
2015, 27, 4013.
[29] Bai, Y.; Chen, H.; Xiao, S.; Xue, Q.; Zhang, T.; Zhu, Z.; Li, Q.; Hu, C.;
Yang, Y.; Hu, Z.; Huang, F.; Wong, K. S.; Yip, H.-L.; Yang, S. Effects of a
Molecular Monolayer Modification of NiO Nanocrystal Layer Surfac-
es on Perovskite Crystallization and Interface Contact toward Faster
Hole Extraction and Higher Photovoltaic Performance. Adv. Funct.
Mater. 2016, 26, 2950‒2958.
[30] Boyd, C. C.; Shallcross, R. C.; Moot, T.; Kerner, R.; Bertoluzzi, L.; Onno,
A.; Kavadiya, S.; Chosy, C.; Wolf, E. J.; Werner, J.; Raiford, J. A.; de
Paula, C.; Palmstrom, A. F.; Yu, Z. J.; Berry, J. J.; Bent, S. F.; Holman, Z.
C.; Luther, J. M.; Ratcliff, E. L.; Armstrong, N. R.; McGehee, M. D.
Overcoming Redox Reactions at Perovskite-Nickel Oxide Interfaces to
Boost Voltages in Perovskite Solar Cells. Joule 2020, 4, 1759‒1775.
[31] Ratcliff, E. L.; Meyer, J.; Steirer, K. X.; Garcia, A.; Berry, J. J.; Ginley, D.
S.; Olson, D. C.; Kahn, A.; Armstrong, N. R. Evidence for near-Surface
NiOOH Species in Solution-Processed NiOx Selective Interlayer Mate-
rials: Impact on Energetics and the Performance of Polymer Bulk
Heterojunction Photovoltaics. Chem. Mater. 2011, 23, 4988‒5000.
[32] Lany, S.; Osorio-Guillén, J.; Zunger, A. Origins of the doping asym-
metry in oxides: Hole doping in NiO versus electron doping in ZnO.
Phys. Rev. B 2007, 75, 241203.
[33] Wu, F.; Yan, K.; Wu, H.; Guo, Y.; Shan, S.; Chen, T.; Fu, W.; Zuo, L.;
Chen, H., Polypropylene Glycol‐Modified Anode Interface for High‐
Performance Perovskite Solar Cells. Chin. J. Chem. 2022, 40, 2694‒
2700.
[34] Wang, T.; Ding, D.; Zheng, H.; Wang, X.; Wang, J.; Liu, H.; Shen, W. Ef-
ficient Inverted Planar Perovskite Solar Cells Using Ultravio-
let/Ozone‐Treated NiOx as the Hole Transport Layer. Sol. RRL 2019, 3,
1900045.
[35] Du, M.; Zhao, S.; Duan, L.; Cao, Y.; Wang, H.; Sun, Y.; Wang, L.; Zhu, X.;
Feng, J.; Liu, L.; Jiang, X.; Dong, Q.; Shi, Y.; Wang, K.; Liu, S. Surface
redox engineering of vacuum-deposited NiOx for top-performance
perovskite solar cells and modules. Joule 2022, 6, 1931‒1943.
[36] Chen, W.; Wu, Y.; Fan, J.; Djurišid, A. B.; Liu, F.; Tam, H. W.; Ng, A.;
Surya, C.; Chan, W. K.; Wang, D.; He, Z.-B. Understanding the Doping
Effect on NiO: Toward High-Performance Inverted Perovskite Solar
Cells. Adv. Energy Mater. 2018, 8, 1703519.
[37] Wan, X.; Jiang, Y.; Qiu, Z.; Zhang, H.; Zhu, X.; Sikandar, I.; Liu, X.; Chen,
X.; Cao, B. Zinc as a New Dopant for NiOx-Based Planar Perovskite
Solar Cells with Stable Efficiency near 20%. ACS Appl. Energy Mater.
2018, 1, 3947‒3954.
[38] Hu, Z.; Chen, D.; Yang, P.; Yang, L.; Qin, L.; Huang, Y.; Zhao, X.
Sol-gel-processed yttrium-doped NiO as hole transport layer in in-
verted perovskite solar cells for enhanced performance. Appl. Surf.
Sci. 2018, 441, 258‒264.
[39] Nie, W.; Tsai, H.; Blancon, J. C.; Liu, F.; Stoumpos, C. C.; Traore, B.;
Kepenekian, M.; Durand, O.; Katan, C.; Tretiak, S.; Crochet, J.; Ajayan,
P. M.; Kanatzidis, M.; Even, J.; Mohite, A. D. Critical Role of Interface
and Crystallinity on the Performance and Photostability of Perovskite
Solar Cell on Nickel Oxide. Adv. Mater. 2018, 30, 1703879.
