Review

Electron Transport Layers www.afm-journal.de

Review on the Application of SnO2 in Perovskite Solar Cells

Liangbin Xiong, Yaxiong Guo, Jian Wen, Hongri Liu, Guang Yang, Pingli Qin,
and Guojia Fang*

The PSC with regular device

SnO2 has been well investigated in many successful state-of-the-art pero- configuration is typically an n–i–p stack. It
vskite solar cells (PSCs) due to its favorable attributes such as high mobility, usually consists of a transparent electrode,
wide bandgap, and deep conduction band and valence band. Several inde- an n-type layer including a compact layer
and a mesoporous (mp) layer (optional),
pendent studies show the performances of PSCs with SnO2 are higher than
an intrinsic layer (perovskite absorber),
that with TiO2, especially in device stability. In 2015, the first planar PSCs a p-type layer (hole transport layer), and
were reported with a power conversion efficiency over 17% using a low tem- a back contact electrode. Generally, the
perature sol-derived SnO2 nanocrystal electron transport layer (ETL). Since compact layer should be very dense and
then, many other groups have also reported high performance PSCs based smooth and serve as electron transport
on SnO2 ETLs. SnO2 planar PSCs show currently the highest performance layers (ETLs) for electron extraction and
hole blocking to prevent the hole from
in planar configuration devices (21.6%) and are close to the record holder of
reaching the transparent electrodes.[3b,g]
TiO2 mesoporous PSCs, suggesting their high potential as ETLs in PSCs. The Additionally, the hole diffusion length
main concerns with the application of SnO2 as ETL are that it suffers from is longer than its electron counterpart in
degradation in high temperature processes and that its much lower conduc- CH3NH3PbX3, naturally needing an extra
tion band compared to perovskite may result in a voltage loss of PSCs. Here, mp oxide scaffold to increase the contact
area for the compensation of the shorter
notable achievements to date are outlined, the unique attributes of SnO2 as
electron diffusion length.[3e,4] Considering
ETLs in PSCs are described, and the challenges facing the successful develop- the important roles of n-type layers in
ment of PSCs and approaches to the problems are discussed. PSCs, the exploration of compact layer and
mp oxide scaffold materials for achieving
high-performance PSCs becomes a subject of high interest and
1. Introduction
one of the most challenging scientific issues.
Perovskite solar cells (PSCs) have rapidly become a hot area of Currently, numerous n-type metal oxides such as TiO2,[1,3f–h,j,5,6]
research in photovoltaic field due to its high efficiency, easy fab- SnO2,[7] ZnO,[8] Zn2SnO4,[9] WO3,[10] In2O3,[11] SrTiO3,[12]
rication, and low cost. The power conversion efficiency (PCE) Nb2O5,[13] CeOx,[14] and BaSnO3[15] have been explored as ETLs.
of PSCs has been swiftly raised from ≈3.8%[1] to recent certi- Among them, TiO2 is the most used ETLs in PSCs, especially in
fied record PCE of 22.7%[2] in a short span of less than 9 years most of highly efficient PSCs[3f–h,j,5,6] including current record
due to their remarkable photophysical properties and intensive holder (steady-state PCE, 22.7%[2]). Unfortunately, TiO2 exhibits
research efforts.[3] The impressive high efficiency surpasses some shortfalls such as not high enough electron mobility and
that of polysilicon solar cells, suggesting its rapid progress and photic instability, especially when TiO2 is used as mp scaffold,
highly potential in commercial application. it negatively affects the device stability under ultraviolet (UV)
illumination.[16] In addition, high-temperature-process (HTP)
is frequently required to remove organics in the fabrication of
Dr. L. B. Xiong TiO2 ETLs, resulting in higher production cost and longer energy
School of Physics and Electronic Information Engineering
Hubei Engineering University payback time. Thus, in spite of the high-performance, PSCs are
Xiaogan 432000, P. R. China usually fabricated using TiO2 ETLs, other alternative n-type metal
Dr. L. B. Xiong, Y. X. Guo, Dr. H. R. Liu, G. Yang, Dr. P. L. Qin, G. J. Fang oxides are also developed. ZnO is the most investigated ETL
School of Physics and Technology after the TiO2. It can be deposited easily and requires no HTP,
Key Laboratory of Artificial Micro- and Nano-structures of the Ministry but PSCs based on the low-temperature-process (LTP) ZnO are
of Education and School of Physics and Technology
Wuhan University
environmentally unstable[8b] due to the OH residue on the ZnO
Wuhan 430072, P. R. China surface causing the decomposition of perovskite absorbers.[17]
E-mail: [email protected] Among the other explored metal oxides, the SnO2 is the only
Dr. J. Wen, Dr. H. R. Liu one like TiO2, which can be both used as compact layers and
College of Physics and Electronic Science mp layers in PSCs. SnO2 shows better optical and electric prop-
Hubei Normal University erties, band alignment to perovskite, and stability than the tra-
Huangshi 435003, P. R. China
ditional TiO2, making it a conceptually more likely candidate
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201802757.
for highly efficient PSCs. Its excellent optical transparency in
the visible region is highly desired for commercial application
DOI: 10.1002/adfm.201802757 in solar energy conversion devices and in photovoltaic cells.[9a]

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The application of SnO2 as ETLs was first demonstrated in dye-

sensitized solar cells (DSSC), but it received little attention due Liangbin Xiong received his
to its relatively poor PCE[18] compared with TiO2 DSSC. It is also Ph.D. in Condensed Matter
attempted to be used as ETLs in some other film photovoltaic Physics from Huazhong
devices, such as Sb2S3 solar cells.[19] The initial studies of SnO2 Normal University in 2010.
in PSCs were almost concurrently carried out in many research He was a search associate
teams such as Dai and co-workers[20] and our groups[7a] who at The Chinese University of
reported an efficiency of ≈3.9% and 17.2%, respectively. After Hong Kong in 2012–2013. In
that, SnO2 ETLs attracted more and more attention and made 2013, he became an asso-
rapid progress.[3l,21,22] Recently, our group harvested a higher ciate professor at Hubei
efficiency of 20.79% with a well optimized SnO2 quantum dot Engineering University,
(QD) planar PSCs.[22a] Hagfeldt and co-workers[22b] developed Hubei, China. He is currently
a chemical bath post-treatment SnO2 PSCs yielded efficien- a postdoctoral associate
cies close to 21%. An impressive certified record efficiency of in the Department of Physics at Wuhan University. His
20.9% has been achieved by You and co-workers with SnO2 research interests include thin film photovoltaic devices
nanoparticle planar PSCs.[22c] A broad range of comparative and photocatalytic field.
studies[7a,21,23] show the performance of SnO2 PSCs is higher
than that of TiO2 PSCs, especially in device stability, suggesting
the great potential and promise of SnO2 as ETLs in PSCs.[24] Yaxiong Guo received a BS
In view of considerable achievements SnO2 as ETLs have degree in 2013 from Wuhan
scored, it is essential to take an overview of the application of University of Technology.
SnO2 in PSCs. However, current review articles mainly follow He is currently pursuing his
with interest of the general situation of n-type material used Ph.D. under the supervision
as ETLs in PSCs.[25] There are only two review papers on SnO2 of Prof. Guojia Fang at Wuhan
used in PSCs so far. The first one was written by Wali et al.,[26] University. His research inter-
who placed emphasis on the comparison of the performance of ests mainly focus on polymer
SnO2 PSCs with that of the TiO2 and ZnO devices. In another solar cells and inorganic–
perspective article, we introduced the recent progress of dif- organic hybrid perovskite
ferent forms of SnO2 ETLs and focused on the device stability solar cells.
of PSCs.[27] The two review papers both well present some
important sides of the SnO2-based PSCs, however it is clearly
not enough to cover all aspects. In this review, we highlight
Guojia Fang received his
the favorable attributes and preparing techniques of SnO2 as
Ph.D. in Physical Electronics
ETLs. We focus on the benefits and drawbacks of pristine SnO2
from Huazhong University
as compact layer and mp scaffold and discuss the challenges
of Science & Technology in
facing the successful development of PSCs. We hope this
2001. He became a search
review will benefit the precise control of SnO2 as ETLs and thus
associate at the Department
further improve the performance of SnO2-based PSCs.
of Electrical & Electronic
Engineering of Imperial
College London in 1996–1997.
2. General Features of SnO2 as ETLs in PSCs He was a postdoctoral
associate in the Department
SnO2 is a highly potential material in photovoltaic field. Of
of Electronic Engineering at
all transparent conductive oxide materials, F-doped SnO2 is
Tsinghua University(Beijing) from 2001–2003. In 2003, he
cheapest and possesses the highest work function, the best
joined the Wuhan University, Hubei, China, where he is
contact to p-Si, the best thermal stability, the best mechanical
currently a professor. He became a visiting professor at
durability, the best chemical durability, and least toxicity.[28] In
Department of Electrical Engineering of Imperial College
particular, SnO2 as ETLs contains diverse advantages including
from 2003–2004. His research interests include thin film
wide bandgap, deep conduction and valence band, excellent
photovoltaic devices, light-emitting diodes, and related
optical and chemical stability, high transparency, high mobility,
devices.
and easy preparation at low temperature. In this section, we
will discuss the unique attributes of SnO2 (Figure 1).

