Journal of Solid State Electrochemistry (2022) 26:295–311

https://doi.org/10.1007/s10008-021-05064-z

REVIEW PAPER

Recent progress in electron transport bilayer for efficient and low‑cost

perovskite solar cells: a review
Wegene Lema Lachore1 · Dinsefa Mensur Andoshe2 · Mulualem  Abebe Mekonnen1 · Fekadu Gashaw Hone3 

Received: 5 June 2021 / Revised: 6 October 2021 / Accepted: 6 October 2021 / Published online: 18 October 2021
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
Today, organic–inorganic perovskite hybrid solar cells are especially attracted by the energy industries to design and develop
new-generation photovoltaic devices. They are the most promising materials for high PCE and cheap solar cells. They can
also solve the current energy demand of society and the global crisis. Over the past few years, the power conversion effi-
ciency (PCE) of perovskite solar cells (PSCs) has increased rapidly from 3.8 to 24.2%. However, the review focuses on the
recent development of the electron transport layer due to the most important parameter perovskite solar cells to enhance the
performance and stability of the device. These summaries discuss device architectures, single and double electron transport
(ETL) layers, ETL optimization, and perovskite active layer interface for efficient perovskite solar cells. Moreover, the dop-
ing effects on the charge transport layer/window layers of PSCs were reviewed. In addition, the performance and stability
issues for organic–inorganic halide perovskite solar cells are discussed here. Finally, future research on bilayer ETL and the
perovskite active layer interface was also offered.

Keywords  Perovskite · Electron transport · Active layer · Doping · Mesoporous

Introduction strong light absorption with a low band gap, long charge
carrier lifetimes, high carrier mobility, and long diffusion
Organic–inorganic perovskite hybrid solar cells are par- length. Beside this, an excellent charge transport properties
ticularly attracted by the energy industries to design and make them very attractive [3, 4]. The crystal structures of
develop new generation photovoltaic systems with the aim the perovskite has a general formula of ­AMX3 as shown
to address the current affordable and green energy demand in Fig. 1 where “A” is an organic cation such as methyl-
of society. As a result, organic–inorganic hybrid perovs- ammonium ­(MA+) or formamidinium ­(FA+), “M” is a metal
kites are the promising materials for high power conver- cation (e.g., P­ b2+ or ­Sn+2) and “X” stands for the halide
sion efficiency (PCE) and low-cost solar cells In recent anion (e.g., ­Br−, ­I−, ­Cl−) or a mixture of them.
years, the PCE of perovskite solar cells (PSCs) has quickly In 2006 and 2009, the first organometallic lead hal-
increased from 3.8 to 24.2% [1, 2]. To date, the highest ide perovskites, methyl-ammonium lead iodide and bro-
efficient organic–inorganic hybrid perovskite solar cells mide ­(MAPbBr3 and ­MAPbI3) were used as sensitizers
shows the power conversion efficiency of over 20%. These in dye-sensitized solar cells by Miyasaka and co-workers,
materials have excellent optoelectronic properties such as and their devices showed a 3.13% and 3.81% efficiency,
respectively [1, 6]. Moreover, in 2011, Park’s and co-
workers demonstrated a highly efficient quantum-dot-
* Fekadu Gashaw Hone
sensitized solar cell with a power conversion efficiency
1
Faculty of Materials Science and Engineering, Jimma of 6.5% using ­CH3NH3PbI3 quantum dots (QD) deposited
Institute of Technology, Jimma University, P. O. Box: 1041, on a nanocrystalline ­TiO2 surface. However, their device
Jimma, Ethiopia had poor stabilty which was degereded 80% of the sensi-
2
Department of Materials Science and Engineering, Adama tizer within 10 min [7]. The liquid electrolyte of the dye
Science and Technology University, P. O. Box 1888, Adama, synthesized solar cell with the ­TiO2 electron transport
Ethiopia
layer was replaced by the solid hole transport layer to
3
Department of Physics, Addis Ababa University, P.O. Box: enhance the conversion efficiency by Spiro-OMeTAD
1176, Addis Ababa, Ethiopia

13
Vol.:(0123456789)
296 Journal of Solid State Electrochemistry (2022) 26:295–311

Fig. 1  Cubic perovskite crystal

structures with the general
formula of A
­ MX3 [adopted
from Ref. 5]