[40] Ge, B.; Qiao, H. W.; Lin, Z. Q.; Zhou, Z. R.; Chen, A. P.; Yang, S.; Hou,
Y.; Yang, H. G. Deepening the Valance Band Edges of NiOx Contacts
by Alkaline Earth Metal Doping for Efficient Perovskite Photovoltaics
with High Open‐Circuit Voltage. Sol. RRL 2019, 3, 1970066.
[41] Wang, S.; Li, Y.; Yang, J.; Wang, T.; Yang, B.; Cao, Q.; Pu, X.; Etgar, L.;
Han, J.; Zhao, J.; Li, X.; Hagfeldt, A. Critical Role of Removing Impuri-
ties in Nickel Oxide on High-Efficiency and Long-Term Stability of In-
verted Perovskite Solar Cells. Angew. Chem. Int. Ed. 2022, 61,
e202116534.
[42] Ru, P.; Bi, E.; Zhang, Y.; Wang, Y.; Kong, W.; Sha, Y.; Tang, W.; Zhang,
P.; Wu, Y.; Chen, W.; Yang, X.; Chen, H.; Han, L. High Electron Affinity
Chin. J. Chem. 2023, 41, 3373—3387

Inorganic Hole-Transport Materials for Perovskite Solar Cells
Enables Fast Hole Extraction for Efficient Flexible Inverted Perovskite
Solar Cells. Adv. Energy Mater. 2020, 10, 1903487.
[43] Wu, T.; Ono, L. K.; Yoshioka, R.; Ding, C.; Zhang, C.; Mariotti, S.;
Zhang, J.; Mitrofanov, K.; Liu, X.; Segawa, H.; Kabe, R.; Han, L.; Qi, Y.
Elimination of light-induced degradation at the nickel ox-
ide-perovskite heterojunction by aprotic sulfonium layers towards
long-term operationally stable inverted perovskite solar cells. Energy
Environ. Sci. 2022, 15, 4612‒4624.
[44] Mao, L.; Yang, T.; Zhang, H.; Shi, J.; Hu, Y.; Zeng, P.; Li, F.; Gong, J.;
Fang, X.; Sun, Y.; Liu, X.; Du, J.; Han, A.; Zhang, L.; Liu, W.; Meng, F.;
Cui, X.; Liu, Z.; Liu, M. Fully Textured, Production-Line Compatible
Monolithic Perovskite/Silicon Tandem Solar Cells Approaching 29%
Efficiency. Adv. Mater. 2022, 34, e2206193.
[45] Sun, J.; Shou, C.; Sun, J.; Wang, X.; Yang, Z.; Chen, Y.; Wu, J.; Yang, W.;
Long, H.; Ying, Z.; Yang, X.; Sheng, J.; Yan, B.; Ye, J. NiOx‐Seeded Self‐
Assembled Monolayers as Highly Hole‐Selective Passivating Contacts
for Efficient Inverted Perovskite Solar Cells. Sol. RRL 2021, 5,
2100663.
[46] Li, L.; Wang, Y.; Wang, X.; Lin, R.; Luo, X.; Liu, Z.; Zhou, K.; Xiong, S.;
Bao, Q.; Chen, G.; Tian, Y.; Deng, Y.; Xiao, K.; Wu, J.; Saidaminov, M. I.;
Lin, H.; Ma, C.-Q.; Zhao, Z.; Wu, Y.; Zhang, L.; Tan, H. Flexible
all-perovskite tandem solar cells approaching 25% efficiency with
molecule-bridged hole-selective contact. Nat. Energy 2022, 7, 708‒
717.
[47] Li, M.; Li, H.; Zhuang, Q.; He, D.; Liu, B.; Chen, C.; Zhang, B.; Pauporte,
T.; Zang, Z.; Chen, J. Stabilizing Perovskite Precursor by Synergy of
Functional Groups for NiOx-Based Inverted Solar Cells with 23.5 % Ef-
ficiency. Angew. Chem. Int. Ed. 2022, 61, e202206914.
[48] Du, Y.; Xin, C.; Huang, W.; Shi, B.; Ding, Y.; Wei, C.; Zhao, Y.; Li, Y.;
Zhang, X. Polymeric Surface Modification of NiOx-Based Inverted
Planar Perovskite Solar Cells with Enhanced Performance. ACS Sus-
tain. Chem. Eng. 2018, 6, 16806‒16812.