group D4h14 symmetry, belonging to the tetragonal system.

2.1. Band Structure of SnO2 The lattice parameters are α = β = γ = 90°, a = b = 0.473 nm,
c = 0.318 nm.[29] The unit cell contains six atoms, two tin, and
The phase of SnO2 currently applied in PSCs is the tetragonal four oxygen as illustrated in Figure 2a. The theory research
rutile structure, which is the most important form of naturally shows that the rutile SnO2 yields a direct bandgap located at
occurring cassiterite SnO2. Rutile SnO2 has tetragonal space the C-point of the Brillouin zone. A typical diagram of band

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then retarded charge recombination and thus increased both

of the VOC and fill factor (FF).[34] The high quality of SnO2/
perovskite heterojunction implies improved electric parameters
such as RS, RSH extracting from the internal resistance of the
device based on the J–V curves.[23d] The improvement in RS and
RSH is a sign of suppression of carrier recombination at SnO2/
perovskite interface, leading to an apparent increase in VOC of
the SnO2 devices.[23b]

2.2. Optical and Electrical Properties of SnO2

SnO2 has superior light transmittance of 90% in glass due to

its wide bandgap and a small reflective index of <2.[35] In ear-
lier work, we observed that the SnO2 films show a higher trans-
mittance than TiO2 films, and can even help to increase the
transmittance of F-doped tin oxide (FTO) glass (Figure 3a).[7a]
Figure 1. Unique and favorable advantages of SnO2 as ETLs in PSCs. Recently, we used the SnO2 QD films as ETLs whose transmit-
tances even surpass 95% in visible region (Figure 3b).[22a,36] The
efficient light management in the UV–visible region offers a
structure of SnO2 is shown in Figure 2b. The bandgaps of SnO2 photon can pass through easily and be absorbed by the pero-
reported in reference range from 3.5 to over 4.0 eV (even up vskite absorber, and enables SnO2 absorb less UV light with
to 4.4 eV for amorphous SnO2), depending on its specific syn- better device stability in comparison with TiO2. In addition,
thesis conditions.[30] SnO2 has a conduction band (CB) of about SnO2 has 100 times higher electron mobility (up to 240 cm2
4.5 eV, which is lower than the CB of about 3.4–3.9 eV for all (V s)−1 and a deeper CB than TiO2.[16]
perovskite materials such as MAPbI3, FAPbI3, MAPbBr3, and
CsSnI3 (Figure 2b). However, the low CB of SnO2 may reduce a
built-in potential of Schottky barrier between the perovskite and 2.3. Low Temperature Preparation
SnO2 ETLs, accordingly decreasing the voltage of PSCs. This
problem could be solved through surface modification[31] and HTP is usually required to eliminate organics or additives in
more details will be discussed later in Section 6.2. Moreover, the process of preparation for ETLs. However, HTP results
the CB of SnO2 primarily derives from the Sn5s–O2p orbital in more production cost and energy payback time. The flex-
interaction. This gives rise to a large CB dispersion with a low ible PSCs based on a plastic substrate are only available in
effective mass, yielding a high electron mobility. The top of the LTP.[37] Thus, the preparation of LTP ETLs ought to be real-
valence band (VB) of SnO2 mostly consists of O(p) states with a ized by improving the fabrication procedure or by developing
relatively deep valence band around 9 eV.[32] novel routes. TiO2 can also be fabricated in LTP. For example,
Figure 2c shows a full device structure of SnO2 PSCs. The Grätzel and co-workers[38] and Snaith and co-workers[39] fabri-
good band alignment of SnO2 with the perovskite layer theo- cated TiO2 at 70 and 150 °C, respectively. However, preparing
retically ensures a high quality of p–n heterojunction. More- LTP TiO2 is relatively complicated and its crystallization is also
over, high electron mobility of SnO2 helps it to extract electron very difficult.[10a] Fortunately, the situation is quite different
from perovskite effectively. Studies showed that higher built-in- for SnO2 ETLs. The LTP has becoming a preferable choice for
potential (0.94 V) of SnO2/perovskite heterojunction could be depositing SnO2 ETLs. One reason is that HTP SnO2 suffers
obtained, compared with 0.89 V of TiO2 based devices, which from performance degradation due to the annealing effects,

Figure 2. a) Bonding geometry of the tetragonal unit cell of SnO2 in the rutile structure. Reproduced with permission.[33] Copyright 2011, American
Physical Society. b) Diagram of energy levels (relative to the vacuum level) of the heterojunction SnO2/perovskite. c) Schematic representation of the
typical full device structure based SnO2 ETL with an optional mp SnO2 layer.

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Figure 3. a) Transmission spectrum of SnO2 films deposited on FTO substrates. Reproduced with permission.[7a] Copyright 2017, American Chemical
Society. b)Transmission spectra of SnO2 films deposited on a silica glass substrate. Reproduced with permission.[36] Copyright 2018, John Wiley and
Sons.