(2,2,7′,7′-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′- performance of inorganic–organic halide perovskite solar

spirobifluorene) and achieved 9.7% PCE [8]. In 2013, Liu cells has been discussed as well.
et al. reported planar heterojunction perovskite solar cells
using both vapor deposition and solution treatment method
and ­TiO2 used as an electron transport layer. The power con- Perovskite solar cells
version efficiency of both methods was reached by 15.4%
and 8.6% without nanostructure and by replacing the tra- Device architectures
ditional one-step solution method [9]. The first introduced
organic–inorganic halide perovskite C ­ H 3NH 3PbCl 3-XI x The typical device architectures of perovskite solar cells
was used as a light absorber and showed good stability in are analogous to solid state dye synsetized solar cells (ss-
the air compared to conventional ­CH3NH3PbI3. Therefore, DSSCs). The basic architectures of perovskite solar cells are
efficiency has been improved by adopting A ­ l2O3 nanopo- mesoporous, planer and inverted planar, which are shown
rous as scaffolding instead of ­TiO2 from 7.6 to 10.9% [10]. in Fig. 2.
Researchers have been working to design new efficient
perovskite photon-absorbing materials, to improve the syn- Mesoporous perovskite solar cells
thesis mechanism/methods, and manipulate the electronic
structure of the photon-absorbing perovskite active layer Mesoporous materials have been studied and used exten-
to harness the highest possible portion of visible light. To sively due to their high porosity and large specific surface
date, the electron and hole transport layers have received area. Its high surface area enables to harvest more density
considerable attention due to their impact on the photogen- of photons and reduces recombination rate and improving
erated carrier collection efficiency of the cell. Moreover, the charge collection the efficiency of the solar cell device.
the interface between the photon absorbing layer, electron Mesoscopic perovskite solar cells were introduced by using
transport layer (ETL), and hole transport layer (HTL) has to methyl-ammonium lead iodide ­CH3NH3PbI3 and bromide
be given due attention to improve the photogenerated charge ­CH3NH3PbBr3 to serve as sensitizer on mesoporous ­TiO2,
carrier collection efficiency [11, 12]. The major function of and PCE of achieved 3.82% and 3.13 with an organic liquid
the ETL is to carry/transport photogenerated electrons from electrolyte [6]. Kim et al. studied perovskite mesoscopic
the perovskite photon active layer to the contact electrode, solar cells using the solid hole transportation layer (Spiro-
and the layer effectively blocks the holes from migrating to OMeTAD), ­TiO2 as ETL, and to prevent rapid degradation
the counter electrode. These phenomena enhance the charge of performance due to the dissolution of the perovskite
carrier separation kinetics due to the kind of ETL used and material into the liquid electrolyte [8]. However, the most
reduce electron–hole recombination at the interface [13, 14]. commonly used perovskite mesoscopic solar cells uses ­TiO2
Therefore, this review article briefly discusses the recent compact thin film as ETL and mesoporous such as ­TiO2,
progress in the PSCs, the single and double ETLs and the ZnO, ­SiO2, ­Al2O3, and ­ZrO2. To date, above 20% power
kinetics of photogenerated carriers at the interface of PSCs. conversion efficiency for mesoscopic perovskite solar cells
A special attention is given for metal oxide layers reporting has been reported [18, 20, 21, 25, 27]. Moreover, perovs-
for the last 5 years. Moreover, the effects of doping on PSC kite solar cells prepared from various mesoporous perovskite
charge transport/window layers were examined. Addition- photon-absorbing layers with different ETL are summarized
ally, the current advancement of PSCs on the stability and in Table 1.