[49] Chen, H.; Teale, S.; Chen, B.; Hou, Y.; Grater, L.; Zhu, T.; Bertens, K.;
Park, S. M.; Atapattu, H. R.; Gao, Y.; Wei, M.; Johnston, A. K.; Zhou,
Q.; Xu, K.; Yu, D.; Han, C.; Cui, T.; Jung, E. H.; Zhou, C.; Zhou, W.;
Proppe, A. H.; Hoogland, S.; Laquai, F.; Filleter, T.; Graham, K. R.;
Ning, Z.; Sargent, E. H. Quantum-size-tuned heterostructures enable
efficient and stable inverted perovskite solar cells. Nat. Photon. 2022,
16, 352‒358.
[50] Li, C.; Zhang, Y.; Zhang, X.; Zhang, P.; Yang, X.; Chen, H. Efficient In-
verted Perovskite Solar Cells with a Fill Factor Over 86% via Surface
Modification of the Nickel Oxide Hole Contact. Adv. Funct. Mater.
2023, 33, 2214774.
[51] Wang, Z.; Liu, L.; Wang, Y.; Ma, Y.; Yang, Z.; Wan, M.; Zhu, H.;
Mahmoudi, T.; Hahn, Y.-B.; Mai, Y. Green antisolvent-mediators sta-
bilize perovskites for efficient NiOx-based inverted solar cells with
VOC approaching 1.2 V. Chem. Eng. J. 2023, 457, 141204.
[52] Li, C.; Wang, X.; Bi, E.; Jiang, F.; Park, S. M.; Li, Y.; Chen, L.; Wang, Z.;
Zeng, L.; Chen, H.; Liu, Y.; Grice, C. R.; Abudulimu, A.; Chung, J.; Xian,
Y.; Zhu, T.; Lai, H.; Chen, B.; Ellingson, R. J.; Fu, F.; Ginger, D. S.; Song,
Z.; Sargent, E. H.; Yan, Y. Rational design of Lewis base molecules for
stable and efficient inverted perovskite solar cells. Science 2023, 379,
690‒694.
[53] Zhai, Z.; Huang, X.; Xu, M.; Yuan, J.; Peng, J.; Ma, W. Greatly Reduced
Processing Temperature for a Solution-Processed NiOx Buffer Layer
in Polymer Solar Cells. Adv. Energy Mater. 2013, 3, 1614‒1622.
[54] Zhang, J.; Yang, J.; Dai, R.; Sheng, W.; Su, Y.; Zhong, Y.; Li, X.; Tan, L.;
Chen, Y. Elimination of Interfacial Lattice Mismatch and Detrimental
Reaction by Self‐Assembled Layer Dual‐Passivation for Efficient and
Stable Inverted Perovskite Solar Cells. Adv. Energy Mater. 2022, 12,
2103674.
[55] Zhou, Y.; Wang, Z.; Jin, J.; Zhang, X.; Zou, J.; Yao, F.; Zhu, Z.; Cui, X.;
Zhang, D.; Yu, Y.; Chen, C.; Zhao, D.; Cao, Q.; Lin, Q.; Tai, Q. Manipu-
lation of the Buried Interface for Robust Formamidinium-based
Sn-Pb Perovskite Solar Cells with NiOx Hole-Transport Layers. Angew.
Chem. Int. Ed. 2023, 62, e202300759.
[56] Ye, T.; Sun, X.; Zhang, X.; Hao, S. Recent advances of Cu-based hole
transport materials and their interface engineering concerning dif-
Chin. J. Chem. 2023, 41, 3373—3387 © 2023 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem.
16147065, 2023, 23, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cjoc.202300252 by University Of Belgrade, Wiley Online Library on [26/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ferent processing methods in perovskite solar cells. J. Energy Chem.
2021, 62, 459‒476.
[57] 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. Copper(I) Thiocya-
nate (CuSCN) Hole-Transport Layers Processed from Aqueous Pre-
cursor Solutions and Their Application in Thin-Film Transistors and
Highly Efficient Organic and Organometal Halide Perovskite Solar
Cells. Adv. Funct. Mater. 2017, 27, 1701818.
[58] Sepalage, G. A.; Meyer, S.; Pascoe, A. R.; Scully, A. D.; Bach, U.; Cheng,
Y.-B.; Spiccia, L. A facile deposition method for CuSCN: Exploring the
influence of CuSCN on J-V hysteresis in planar perovskite solar cells.
Nano Energy 2017, 32, 310‒319.
[59] Yang, I. S.; Sohn, M. R.; Sung, S. D.; Kim, Y. J.; Yoo, Y. J.; Kim, J.; Lee,
W. I. Formation of pristine CuSCN layer by spray deposition method
for efficient perovskite solar cell with extended stability. Nano Ener-
gy 2017, 32, 414‒421.