causing poor interfacial contact and electrical properties, and all of which are summarized in Table 1. Among these prepa-
unaligned energy level with adjacent perovskite. Moreover, LTP ration techniques, most popularly used methods are sol–gel
SnO2 is of easy operation at low cost and proved to be an excel- technique with a spin-coating process and ALD technique.
lent ETL material for efficient PSCs. Our group[7a] first devel- SnO2 nanoparticles or QDs can be fabricated by forming SnO2
oped a low temperature solution processed SnO2 as ETLs for sol–gel through hydrolysis and polymerization of metal pre-
planar PSCs. The PSCs with LTP SnO2 achieved an average effi- cursors. The process was quite spontaneous with great poten-
ciency of 16.02% with an open circuit voltage (VOC) of 1.11 V, tial for the manufacturing of thin film coatings, especially for
even better than TiO2.[7a] The excellent performance of LTP obtaining high quality of SnO2 ETLs. Indeed, most of efficient
SnO2 as ETLs was subsequently demonstrated by many other PSCs based SnO2 ETLs are fabricated through a low tempera-
groups’ works.[21,23d,40] In all, LTP is especially favorable for fab- ture sol–gel process. When a precursor sol–gel of SnO2 is ready,
rication of SnO2 ETLs due to its low cost, easy preparation, and a typical fabrication process of SnO2 ETLs is to spin-coat the
outstanding performance in PSCs. precursor sol–gel solution onto substrates, followed by thermal
treatment at certain temperature, as shown in Figure 4a. ALD
as a versatile and robust deposition technique can be used to
2.4. Stability of SnO2 generate high quality of inorganic thin metal oxide films.[45]
This self-limiting surface reactions of ALD can result in contin-
The stabilities of PSCs are highly related to its ambient con- uous, dense, and virtually pinhole-free thin films with excellent
ditions including the atmosphere and the contact layers of surface coverage and unrivalled conformality for coating layers
perovskite absorbers. The most used contact layers of pero- on substrates. Figure 4b shows the schematic representation of
vskite such as TiO2 or ZnO degrade significantly to 10–30% of one ALD cycle for a binary compound (e.g., SnO2). Self-limiting
the initial value after only dozens of hours storage, no matter reactions occur between the OH-terminated surface and the
what atmosphere the devices are stored in.[3i,41] The origins Sn-precursor (tin(IV) isopropoxide) (first half-cycle). The core-
of such instability for TiO2 and ZnO PSCs are mainly attrib- actant (second half-cycle) is H2O in the case of thermal ALD or
uted to photic instability of TiO2[16,42] and the decomposition O2 plasma in the case of a plasma assisted ALD process. The
of perovskite absorbers caused by the OH residues on the purge steps avoid parasitic chemical vapor deposition contri-
ZnO surface,[8b,17] respectively. As for SnO2, the relatively wide bution during the ALD process leading to the desired accurate
bandgap SnO2 enables it to absorb less UV light with better control of film thickness by repeating the ALD cycle.[46] Never-
device stability. Moreover, the lower hygroscopicity and acidity theless, spin-coating process and ALD technique are frequently
resistance of the SnO2 also contribute to the durability of the limited in laboratory research and it is not easy to develop for a
PSC device.[31,43] Our work[44] and several other independent large-scale. Our group[47] attempted to fabricate e-beam evapo-
studies[25c,31,34] also indicated SnO2 PSCs have better stability rated SnO2 as ETL in PSCs for possible commercial feasibility.
and larger potential in the real-world applications. Figure 4c shows the deposition process of SnO2 using e-beam
evaporation technique. In an e-beam evaporation process, SnO2
target source is evaporated to its vaporous counterpart, subse-
3. The Preparing Techniques of SnO2 quently condensing into a layer of compact film on the top of
the FTO. Hundreds of FTO substrates can be fabricated at one
Used in PSCs
time by changing the position of substrates holder. The SnO2
Currently, the explored techniques for the preparation of SnO2 film can be formed uniformly by rotating substrate holder and
ETLs have been over ten different methods, mainly including its thickness can be precisely controlled, contributing to high
sol–gel method, atomic layer deposition (ALD) technique, dual- quality film deposition with desired repeatability. It is a low-cost
fuel combustion, chemical-bath deposition, electrodeposition, and large-scale manufacture technology which can uniformly
e-beam evaporation, hydrothermal method, and ball milling, process SnO2 films for commercialization.[47]

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Table 1. Preparation methods of SnO2 used as ETLs in PSCs. The precursors, temperatures, devices configuration, and PCE are also included.

Preparation method Precursor T [°C] Functional layer PCE (%) and Ref.
Sol–gel process SnCl2 180 FTO/SnO2/MAPbI3/spiro/Au 17.2[7a]
Sol–gel process SnCl2 180 FTO/SnO2/MAPbI3/carbon/Au 14.5[34]
Sol–gel process SnCl2 200 FTO/SnO2/MAPbI3/CuSCN/Au 8.38[48]
Sol–gel process SnCl2 80 FTO/SnO2/(FAPbI3)0.85–(MAPbBr3)0.15/spiro/Au 19.20[23d]
Sol–gel process SnCl2 70 FTO/SnO2/MAPbI3/spiro/Ag 16.21[49]
Sol–gel process SnCl2 180 FTO/SnO2/MAPbI3/spiro/Au 15.07[50]
Sol–gel process SnCl2 180 FTO/SnO2/(FAPbI3)0.85–(MAPbBr3)0.15/spiro/Au 15.8[23b]
Sol–gel process SnCl2 450 FTO/BL SnO2-mp TiO2/MAPbI3/Spiro/Ag 12.18[51]
Sol–gel process Commercial SnO2 colloid 150 ITO/SnO2/(FAPbI3)0.97–(MAPbBr3)0.03/spiro/Au 20.90[22c]
Sol–gel process Tin(IV) isopropoxide 250 FTO/SnO2/(FAPbI3)0.875–(CsPbBr3)0.125/spiro/Au 19.40[52]
Sol–gel process SnCl2 200 FTO/SnO2/Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3/spiro/Au 20.79[22a]
Dual-fuel combustion SnCl2 140 ITO/SnO2/ MAPbI3/spiro/Ag 12.93[53]
CBDa) SnCl2 180 FTO/SnO2/perovskite/spiro/Au 20.7[22b]
CBDa) SnCl4·5H2O 180 FTO/SnO2/FA0.83MA0.17Pb–(I0.87Br0.17)3/SWNT-spiro/Ag 18.8[54]
a)
CBD SnCl4 55 ITO/SnO2/ MAPbI3/spiro/Au 14.8[23a]
ALD T-tin(IV)b) 118 FTO/SnO2/(FAPbI3)0.85–(MAPbBr3)0.15/spiro/Au 18.4[21]
PE-ALD T-tin(IV)b) 100 FTO/SnO2/MAPbI3/spiro/Au 17.16[55]
b)
PE-ALD T-tin(IV) 100 (FTO)/SnO2/C60-SAM/MA0.7FA0.3PbI3/Spiro/Au 20.3[56]
PE-ALD T-tin(IV)b) 100 Flexible ITO/SnO2/spiro/Au 18.36[37a]
Template self-etching Sodium stannate 60 FTO/SnO2-NTs/MAPbI3/P3HT/Au 12.1[24]
Spray pyrolysis Butyltin trichloride 450 AZO/BL-SnO2/mp-SnO2/MAPbI3/spiro/Au 13.1%[16]
Photonic annealing SnCl4, RTe) FTO/SnO2/MAPbI3/PTAA/Au 15.3[57]
Electrodeposition SnCl2∙2H2O 60 FTO/SnO2/MAPbI3-xClx/EM 10.83[58]
Electrodeposition SnCl2 50 ITO/SnO2/MAPbI3/spiro/Ag 13.88[59]
c)
VLS-reaction Tin powder 700 FTO/SnO2-TiO2/MAPbI3/Spiro/Au 14.2[25b]
E-beam evaporation SnO2 powders 180 FTO/SnO2/Cs5(MA0.17FA0.83)95Pb(I0.83Br0.17)3 /Spiro/Au 18.2[47]
Microwave-synthesized SnCl4 130 ITO/SnO2/MAPbI3/spiro/Au 14.2[60]
LTP hydrothermally Tin oxalate 95 FTO/ hierarchical SnO2/MAPbI3/spiro/Au 16.17[44]
d)
Ball milling C-SnO2 NPs 500 FTO/BL-SnO2/mp-SnO2/MAPbI3/spiro/Au 19.12[36]
Ball milling C-SnO2 NPsd) 500 FTO/BL-SnO2/mp-SnO2/MAPbI3/spiro/Au 6.5[20]

a)
Chemical-bath deposition; b)Tetrakis(dimethylamino)-tin(IV); c)Vapor–liquid–solid reaction; d)Commercial SnO2 nanoparticles; e)Room temperature.

4. Application of SnO2 as Compact Layers 4.1. Electrons Collection of SnO2 as Compact Layers

A compact layer is crucial for determining the performance The electron collection ability of compact layers is highly related
of PSCs. Generally, to make efficient PSCs, the compact to the compatibility of its band structure with the adjacent per-
layers should meet several requirements: high transparency, ovskite and its electric properties including mobility and con-
being compact and pinhole-free, suitable bandgap, and good ductivity. As shown in Figure 2b, the favorable CB and the deep
electron collection and hole blocking ability. As discussed VB of the SnO2 can offer efficient electron transfer from the
in Section 2, SnO2 enjoys almost all these advantages. perovskite layer to the SnO2 compact layers and block effec-
Moreover, it also possesses excellent optical and chemical tively holes, respectively. Moreover, the pristine SnO2 has high
stability, well band alignment to perovskite and easy prepa- electron mobility (up to 240 cm2 (V s)−1, 100 times higher than
ration at low temperature. A main issue on the use of SnO2 those of TiO2) and a high conductivity of 103 Ω cm (ND over
as compact layers is that it suffers from degradation in HTP, 1018 cm−3),[61] suggesting a high electron collection efficiency
which is still a challengeable problem in HTP SnO2 PSCs.[40] and transport ability.
In this section, we will highlight these competitive advan- To address the high electron collection efficiency of SnO2
tages of SnO2 as compact layers and the approaches to the compact layers, we retrieved all publications involved in the
problem. comparative studies on SnO2 and TiO2 as compact layers in

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Figure 4. a) Schematic procedure for the preparation of the SnO2 ETL using SnO2 precursor sol–gel solution. b) Schematic representation of one
ALD cycle for a binary compound (e.g., SnO2). c) Schematic illustration of SnO2 deposition process of electron beam evaporation. Reproduced with
permission.[47] Copyright 2017, John Wiley and Sons.

PSCs with similar fabrication processes. The detailed descrip- photoluminescence (TRPL). The PL quenching is expected to
tions on parameters of the two kinds of devices are listed in originate from the charge-carrier extraction across the inter-
Table 2, from which one can see that the performance of the face.[63] As shown in Figure 5a, under identical experimental
SnO2 PSCs is higher than that of the TiO2 PSCs. In particular, condition, the PL quantum yield is greatly reduced when the
the VOC and JSC of the SnO2 PSCs are significantly higher than perovskite is interfaced with SnO2 and TiO2 ETLs in com-
those of the TiO2 PSCs, suggesting higher electron collection parison with perovskite/glass. The lowest PL peak for SnO2/
efficiency of SnO2 than that of TiO2. Additionally, we note that perovskite suggests the highest quenching efficiency, thus
in some highly efficient SnO2 PSCs, the VOC of up to 1.14 the highest electron extraction efficiency. Figure 5b shows the
and 1.19 V, which are close or even exceeds most devices and TRPL (λexcitation = 507 nm) of the perovskite on SnO2 film, TiO2
approach the thermodynamic maximum VOC of ≈1.32 V.[62] film, and glass. The PL decay of 5.1 ± 0.4 ns at SnO2/perovskite
This suggests exceptionally good charge selectivity and a low interface is shorter than that of 5.5 ± 0.4 nm at TiO2/perovskite
degree of charge recombination in SnO2 PSCs.[21] interface, indicating that charge carriers within the perovskite
The electron collection efficiency of SnO2 can be evaluated layer can be separated more effectively and faster extraction
by the steady-state photoluminescence (PL) and time-resolved and transfer by SnO2 compact layers. The efficient carrier dis-
sociation in SnO2 PSCs is due to the high electron mobility and
Table 2. The devices’ parameters of the SnO2 PSCs (left figure) and TiO2 lower CB of SnO2 compact layers.[23c]
PSCs (right figure) compact layers with the similar fabrication process.
High electron collection efficiency of SnO2 helps to decease
and even eliminate J–V hysteresis. The J–V hysteresis char-
PCE [%] JSC [mA cm−2] VOC [V] Fill factor Ref.
acter may primarily originate from slow transient capaci-
17.2, 15.2 23.3, 22.5 1.11, 1.06 0.67, 0.64 [7a] tive current, dynamic trapping, and detrapping processes of
14.8, 12.8 21.3, 20.8 1.05, 0.99 0.66, 0.61 [23a] charge carriers, and band bending due to ion migration or
15.8, 11.4 22.8, 21.1 1.05, 0.97 0.66, 0.56 [23b] ferroelectric polarization.[64] The J–V hysteresis behavior can
12.1, 7.16 20.7, 19.4 0.91, 0.81 0.64, 0.46 [23c]
be effectively suppressed or even eliminated by improving
charge collection at ETL/perovskite interface if the ETL has
19.2, 16.6 22.2, 20.9 1.17, 1.13 0.74, 0.70 [23d]
sufficient ability to extract the charges.[56] Figure 5c,d shows

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Figure 5. a) Steady-state PL of perovskite deposited on SnO2 film, TiO2 film, and glass. b) TRPL (excitation wavelength at 507 nm) of the perovskites
on SnO2 film, TiO2 film, and glass. Reproduced with permission.[23c] 2017, Springer Nature. c) Scan rate effects on J–V characteristics of SnO2 and
d) TiO2-based devices. Reproduced with permission.[21] Copyright 2015, Royal Society of Chemistry.

the scan rate effects on J–V characteristics of SnO2 and TiO2- thin compact layers for efficient electron extraction and the
based devices. For the SnO2 devices, the energy levels are hole-blocking.
already well aligned without biasing the devices. Thus, charge It is expected that the optimized thickness of SnO2 com-
collection is efficient showing high FF and JSC independent of pact layers will vary as different preparation conditions. Sev-
the scan rate (Figure 5c). However, TiO2 devices have all been eral independent studies including our group’ work have
demonstrated to yield highly J–V hysteresis in PSCs, as the demonstrated different optimized thickness of the SnO2 ETLs
CBs between perovskite and TiO2 are misaligned, highlighting depending on specific preparation conditions. Table 3 lists the
the importance of correct band alignment in all planar PSCs. optimized thicknesses of SnO2 ETLs with corresponding prepa-
A broad range of studies have also shown similar or even more ration methods and the PCEs of derived devices.
pronounced trends of hysteretic behaviors in SnO2 and TiO2 From Table 3, one can see that highly efficient PSCs trend
devices.[23a,56,61,65] toward thin compact layers. It is reasonable that a thin compact
layer can offer faster electron extraction and decrease the com-
bination of charge carriers due to short diffusion length. Based
4.2. Holes Blocking of SnO2 as Compact Layers on these results and the surface roughness of TCO, the pre-
ferred nanostructure of SnO2 compact layers should be 0D nan-
Besides selective extraction of electron, another important func- oparticles with small enough size. In this case, it is expected
tion of compact layers is to block hole from perovskite layers. that the extremely small particles SnO2 such as nanoparticles or
To obtain an efficient blocking effect, the compact layers should QDs could be efficient ETLs for PSCs.
be uniform for complete cover of transparent conductive oxide
(TCO) substrates, thereby avoiding the direct contact of the
upper layers with TCO substrates and minimizing the charge Table 3. Optimized thicknesses of SnO2 ETLs and their corresponding
preparation methods and PECs of derived PSCs.
shunt pathway. In this case, increasing the thickness of com-
pact layers always might be enough to ensure blocking effect.
Method PEC [%] Optimized thickness [nm] Ref.
However, for improving electron extraction and decreasing
charge recombination, thin compact layers are required. Thus, SnO2 sol–gel 12.18 100 [51]
this trend may be understood by the balance between the elec- SnO2 sol–gel 15.07 70 [50]
tron transport properties and the hole-blocking ability of com- SnO2 sol–gel 17.21 60 [7a]
pact layers.[55] To satisfy the bifunction of compact layers, on Commercial SnO2 20.51 25 [7b]
one hand is to optimize the thickness of compact layers, on
ALD 17.16 15 [55]
the other hand is to seek and develop high quality of enough