[60] Shlenskaya, N. N.; Tutantsev, A. S.; Belich, N. A.; Goodilin, E. A.;
Grätzel, M.; Tarasov, A. B. Electrodeposition of porous CuSCN layers
as hole-conducting material for perovskite solar cells. Mendeleev
Commun. 2018, 28, 378‒380.
[61] Ye, S.; Sun, W.; Li, Y.; Yan, W.; Peng, H.; Bian, Z.; Liu, Z.; Huang, C.
CuSCN-Based Inverted Planar Perovskite Solar Cell with an Average
PCE of 15.6%. Nano Lett. 2015, 15, 3723‒3728.
[62] Ye, S.; Rao, H.; Yan, W.; Li, Y.; Sun, W.; Peng, H.; Liu, Z.; Bian, Z.; Li, Y.;
Huang, C. A Strategy to Simplify the Preparation Process of Perov-
skite Solar Cells by Co-deposition of a Hole-Conductor and a Perov-
skite Layer. Adv. Mater. 2016, 28, 9648‒9654.
[63] Lyu, M.; Chen, J.; Park, N. G. Improvement of efficiency and stability
of CuSCN-based inverted perovskite solar cells by post-treatment
with potassium thiocyanate. J. Solid State Chem. 2019, 269, 367‒374.
[64] Jin, I. S.; Lee, J. H.; Noh, Y. W.; Park, S. H.; Jung, J. W. Molecular dop-
ing of CuSCN for hole transporting layers in inverted-type planar
perovskite solar cells. Inorg. Chem. Front. 2019, 6, 2158‒2166.
[65] Xu, P.; Liu, J.; Huang, J.; Yu, F.; Zhang, R.; Li, C.-H.; Zheng, Y.-X.; Zuo,
J.-L. Coordination Strategy Driving the Formation of Compact CuSCN
Hole‐Transporting Layers for Efficient Perovskite Solar Cells. Sol. RRL
2021, 5, 2000777.
[66] Liang, J.-W.; Firdaus, Y.; Azmi, R.; Faber, H.; Kaltsas, D.; Kang, C. H.;
Nugraha, M. I.; Yengel, E.; Ng, T. K.; De Wolf, S.; Tsetseris, L.; Ooi, B.
S.; Anthopoulos, T. D. Cl2-Doped CuSCN Hole Transport Layer for Or-
ganic and Perovskite Solar Cells with Improved Stability. ACS Energy
Lett. 2022, 7, 3139‒3148.
[67] Kim, J.; Lee, Y.; Yun, A. J.; Gil, B.; Park, B. Interfacial Modification and
Defect Passivation by the Cross-Linking Interlayer for Efficient and
Stable CuSCN-Based Perovskite Solar Cells. ACS Appl. Mater. Inter-
faces 2019, 11, 46818‒46824.
[68] Cao, J.; Yu, H.; Zhou, S.; Qin, M.; Lau, T.-K.; Lu, X.; Zhao, N.; Wong,
C.-P. Low-temperature solution-processed NiOx films for air-stable
perovskite solar cells. J. Mater. Chem. A 2017, 5, 11071‒11077.
[69] Arora, N.; Dar, M. I.; Hinderhofer, A.; Pellet, N.; Schreiber, F.; Zakee-
ruddin, S. M.; Gratzel, M. Perovskite solar cells with CuSCN hole ex-
traction layers yield stabilized efficiencies greater than 20%. Science
2017, 358, 768‒771.
[70] Liu, C.; Zhang, L.; Li, Y.; Zhou, X.; She, S.; Wang, X.; Tian, Y.; Jen, A. K.
Y.; Xu, B. Highly Stable and Efficient Perovskite Solar Cells with 22.0%
Efficiency Based on Inorganic–Organic Dopant‐Free Double Hole
Transporting Layers. Adv. Funct. Mater. 2020, 30, 1908462.
[71] Perumbalathodi, N.; Su, T. S.; Wei, T. C. Antisolvent Treatment on
Wet Solution‐Processed CuSCN Hole Transport Layer Enables Effi-
cient and Stable Perovskite Solar Cells. Adv. Mater. Interfaces 2022, 9,
2201191.
[72] Li, M.; Wang, Z.-K.; Yang, Y.-G.; Hu, Y.; Feng, S.-L.; Wang, J.-M.; Gao,
X.-Y.; Liao, L.-S. Copper Salts Doped Spiro-OMeTAD for
High-Performance Perovskite Solar Cells. Adv. Energy Mater. 2016, 6,
1601156.
[73] Mashhoun, S.; Hou, Y.; Chen, H.; Tajabadi, F.; Taghavinia, N.; Egel-
haaf, H.-J.; Brabec, C. J. Resolving a Critical Instability in Perovskite
www.cjc.wiley-vch.de 3385
Recent Advances
Solar Cells by Designing a Scalable and Printable Carbon Based Elec-
trode-Interface Architecture. Adv. Energy Mater. 2018, 8, 1802085.
[74] Tennakone, K.; Kumara, G. R. R. A.; Kottegoda, I. R. M.; Perera, V. P.
S.; Aponsu, G. M. L. P.; Wijayantha, K. G. U. Deposition of thin con-
ducting films of CuI on glass. Sol. Energy Mater. Sol. Cells 1998, 55,
283‒289.
[75] Cao, J.; Wu, B.; Peng, J.; Feng, X.; Li, C.; Tang, Y. Copper-copper io-
dide hybrid nanostructure as hole transport material for efficient and
stable inverted perovskite solar cells. Sci. China Chem. 2019, 62, 363‒
369.
[76] Gharibzadeh, S.; Moshaii, A.; Abdollahi Nejand, B.; Ahmadi, V. Large
grain γ-CuI thin film growth on a copper foil as a hole transport ma-
terial by an easy and facile method. Mater. Lett. 2017, 202, 154‒157.
[77] Zuo, C.; Ding, L. Solution-Processed Cu2O and CuO as Hole Transport
Materials for Efficient Perovskite Solar Cells. Small 2015, 11, 5528‒
5532.
[78] Wang, H.; Yu, Z.; Jiang, X.; Li, J.; Cai, B.; Yang, X.; Sun, L. Efficient and
Stable Inverted Planar Perovskite Solar Cells Employing CuI as
Hole-Transporting Layer Prepared by Solid-Gas Transformation. En-
ergy Technol. 2017, 5, 1836‒1843.
[79] Meng, F.; Jia, P.; Li, X.; Tang, Y.; Song, B.; Guo, J.; Qin, L.; Hu, Y.; Teng,
F.; Lou, Z.; Hou, Y. Efficient Perovskite Solar Cells with a CuI-Modified
Polymer Hole-Transport Layer. ACS Appl. Energ. Mater. 2022, 5,
11034‒11041.
[80] Sun, W.; Ye, S.; Rao, H.; Li, Y.; Liu, Z.; Xiao, L.; Chen, Z.; Bian, Z.;
Huang, C. Room-temperature and solution-processed copper iodide
as the hole transport layer for inverted planar perovskite solar cells.
Nanoscale 2016, 8, 15954‒15960.
[81] Saranin, D.; Gostischev, P.; Tatarinov, D.; Ermanova, I.; Mazov, V.;
Muratov, D.; Tameev, A.; Kuznetsov, D.; Didenko, S.; Di Carlo, A.
Copper Iodide Interlayer for Improved Charge Extraction and Stabil-
ity of Inverted Perovskite Solar Cells. Materials 2019, 12, 1406.
[82] Hu, W.-D.; Dall’Agnese, C.; Wang, X.-F.; Chen, G.; Li, M.-Z.; Song, J.-X.;
Wei, Y.-J.; Miyasaka, T. Copper iodide-PEDOT:PSS double hole
transport layers for improved efficiency and stability in perovskite
solar cells. J. Photochem. Photobiol. A 2018, 357, 36‒40.
[83] Ye, S.; Rao, H.; Zhao, Z.; Zhang, L.; Bao, H.; Sun, W.; Li, Y.; Gu, F.;
Wang, J.; Liu, Z.; Bian, Z.; Huang, C. A Breakthrough Efficiency of 19.9%
Obtained in Inverted Perovskite Solar Cells by Using an Efficient Trap
State Passivator Cu(thiourea)I. J. Am. Chem. Soc. 2017, 139, 7504‒
7512.
[84] Zhang, H.; Yuan, S.; Qiu, Z.; Jiang, Y.; Zhu, X.; Wan, X.; Cao, B. Excess
iodine as the interface recombination center limiting the open-circuit
voltage of CuI-based perovskite planar solar cell. J. Mater. Sci. Mater.
Electron. 2018, 29, 8838‒8846.
[85] Sepalage, G. A.; Meyer, S.; Pascoe, A.; Scully, A. D.; Huang, F.; Bach,
U.; Cheng, Y.-B.; Spiccia, L. Copper(I) Iodide as Hole-Conductor in
Planar Perovskite Solar Cells: Probing the Origin of J-V Hysteresis.
Adv. Funct. Mater. 2015, 25, 5650‒5661.
[86] Li, X.; Yang, J.; Jiang, Q.; Chu, W.; Zhang, D.; Zhou, Z.; Xin, J. Synergis-
tic Effect to High-Performance Perovskite Solar Cells with Reduced
Hysteresis and Improved Stability by the Introduction of Na-Treated
TiO2 and Spraying-Deposited CuI as Transport Layers. ACS Appl. Ma-
ter. Interfaces 2017, 9, 41354‒41362.