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Figure 6. a) TEM and b) HRTEM images of SnO2 nanoparticles. c) Electron diffraction of SnO2 nanoparticles. d) Scanning electron microscopy (SEM)
image of SnO2 nanoparticles deposited on a glass/ITO substrate. (a–d) Reproduced with permission.[7b] Copyright 2016, Springer Nature. J–V curves
of the best devices in e) small size (0.0737 cm2) and f) large size (1 cm2) measured from reverse and forward scan under one sun condition (AM1.5G,
100 mW cm−2). Inset shown in (f) is the image of large area device. The tables shown in (e) and (f) are the corresponding device performance parameters.
(e,f) reproduced with permission.[22c] Copyright 2017, John Wiley and Sons.

This issue can be addressed according to the previous studies. poor interface contact with TCO substrate, increasing the series
You and co-workers[7b] used very uniform LTP SnO2 nanoparti- resistance and decreasing JSC and FF. Therefore, the thickness
cles, as shown in the transmission electron microscopy (TEM) of the SnO2 ETLs should be optimized according to the spe-
(Figure 6a). High-resolution TEM (HRTEM) (Figure 6b) and cific fabrication process. In the process of preparation of SnO2,
electron diffraction circles in Figure 6c indicated the SnO2 nano­ it is suggested that it is better not to induce aggregation and
particles are highly crystallized and of polycrystalline, helpful for rapid growth of the intermediate phase, leading to the forma-
reducing the number of defect traps in SnO2 and beneficial for tion of large size nanoparticles. Therefore, to fabricate efficient
charge transfer. The spin-coated SnO2 ETL on indium doped tin devices, well-dispersed single-crystalline particles should be pre-
oxide (ITO) substrate forms a dense, pinhole-free film (Figure 6d), pared and the morphology and phase of the crystalline particles
and the film quality is much better than that of the conventionally must also be controlled.[9a,22b,37a,66] Motovated by this idea, our
used TiO2 nanoparticle films. The SnO2 nanoparticle ETLs can group[67] synthesized the SnO2 QDs using a simple LTP with
enhance the electron extraction of corresponding planar devices. the presence of thiourea as reaction stabilizer, which inhibits
The optimized SnO2 PSC can achieve a close to 20% PCE with the aggregation of SnO2 QDs. The well dispersed SnO2 QDs
almost free of hysteresis.[7b] Using the same SnO2 nanoparticle are very small in size (3–5 nm), enabling an intimate interface
ETL, You and co-workers[22c] further optimized the perovskite contact between SnO2 and FTO substrate, efficient for exciton
layers by adjusting the content of residual PbI2, promoting dissociation and charge transfer. Moreover, the loading of QDs
the efficiencies to current record of 21.6% in planar PSCs. increases the contact of ETL/active layer interface, which can
Figure 7 further demonstrates that the
small size nanoparticles are preferable choice
for SnO2 as compact layers. From Figure 7
one can find both large and small SnO2
nanoparticles can fully cover FTO. However,
large SnO2 nanoparticles inevitably produce
a thicker layer than small ones to completely
cover TCO. Otherwise, the pinholes will
exist, resulting in a leakage current pathway. Figure 7. Schematic representation of SnO2 compact layer with a) large particles and b) small
Moreover, large SnO2 nanoparticles have a particles.

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make more electron transport to the corresponding electrodes of ultrathin SnO2 films on FTO might be due to the close simi-
and optimize carrier transfer and collection ability. Using an larity in lattice structure of SnO2 and FTO.[61]
optimized SnO2 QD ETL, we fabricated triple cation PSCs
with a champion PCE of 20.79% and stabilized power output
of 20.32%.[22a] Moreover, using the LTP SnO2 QD ETLs, a high 4.3. Annealing Effect of SnO2 as Compact Layers
performance flexible PSC and a large active area (1.0 cm2) PSC
can achieve an efficiency approaching 17% and up to 19.05%, Generally, materials treated at higher temperatures will exhibit
respectively. Our results demonstrate the promise of SnO2 QD higher charge carrier mobility due to better crystallinity, and
ESLs for fabricating stable, efficient, reproducible, large-scale, thus achieving high device performance. However, HTP SnO2
and flexible planar PSCs.[22a] ETLs suffer from significant degradation such as worse inter-
The quality of the blocking layers of SnO2 can be evaluated facial contact, electrical properties, and unaligned energy level
by electrochemical cyclic voltammetry (CV) technique, which with adjacent perovskite.
even allows quantifying the pinhole concentration from the In earlier study, we have systematically examined the influ-
peak current.[68] SnO2 is an electrochemically silent dielectric ence of annealing temperature of SnO2 on the performance of
material against the Fe(CN)6 3−/4− redox couple. The charge- PSCs.[40,70] Figure 9 shows the scanning electron microscopy
transfer reaction is therefore assumed to occur exclusively at (SEM) images of LTP and HTP SnO2 films deposited on FTO
the bare TCO surface.[16] Figure 8 shows CV of Fe(CN)6 3−/4− substrates at different magnifications. The LTP SnO2 films with
redox couple at the LTP ALD SnO2 films with different thick- the dense SnO2 nanoparticles can fully and uniformly cover
nesses (1–100 nm) on FTO. An absence of the oxidation peak in the FTO substrates (Figure 9a,b). However, HTP SnO2 nano-
the CV is expected for pinhole-free SnO2 films. For 1 nm SnO2 particles agglomerate seriously (Figure 9c,d) and increase in
film, the scan rate dependence and the Nernstian peaks-shaped size as increasing film thickness (Figure 9e,f). Therefore, HTP
CV curve indicate the film does not function well in blocking SnO2 cannot effectively block holes, leading to severe interface
effect.[68,69] From 2 nm onward, the LTP ALD SnO2 films fully recombination and shunting paths. As a result, the cells using
suppress the oxidation of ferrocyanide even at potential as high HTP SnO2 exhibit lower FFs, VOCs, and PCEs than those using
as 1.4 VRHE and thus show perfect blocking behavior. Solely, the LTP SnO2.
1 nm thick SnO2 exhibits pinholes, which exposes part of the
FTO surface to the electrolyte solution. The excellent blocking
5. Application of SnO2 as mp Layers
SnO2 has been successfully implemented on lab scale as ETLs
in LTP planar PSCs.[21,71] However, the rapid and poorly con-
trolled perovskite crystallization makes it difficult to scale up
planar PSCs for industrial application. An mp ETL can over-
come this problem by changing the surface wettability to
achieve uniform perovskite coverage over large area.[16] More-
over, it helps to extract electrons from perovskite layer to sup-
press or even eliminate the notorious I–V hysteresis. As for
SnO2 mp PSCs, they are particularly important because of
their increased stability compared to TiO2 mp PSCs and SnO2
planar PSCs.[16] Apparently, it is highly of interest to develop
an SnO2 mp ETL for the industrial production of stable and
efficient PSCs. However, SnO2 mp PSCs experienced an unfa-
vorable beginning with relatively low device performance due
to the degradation of SnO2 after HTP.[40,51,70] Fortunately, our
passionate researchers[36,72] have always been putting unremit-
ting efforts to solve the problems of SnO2 mp PSCs and made
encouraging progress as shown in Table 4.
Thus, to achieve highly efficient SnO2 mp PSCs, one
approach is to synthesize both SnO2 compact layers and SnO2
mp layers at low temperature, the other is to develop high
quality of HTP SnO2 ETLs especially compact layers, since
HTP inevitably causes the degradation of SnO2 compact layers.
In previous work,[44] we employed a one-step hydrothermal
approach at a low temperature of 95 °C to obtain SnO2 ETLs,
Figure 8. CV at bare FTO electrode (top dashed line) and those covered which contains a thin compact SnO2 layer underneath an mp
by SnO2 layers made by ALD. The layer thickness (in nm) is labeled in
annotations. Scan rate: 50 mV s−1. The electrolyte solution is 1 × 10−3 m
scaffold of SnO2 nanosheets. Figure 10a displays in situ growth
K4Fe(CN)6 + 1 × 10−3 m K3Fe(CN)6 in aqueous 0.5 m KCl, pH 2.5. The vol- process of hierarchical structure of the SnO2 ETL after hydro-
tammograms (except “FTO” and “100”) are offset for clarity. Reproduced thermal reaction for 0 (bare FTO), 2, 3, 4, 5, and 6 h, respec-
with permission.[61] Copyright 2017, American Chemical Society. tively. It is obvious that no defect exists between the interface