[87] Sun, Q.; Zhou, S.; Shi, X.; Wang, X.; Gao, L.; Li, Z.; Hao, Y. Efficiency
Enhancement of Perovskite Solar Cells via Electrospun CuO Nan-
owires as Buffer Layers. ACS Appl. Mater. Interfaces 2018, 10,
11289‒11296.
[88] Bu, I. Y. Y.; Fu, Y.-S.; Li, J.-F.; Guo, T.-F. Large-area elec-
trospray-deposited nanocrystalline CuxO hole transport layer for
perovskite solar cells. RSC Adv. 2017, 7, 46651‒46656.
[89] Elseman, A. M.; Selim, M. S.; Luo, L.; Xu, C. Y.; Wang, G.; Jiang, Y.; Liu,
B.; Liao, L. P.; Hao, Z.; Song, Q. L. Efficient and Stable Planar n-i-p
Perovskite Solar Cells with Negligible Hysteresis through Solu-
tion-Processed Cu2O Nanocubes as a Low-Cost Hole-Transport Mate-
rial. ChemSusChem 2019, 12, 3808‒3816.
[90] Liu, L.; Xi, Q.; Gao, G.; Yang, W.; Zhou, H.; Zhao, Y.; Wu, C.; Wang, L.;
Xu, J. Cu2O particles mediated growth of perovskite for high efficient
3386 www.cjc.wiley-vch.de © 2023 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Wang, Dong & Liu
16147065, 2023, 23, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cjoc.202300252 by University Of Belgrade, Wiley Online Library on [26/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
hole-transporting-layer free solar cells in ambient conditions. Sol.
Energ. Mat. Sol. Cells 2016, 157, 937‒942.
[91] Han, G.; Du, W. H.; An, B.-L.; Bruno, A.; Leow, S. W.; Soci, C.; Zhang,
S.; Mhaisalkar, S. G.; Mathews, N. Nitrogen doped cuprous oxide as
low cost hole-transporting material for perovskite solar cells. Scripta
Mater. 2018, 153, 104‒108.
[92] Guo, Y.; Lei, H.; Xiong, L.; Li, B.; Fang, G. An integrated organic–
inorganic hole transport layer for efficient and stable perovskite solar
cells. J. Mater. Chem. A 2018, 6, 2157‒2165.
[93] Sun, M.; Shu, J.; Zhao, C.; Wu, J.; Guo, H.; Guo, Y.; Yin, X.; Lin, Y.; Tan,
Z.; He, M.; Wang, L., Interface Modification with CuCrO(2) Nanocrys-
tals for Highly Efficient and Stable Planar Perovskite Solar Cells. ACS
Appl. Mater. Interfaces 2022, 14, 13352‒13360.
[94] Sun, W.; Li, Y.; Ye, S.; Rao, H.; Yan, W.; Peng, H.; Li, Y.; Liu, Z.; Wang,
S.; Chen, Z.; Xiao, L.; Bian, Z.; Huang, C. High-performance inverted
planar heterojunction perovskite solar cells based on a solu-
tion-processed CuOx hole transport layer. Nanoscale 2016, 8, 10806‒
108013.
[95] Rao, H.; Ye, S.; Sun, W.; Yan, W.; Li, Y.; Peng, H.; Liu, Z.; Bian, Z.; Li, Y.;
Huang, C. A 19.0% efficiency achieved in CuOx-based inverted
CH3NH3PbI3−xClx solar cells by an effective Cl doping method. Nano
Energy 2016, 27, 51‒57.
[96] Yu, Z.-K.; Fu, W.-F.; Liu, W.-Q.; Zhang, Z.-Q.; Liu, Y.-J.; Yan, J.-L.; Ye, T.;
Yang, W.-T.; Li, H.-Y.; Chen, H.-Z. Solution-processed CuO as an effi-
cient hole-extraction layer for inverted planar heterojunction perov-
skite solar cells. Chin. Chem. Lett. 2017, 28, 13‒18.
[97] Liu, C.; Zhou, X.; Chen, S.; Zhao, X.; Dai, S.; Xu, B. Hydrophobic Cu2O
Quantum Dots Enabled by Surfactant Modification as Top
Hole-Transport Materials for Efficient Perovskite Solar Cells. Adv. Sci.
2019, 6, 1801169.
[98] Schulz, P.; Tiepelt, J. O.; Christians, J. A.; Levine, I.; Edri, E.; Sanehira,
E. M.; Hodes, G.; Cahen, D.; Kahn, A. High-Work-Function Molyb-
denum Oxide Hole Extraction Contacts in Hybrid Organic-Inorganic
Perovskite Solar Cells. ACS Appl. Mater. Interfaces 2016, 8, 31491‒
31499.