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constructing a planar PSC yielding a high

efficiency of close to 17%. Particularly, as
shown in Figure 11a, the arrangement of a
thin SnO2 mp scaffold on the top of planar
SnO2 is awesome and can provide respect-
able electron transport to yield hysteresis
free, stable PSCs with a high PCE of 19.12%
(Figure 11b). The incorporation of mp
SnO2 on the top of Mg-SnO2 is something
like an anode buffer layer. Here, the mp
SnO2 plays a friendly bridging role between
Mg-SnO2 and CH3NH3PbI3 and forms a
cascade energy level sequence (Figure 11c).
Figure 10b shows the SnO2 mp PSC ben-
efits from an increased JSC, partly suggesting
faster transfer dynamics after the incorpo-
ration of mp SnO2. Thus, the full SnO2 as
compact layer/mp layer ETL can facilitate
charge transfer and improve charge collec-
tion efficiency than a single Mg-SnO2 com-
pact layer.[36]
The stability is further addressed, as it
is becoming the most critical issue on the
practical application of PSCs. Figure 11d
shows the PCEs of mp SnO2 and planar
500-Mg-SnO2 devices dropped from 18.59%
to 17.02% (red line) and 15.95% to 13.25%
(green line), i.e., 91.6% and 83.1% of
their initial PCEs can be retained for after
30 days storage, respectively. The results sug-
gest that the inclusion of the thin mp SnO2
Figure 9. Top view SEM images of a,b) 40 nm thick LTP SnO2; c,d) 40 nm thick HTP SnO2; and layer improves long-term stability of the
e,f) 100 nm thick HTP SnO2 films deposited on FTO substrates at different magnifications. All
[40]
panels reproduced with permission. Copyright 2015, Royal Society of Chemistry.
device. The stability of the mp SnO2 PSCs
and mp TiO2 PSCs was also comparatively
investigated. Here, mp TiO2 PSC was fabri-
of the SnO2 compact layer and in situ growth SnO2 scaffold, cated with the same process of mp SnO2 PSC as reference. The
greatly reducing the recombination of charge carriers. The inte- red line in Figure 11e shows the PCE of mp TiO2 PSC dras-
grative SnO2 compact layer/scaffold ETLs play multiple roles tically dropped 16.15% to 3.03% and only 18.7% of its initial
in enhancing photon collection, preventing moisture penetra- PCE retained after 6 h irradiation due to its instability under
tion, and improving the long-term stability. The derived PSCs light exposure.[75] By contrast, the PCE slightly decreased from
can achieve the highest efficiency of 16.17% with high stability. 18.09% to 17.11% and over 95% of its initial PCE (green line in
The results shown in Figure 10b–d suggest that the PSCs Figure 11e) retained for mp SnO2 PSC under the same aging
using hierarchical SnO2 ETLs have better moisture-stability in condition, suggesting perfect stability during the period of aged
comparison with planar counterparts. More-
over, the PSCs’ moisture tolerance can be Table 4. Application of mp SnO2 as scaffold in PSCs. The device configurations and PCEs and
dramatically improved by using hierarchical thicknesses of mp SnO2 are included.
SnO2 ETLs. Figure 10e presents the results
of the long-term stability tests of a hierar- Functional layer PEC [%] Thickness [nm] Ref.

chical SnO2 device. Impressively, the PCE FTO/mp-SnO2/MAPbI3/spiro/Au 12.18 300 [73]
of the tested device without encapsulation FTO/hierarchical nano-SnO2/MAPbI3/spiro/Au 16.17 – [44]
at humidity (20%) and temperature (25 °C) FTO/BL-TiO /SnO nanosheets/MAPbI /spiro/Au 7.81 – [74]
2 2 3
sustains above 90% of its initial value after
FZO/SnO2-NTs/MAPbI3/P3HT/Au 12.1 500 [24]
3000 h.[44]
Most recently, we used a relatively wide AZO/BL-SnO 2 /mp-SnO2 /MAPbI3 /spiro/Au 13.1 100 [16]

bandgap of SnO2 QD as compact layers, FTO/BL SnO2/Ga-mp-SnO2/perovskitea)/Spiro/Au 16.4 100 [72]

which is almost transparent to sunlight and FTO/BL-TiO2/SnO2 nanorods/MAPbI3/triarylamine/Au 16.18 100 [9a]
insensitive to annealing effects. We reengi- FTO/BL-SnO /mp-SnO /MAPbI /spiro/Au 19.12 100 [36]
2 2 3
neered the SnO2 QD by Mg incorporation at
500 °C to obtain a high quality of SnO2 for a)Csx(MA0.17FA0.83)(100−x)Pb(I0.83Br0.17)3.

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Figure 10. a) Scheme of the SnO2 ETL growth process. Box chart data of PCEs for 10 solar cells (≈70% humidity): b) without ETL, c) with planar
SnO2 ETLs, and d) with hierarchical SnO2 ETLs measured under reverse voltage scanning. e) Long-term stability tests (≈20% humidity) for 3000 h of
a prototypical PSC device with a hierarchical SnO2 ETL grown at 4 h of reaction time. All panels reproduced with permission.[44] Copyright 2016, John
Wiley and Sons.

time. The mp SnO2 has an excellent photostability[16] and can 6.1. Elemental Doping
inhibit the degradation or phase segregation of the perovskite,
and the penetration of harmful substances such as moisture, Doping ETLs with metal aliovalent cations is an effective
oxygen,[76] or gold[77] into the perovskite layer. method to improve properties of both ETLs and ETLs/pero-
vskite interfaces.[79] For example, doping metal oxide can offer
a good surface coverage of thin films and provide a shift in the
6. Application of SnO2 as ETLs after Modification energy levels, effectively inducing the suitable alignment of the
energy levels to adjacent layers. It can also increase the con-
Photoanode modifications are frequently used to improve ductivity of thin films, resulting in the improvement of device
electron injection and suppress electron recombination.[78] performance.
Elemental doping, combination with other ETLs, and surface Currently, Al3+, Y3+, Li+, Nb5+, Mg2+, and Ga3+ were used to
modification were frequently used in photoanodes modifica- incorporate into SnO2 ETLs. The PCEs of the PSCs with doped
tion. The modification of SnO2 can significantly enhance the SnO2 ETLs versus the undoped ones are listed in Table 5. It
performance of PSCs in a number of ways: 1) to modify band is clear that all PCEs of devices are improved after elemental
energy that allows electron injection but blocks the holes at doping.
an interface; 2) to passivate the surface states for the sup- In our previous work, we found the device with HTP
pression of recombination, 3) to improve the morphology of SnO2 suffered from performance degradation.[70] As shown
the active absorber layer and the intimacy of the contact at in Figure 12a, SnO2 film becomes discontinuous and appear-
the interface, and 4) to increase the long-term stability of the ance of many cracks after HTP. Interestingly, appropriate
devices. Mg doping (2.5, 5, and 7.5%) significantly improves the film