[99] Tirado, J.; Roldán-Carmona, C.; Muñoz-Guerrero, F. A.; Bonil-
la-Arboleda, G.; Ralaiarisoa, M.; Grancini, G.; Queloz, V. I. E.; Koch, N.;
Nazeeruddin, M. K.; Jaramillo, F. Copper sulfide nanoparticles as
hole-transporting-material in a fully-inorganic blocking layers n-i-p
perovskite solar cells: Application and working insights. Appl. Surf. Sci.
2019, 478, 607‒614.
[100] Han, D.; Wu, C.; Zhang, Q.; Wei, S.; Qi, X.; Zhao, Y.; Chen, Y.; Chen, Y.;
Xiao, L.; Zhao, Z. Solution-Processed Cu9S5 as a Hole Transport Layer
for Efficient and Stable Perovskite Solar Cells. ACS Appl. Mater. In-
terfaces 2018, 10, 31535‒31540.
[101] Chen, X.; Xu, W.; Ding, N.; Ji, Y.; Pan, G.; Zhu, J.; Zhou, D.; Wu, Y.;
Chen, C.; Song, H. Dual Interfacial Modification Engineering with 2D
MXene Quantum Dots and Copper Sulphide Nanocrystals Enabled
High‐Performance Perovskite Solar Cells. Adv. Funct. Mater. 2020, 30,
2003295.
[102] Lv, M.; Zhu, J.; Huang, Y.; Li, Y.; Shao, Z.; Xu, Y.; Dai, S. Colloidal
CuInS2 Quantum Dots as Inorganic Hole-Transporting Material in
Perovskite Solar Cells. ACS Appl. Mater. Interfaces 2015, 7, 17482‒
17488.
[103] Hu, R.; Zhang, R.; Ma, Y.; Liu, W.; Chu, L.; Mao, W.; Zhang, J.; Yang, J.;
Pu, Y.; Li, X. Enhanced hole transfer in hole-conductor-free perov-
skite solar cells via incorporating CuS into carbon electrodes. Appl.
Surf. Sci. 2018, 462, 840‒846.
[104] Zeng, Q.; Di, Y.; Huang, C.; Sun, K.; Zhao, Y.; Xie, H.; Niu, D.; Jiang, L.;
Hao, X.; Lai, Y.; Liu, F. Famatinite Cu3SbS4 nanocrystals as hole trans-
porting material for efficient perovskite solar cells. J. Mater. Chem. C
2018, 6, 7989‒7993.
[105] Lei, H.; Yang, G.; Zheng, X.; Zhang, Z.-G.; Chen, C.; Ma, J.; Guo, Y.;
Chen, Z.; Qin, P.; Li, Y.; Fang, G. Incorporation of High-Mobility and
Room-Temperature-Deposited CuxS as a Hole Transport Layer for Ef-
ficient and Stable Organo-Lead Halide Perovskite Solar Cells. Sol. RRL
2017, 1, 1700038.
[106] Rao, H.; Sun, W.; Ye, S.; Yan, W.; Li, Y.; Peng, H.; Liu, Z.; Bian, Z.;
Chin. J. Chem. 2023, 41, 3373—3387

Inorganic Hole-Transport Materials for Perovskite Solar Cells
Huang, C. Solution-Processed CuS NPs as an Inorganic Hole-Selective
Contact Material for Inverted Planar Perovskite Solar Cells. ACS Appl.
Mater. Interfaces 2016, 8, 7800‒7805.
[107] Zhou, X.; Li, Z.; Deng, X.; Yan, B.; Wang, Z.; Chen, X.; Huang, S. High
performance perovskite solar cells using Cu9S5 supraparticles incor-
porated hole transport layers. Nanotechnology 2019, 30, 445401.
[108] Yang, C.; Wang, Z.; Lv, Y.; Yuan, R.; Wu, Y.; Zhang, W.-H. Colloidal
CsCu5S3 nanocrystals as an interlayer in high-performance perovskite
solar cells with an efficiency of 22.29%. Chem. Eng. J. 2021, 406,
126855.
[109] Pérez-del-Rey, D.; Gil-Escrig, L.; Zanoni, K. P. S.; Dreessen, C.; Sessolo,
M.; Boix, P. P.; Bolink, H. J. Molecular Passivation of MoO3: Band
Alignment and Protection of Charge Transport Layers in Vacu-
um-Deposited Perovskite Solar Cells. Chem. Mater. 2019, 31, 6945‒
6949.
[110] Hou, F.; Su, Z.; Jin, F.; Yan, X.; Wang, L.; Zhao, H.; Zhu, J.; Chu, B.; Li,
W. Efficient and stable planar heterojunction perovskite solar cells
with an MoO3/PEDOT:PSS hole transporting layer. Nanoscale 2015, 7,
9427‒9432.
[111] Olthof, S.; Meerholz, K. Substrate-dependent electronic structure
and film formation of MAPbI3 perovskites. Sci. Rep. 2017, 7, 40267.
[112] Liu, P.; Liu, X.; Lyu, L.; Xie, H.; Zhang, H.; Niu, D.; Huang, H.; Bi, C.;
Xiao, Z.; Huang, J.; Gao, Y. Interfacial electronic structure at the
CH3NH3PbI3/MoOx interface. Appl. Phys. Lett. 2015, 106, 193903.
[113] Sung, H.; Ahn, N.; Jang, M. S.; Lee, J.-K.; Yoon, H.; Park, N.-G.; Choi, M.
Transparent Conductive Oxide-Free Graphene-Based Perovskite So-
lar Cells with over 17% Efficiency. Adv. Energy Mater. 2016, 6,
1501873.
[114] Chen, L.; Xie, Q.; Wan, L.; Zhang, W.; Fu, S.; Zhang, H.; Ling, X.; Yuan,
J.; Miao, L.; Shen, C.; Li, X.; Zhang, W.; Zhu, B.; Wang, H.-Q. Solu-
tion-Processed MoOx Hole-Transport Layer with F4-TCNQ Modifica-
tion for Efficient and Stable Inverted Perovskite Solar Cells. ACS Appl.
Energy Mater. 2019, 2, 5862‒5870.
[115] Lin, L.; Gu, C.; Zhu, J.; Ye, Q.; Jiang, E.; Wang, W.; Liao, M.; Yang, Z.;
Zeng, Y.; Sheng, J.; Guo, W.; Yan, B.; Gao, P.; Ye, J.; Zhu, Y. Engineer-
Chin. J. Chem. 2023, 41, 3373—3387 © 2023 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem.
16147065, 2023, 23, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cjoc.202300252 by University Of Belgrade, Wiley Online Library on [26/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ing of hole-selective contact for high-performance perovskite solar
cell featuring silver back-electrode. J. Mater. Sci. 2019, 54, 7789‒
7797.
[116] Zhou, T.; Xu, Z.; Wang, R.; Dong, X.; Fu, Q.; Liu, Y. Crystal Growth
Regulation of 2D/3D Perovskite Films for Solar Cells with Both High
Efficiency and Stability. Adv. Mater. 2022, 34, e2200705.
[117] Chen, L.; Wang, P.; Li, F.; Yu, S.; Chen, Y. Efficient bulk heterojunction
polymer solar cells using PEDOT/PSS doped with solution-processed
MoO3 as anode buffer layer. Sol. Energy Mater. Sol. Cells 2012, 102,
66‒70.
[118] Shao, S.; Liu, J.; Bergqvist, J.; Shi, S.; Veit, C.; Würfel, U.; Xie, Z.; Zhang,
F. In Situ Formation of MoO3 in PEDOT:PSS Matrix: A Facile Way to
Produce a Smooth and Less Hygroscopic Hole Transport Layer for
Highly Stable Polymer Bulk Heterojunction Solar Cells. Adv. Energy
Mater. 2013, 3, 349‒355.
[119] Sanehira, E. M.; Tremolet de Villers, B. J.; Schulz, P.; Reese, M. O.;
Ferrere, S.; Zhu, K.; Lin, L. Y.; Berry, J. J.; Luther, J. M. Influence of
Electrode Interfaces on the Stability of Perovskite Solar Cells: Re-
duced Degradation Using MoOx/Al for Hole Collection. ACS Energy
Lett. 2016, 1, 38‒45.
[120] Liu, Y.; Chen, Q.; Duan, H.-S.; Zhou, H.; Yang, Y.; Chen, H.; Luo, S.;
Song, T.-B.; Dou, L.; Hong, Z.; Yang, Y. A dopant-free organic hole
transport material for efficient planar heterojunction perovskite so-
lar cells. J. Mater. Chem. A 2015, 3, 11940‒11947.
[121] Liu, Y.; Hong, Z.; Chen, Q.; Chen, H.; Chang, W. H.; Yang, Y. M.; Song,
T. B.; Yang, Y. Perovskite Solar Cells Employing Dopant-Free Organic
Hole Transport Materials with Tunable Energy Levels. Adv. Mater.
2016, 28, 440‒446.
Manuscript received: April 26, 2023
Manuscript revised: June 19, 2023
Manuscript accepted: July 5, 2023
Accepted manuscript online: July 9, 2023
Version of record online: September 7, 2023
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