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Figure 11. a) Cross-sectional SEM images of 100 nm thick SnO2 mp PSCs. b) J–V curves measured under backward and forward voltage scanning
under AM 1.5G conditions with input solar power pin of 100 mW cm−2. c) Experimentally determined diagram of energy levels (relative to the vacuum
level) of Mg incorporated SnO2, mp SnO2, and other layers in the device. d) PCEs as a function of time measured directly during storage of planar
Mg-SnO2 and mp SnO2 PSCs monitored every 3 d. e) PCEs as a function of time measured directly during aging of mp SnO2 PSC and mp TiO2 PSC
monitored every 30 min; measured under AM 1.5G conditions with input solar power pin of 100 mW cm−2. All panels reproduced with permission.[36]
Copyright 2018, John Wiley and Sons.

quality and contributes to uniform, smooth, and dense SnO2 can promote the formation of well-aligned CBs between pero-
films (Figure 12b–d). However, excess Mg content (10 and vskite and ETL, improving electron transfer from perovskite to
20%) degrades the quality of the film, leading to surface irreg- ETL and reducing charge recombination.[83] Some other inde-
ularity (Figure 12e,f). Moreover, Mg doping can significantly pendent studies also found that the doping can improve the
increases the resistance (Figure 13a) and dramatically reduces properties of SnO2 and thus enhance the performance of PSCs.
the carrier density and effectively regulates the carrier mobility For example, Al and Li dopants in SnO2 enhance the charge
(Figure 13b). As a result, an optimized Mg content of 7.5% in transport and reduce the charge recombination of PSCs, com-
SnO2 achieved the highest PCE of 14.55%.[70] pared with the undoped SnO2 ETLs.[37b,80] Nb dopant effectively
As discussed in Section 5, we used a relatively wide bandgap passivates electron traps in the SnO2, leading to higher electron
of SnO2 QDs as ETLs, which is nearly transparent to sun- mobility. The champion cell with Nb doped SnO2 shows sig-
light.[36] The quality of SnO2 QDs can be improved by Mg nificantly higher PCE of 17.57% than those of devices based on
incorporation at 500 °C. We also found that Y dopant in SnO2 pristine SnO2 ETLs.[81]

Table 5. The doped elemental names (valences) and quality in SnO2. The corresponding device architectures and PECs of the doped cells (right
figure) versus undoped cells (left figure) are included.

Doped elements Doped quality Solar cell architecture PCE [%] Ref.
Al(+3) 1 wt% FTO/Al-SnO2/MAPbI3/Spiro/Au 9.02, 12.1 [80]
Li(+) 1.7 wt% FTO/Li-SnO2/MAPbI3/Spiro/Au 15.29,18.2 [37b]
Nb(+5) 1 wt% (FAPbI3)0.85(MAPbBr3)0.15PbI3)0.85(MAPbBr3)0.15 15.13,17.57 [81]
Mg(+2) 7.5 wt% FTO/Mg-SnO2/MAPbI3/Spiro/Au 7.5,14.6 [70]
Ga(+3) 2.5 wt% FTO/BL SnO2/Ga-SnO2-perovskitea)/Spiro/Au 12.7, 16.4 [72]
Sb(+5) 4 mol% ITO/Sb-SnO2/MAPbI3/Spiro/Au 15.7,17.2 [82]
Y(+3) 3 wt% FTO/Y-SnO2/MAPbI3/Spiro/Au 13.38, 17.29 [83]

a)Ga-mp SnO2/Csx(MA0.17FA0.83)(100−x)Pb(I0.83Br0.17)3.

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interlayer of electron collection materials

(Figure 14a). Such a GHJ structure formed
at the boundaries of the interconnected SnO2
and TiO2 networks can extract electrons from
the low electron mobility TiO2 network to the
high electron mobility SnO2 network, pre-
venting the electrons back-flow and allowing
the use of SnO2 network as electron trans-
port highway (Figure 14b). Huang et al.[90]
systematically studied the SnO2/TiO2 com-
posite layer and suggested that the combina-
tion of SnO2 and TiO2 provides a simple and
effective route to facilitate charge transfer
and suppress the charge recombination in
PSCs. In addition, the surface of SnO2 can be
modified by directly deposition of TiO2 on it.
For example, one simple way to do this is to
treat SnO2 by TiCl4. TiCl4 treatment usually
results in a decreased contact angle, helping
to form smooth, conformal perovskite films
for improving the surface coverage.[73,74,97c]
Figure 12. SEM images of a) 0, b) 2.5, c) 5, d) 7.5, e) 10, and f) 20% Mg-doped SnO2 films
The surface modification of SnO2 by
coated on FTO substrates. All panels reproduced with permission.[70] Copyright 2016, Royal
Society of Chemistry. other metal oxides ZnO and Sb2O3 can also
benefit electron extraction and suppress
electron–hole recombination.[18b,92,98] It is
6.2. Combination and Surface Modification well to be reminded that MgO is a good tunneling and spin-
tronics material, which could modify the interface and retard
Recently, there has been a focus on the combination and sur- electron–hole recombination.[99] Our group[93] incorporated an
face modification of ETLs to improve the performance of PSCs. ultrathin dielectric MgO nanolayer between FTO electrode and
Combination and surface modification can be used to modu- SnO2 ETL of PSCs, realizing enhanced electron transporting
late band energy offsets at an interface and decrease interfacial and hole blocking properties. With the modification of MgO,
loss caused by surface recombination.[3i,84] It can also improve the device achieved a PCE of 18.23% which is 11% increment
the morphology of the active absorber layer, the work function compared with that without MgO modifier. MgO passivation
of contact layers, the intimacy of the contact at the interface, improves surface roughness, decreases FTO surface defects,
and the long-term stability of the devices.[78b,85] Currently, inor- and suppresses the recombination. Moreover, extremely wide
ganic metal oxides (TiO2, MgO, Sb2O3, ZnO) and organics such bandgap MgO nanolayer with deep VB level functions well in
as self-assembling monolayers (SAM), polymers, carbon based hole blocking. As a result, the device with the MgO exhibits a
materials are used to combine with or modify SnO2 in PSCs, all remarkable improvement in all cell parameters.[93]
of which are included in Table 6. SAM is an effective strategy for fine-tuning the interfacial
TiO2 is the most preferable metal oxide chosen to be com- optoelectronic properties by bonding the perovskite layer to the
bined with SnO2.[73,74,86–91,97] Combination of SnO2 and TiO2 contact layer.[84,100] The deposition of SAMs on substrates offers
may be a viable avenue to improve PCE and broaden the appli- diverse linkages between the substrates and the ionic perovskite
cation of PSCs.[90] Hou et al.[88] adapted a gradient heterojunc- films.[84] SAM can increase the surface energy and enhance the
tion (GHJ) concept to construct SnO2/TiO2 composite gradient affinity of SnO2 ETLs, which would favor the growth of smooth

Figure 13. a) Resistivity and resistance, b) carrier density, and mobility of 0, 2.5, 5, 7.5, 10, and 20% Mg-doped SnO2 films. All panels reproduced with
permission.[70] Copyright 2016, Royal Society of Chemistry.

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Table 6. Examples of combination and surface modification of SnO2 in effectively reduce the recombination at the interface.[84] Zuo
PSCs. The corresponding device architectures and PECs are included. et al.[84] demonstrated that the ionic-covalent nature of pero-
vskite films makes it easy to form various chemical interac-
Surface modification Solar cell architecture PEC [%] Ref. tions with different chemical groups. Through delicate control
TiO2-SnO2 FTO/TiO2-SnO2/MAPbI3/PATT/Au 19.8 [86] of the interfacial chemical interactions, the PSCs with SnO2
SnO2-TiO2 FTO/SnO2-TiO2/MAPbI3/spiro/Ag 8.54 [73] modified by SAM achieved a PCE of reaching 18.8%, which
TiO2-SnO2 FTO/ TiO2-SnO2/MAPbI3/spiro/Ag 21.1 [87]
is 10% improvement compared to the that without SAM.[84]
In addition, the surface modification of SnO2 by SAM helps
SnO2-TiO2 FTO/SnO2-TiO2 /perovskitea)/spiro/Ag 18.08 [88]
to improve the junction quality of SnO2/perovskite.[66,101] Xiao
SnO2-TiO2 FTO/TiO2-SnO2/MAPbI3/spiro/Ag 17.58 [89] et al.[66] investigated the differences of performance param-
SnO2-TiO2 FTO/SnO2-TiO2/MAPbI3/spiro/Ag 14.8 [90] eters in the junctions of ETL-free, SnO2 ETL, and SnO2 + SAM
SnO2-Sb2O3 FTO/TiO2-SnO2-Sb2O3/MAPbI3-xClx/spiro/Ag 7.7 [91] with perovskite. These junctions give a diode ideality factor of
ZnO-SnO2 FTO/ZnO-SnO2/MAPbI3/spiro/Ag 12.17 [92]
1.76, 1.54, and 1.38, respectively, suggesting a difference in
the junction quality and a large difference in carrier transport,
MgO-SnO2 FTO/MgO-SnO2/MAPbI3/spiro/Au 18.23 [93]
including barriers in the front junction and back interface.[66]
b)
SnO2-SAM FTO/SnO2-SAM/MAPbI3/spiro/Au 18.8 [84] The electric-field ratio between the ETL/perovskite interfaces
SnO2-C60 FTO/SnO2-C60/MAPbI3/spiro/Au 19.03 [55] increases in devices as follows: FTO < SnO2-ETL < SnO2 +
SnO2-C60 FTO/NiO/MAPbI3/C60-SnO2/Ag 18.8 [71] SAM. This sequence explains the improvement of the FF and
PCBM FTO/SnO2-PCBM/perovskitec)/spiro/Ag 17.1 [3l]
VOC. The improvement by the surface modification of SAM is
caused by the defect passivation at the SnO2/perovskite inter-
PCBM FTO/SnO2/PCBM/perovskite/spiro/PbS/Au 19.58 [94]
face, and hence, improving the junction quality.
PCBM FTO/SnO2-PCBM/MAPbI3/spiro/Au 19.12 [95] Other organics C60, [6,6]-phenyl-C61-butyric acid methyl
SnO2-GQDs ITO/SnO2-GQDs/MAPbI3/spiro/Au 20.23 [96] ester (PCBM), and graphene QDs (GQDs) can also promote
a)Cs (MA b)4-pyridinecarboxylic acid, 3-aminopropanoic
electron transfer and reduce charge recombination.[96,102] As we
5 0.17FA0.83)95Pb(I0.83Br0.17)3;
acid, 4-aminobenzoic acid, 4-cyanobenzoic acid; c)FA0.83Cs0.17Pb(I0.6Br0.4)3. discussed in Section 2.1, CB of SnO2 is well in alignment to the
CB of perovskite materials (Figure 2b), but the relatively low CB
and high crystalline perovskite films. Figure 15 shows the ter- of SnO2 may reduce a built-in potential of Schottky barrier in
minal functional groups of SAM formed dipoles on the SnO2 the perovskite/SnO2 heterojunction, resulting in the decrease in
surface can passivate the trap states at the perovskite surface voltage of PSCs. Here, we can see this problem could be solved
via hydrogen bonding and can hinder electron back flow and through surface modification of SnO2. Figure 16a shows a

Figure 14. a) Schematic diagram of the potential GHJ ETL-based PSCs, showing the extraction and transport of photogenerated electrons. b) Possible
schematic illustration of the separation and recombination of photogenerated electrons and holes in the device with SnO2/TiO2 composite ETL. All
panels reproduced with permission.[88] Copyright 2017, John Wiley and Sons.

Figure 15. Schematic diagram of the PSCs structure (left) and the SAM between the SnO2 and perovskite film (right) (BA is benzoic acid, PA is 4-pyridine
carboxylic acid, CBA is 4-cyanobenzoic acid, ABA is 4-aminobenzoic acid, and C3 is 3-propanoic acid). All panels reproduced with permission.[84]
Copyright 2017, American Chemical Society.

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schematic diagram of the PSC with C60-modified SnO2 as ETL. ETLs in PSCs are summarized. The benefits and drawbacks of
The CB of SnO2 is 0.6 eV below that of CH3NH3PbI3, which SnO2 as ETLs and the corresponding remedial schemes for this
might lead to unfavorable charge accumulation and potential are also discussed. A PCE of 21.6% has been achieved for SnO2
loss while charges transfer across this interface.[71] The inserting planar PSCs, which is close to that of current record holder
of C60 as a thin buffer layer between perovskite and SnO2 TiO2 PSCs. SnO2 is an effective charge collection material for
layer facilitates the electron transfer across this corresponding PSCs and provides a new direction for the future green energy
interface to mitigate charge recombination as considering the technology. Looking toward the future, there are still substan-
well energy level alignment between perovskite and C60. PL tial opportunities for SnO2 PSCs in several aspects. First, con-
quenching efficiency (Figure 16c) enhances after the modifica- trollable synthesis of SnO2 nanocrystals is still a significant
tion of the thin C60 layer, revealing the positive effect of C60 challenge to tune its band structure, size, and morphology for
that facilitates the charge extraction from perovskite absorber high quality of LTP and HTP SnO2 compact layers; second, the
to SnO2. Benefiting from its efficient electron extraction, the advantages of stability of SnO2 need to be further addressed
C60-modified SnO2 ETL can provide respectable electron to achieve better reproducibility and longer lifetimes for PSCs
transport to yield a high PCE of 18.8% in the derived devices with high conversion efficiency; third, developing new synthetic
(Figure 16d), which is among the highest performance reported methods and effective optimization strategies for fabrication of
in the inverted PSCs employing inorganic ETLs.[71] SnO2 mp PSCs, which is a necessary step on the path for mass
production and commercialization, especially for the modula-
tion of stability of mp SnO2 PSCs; finally, based on interfacial
7. Summary and Future Outlook engineering and energy band engineering, different modifica-
tion approaches such as doping, coupled or mixed with other
An overview of the application of SnO2 in PSCs has been given. materials, need further screening and investigation for the
General characteristics, preparation, and application of SnO2 as improvement of SnO2 as ETLs. We hope a comprehensive

Figure 16. a) Schematic diagram of the PSC with a structure of FTO/NiO/MAPbI3/C60/SnO2. b) The corresponding energy level diagram of the
studied PSC. c) Steady-state PL spectra of the perovskite film capped with different SnO2-based ETLs. d) J–V curves of the studied PSCs using C60
SnO2 measured under forward (from 0 to 1.2 V) and reverse (from 1.2 to 0 V) scans. All panels reproduced with permission.[71] Copyright 2016, John
Wiley and Sons.

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