13
Journal of Solid State Electrochemistry (2022) 26:295–311 297

Fig. 2  Various device architectures of perovskite solar cells: a mesoporous, b planar, and c inverted planar device [adopted from Ref. 15]

Scaffold material in  perovskite solar cells In perovskite 10% ­SiO2 [32], ­Al2O3 [33, 34], and ­ZrO2 [35]. The A
­ l2O3
solar cells, a scaffold material serves as a support layer interlayer was introduced between the Li-SnO2 ­(Li+-SnO2)
and frame, but it cannot transfer electrons into the cells. ETL and the ­CH3NH3PbI3 layer using the low-temperature
These materials have wide band gaps and a conduction process sol–gel technique, and the ­Al2O3 layer covers the
band border that is substantially higher than the perovs- top of the perovskite layer. The device’s performance and
kite layer’s conduction band, preventing smooth electron stability have been improved, and the power conversion effi-
injection into both ­SiO2 and ­ZrO2. As a result, the excited ciency has been boosted to 10%. The fill factor drops due
electron spends more time in the perovskite layer’s conduc- to a weak interface contact between the perovskite layer
tion band. Various research groups have reported employ- and the carbon counter electrode. At the interface between
ing ­TiO2, ZnO, A­ l2O3, ­Nb2O5, ­SiO2, and Z
­ rO2 as scaffold the ETL and the perovskite layers, the ­Al2O3 layer in the
materials in perovskite solar cells, with a PCE of around device reduces electron–hole recombination, resulting in

Table 1  The performances of mesoscopic perovskite solar cells with ETL layer

Perovskite active layers ETLs Voc(V) Jsc(mA/cm2) PCE (%) Ref

MAPbI3(CH3NH3PbI3) c-TiO2/mp-TiO2 1.04 20.44 15.51 [16]

(FA0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 mp-TiO2-Ba(OH)2 1.09 20.81 17.53 [17]
(CsFAMA)
MAPbI3(CH3NH3PbI3) MgTiO3/mp-TiO2 with hole-conductor-free 0.95 14.05 22.62 [18]
MAPbI3(CH3NH3PbI3) Bl-Mg-SnO2/mp-SnO2 1.112 22.80 19.12 [19]
MAPbI3(CH3NH3PbI3) c-TiO2/mp-Sb doped ­SnO2 1.10 23.81 20.1 [20]
(FA0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 c-SnO2/mp-Sc3+doped brookite ­TiO2 1.145 23.63 21.75 [21]
(CsFAMA)
CH3NH3PbI3-xClx/ (GO or m GO) c-TiO2/ mp-TiO2 0.85/0.93 20.49/ 24.43 8.96/13.25 [22]
MAPbI3(CH3NH3PbI3) PET/ITO/SnO2/meso-TiO2 1.036 ± 0.011 20.70 ± 0.28 14.07 ± 0.58 (14.8) [23]
MAPbI3 ­(CH3NH3PbI3) c-TiO2/mp-TiO2 1.059 19.62 15.12 [24]
(FAPbI3)0.85(MAPbBr3)0.15 c-TiO2/GQD-x/mp- ­TiO2 1.08 24.92 20.45 [25]
MAPbI3(CH3NH3PbI3) O-mp-TiO2 1.13 22.4 19.7 [26]
CH3NH3PbI3-xBrx c-TiO2/mp-TiO2 1.141 23.42 20.43 [27]
MAPbIxCl3-x mp-Al2O3/mp-TiO2 1.069 20.78 16.84 [28]
CH3NH3PbI2.6Cl0.4 c-TiO2/mp-TiO2 1.045 20.1 12 [29]
MAPbI3-XBrx Bl-TiO2/H3PW12O40·nH2O/mp-TiO2 1.03 23.55 18.20 [30]
(FAPbI3)1-X(MAPbBr3)3 c-Nb2O5/m-Nb2O5 1.04 23.2 17.4 [31]

13
298 Journal of Solid State Electrochemistry (2022) 26:295–311

better perovskite solar cells. Also, a good way to increase deterioration. In addition, it reduces electron–hole recom-
the short-circuit current density [36]. Xiong et al. Reported bination at the ­TiO2 surface and spiro-OMeOTAD shown
carbon-based perovskite star cells with hole-conductor free in Fig.  3a. The device post-modified by ­Al2O3 has shown
associate degreed incorporation of an ­Al2O3 layer modi- more brilliant stability than that without modification when
fies the interface between the electron transport layer and exposed to moisture [33]. Similarly, Dong et al. introduced
perovskite active layer. It also reduced the energy loss at an interface modification method using ultra-thin ­Al2O3 lay-
the interface between ETL and perovskite layer and counter ers to improve the ambient stability of perovskite solar cells.
conductor leads, preventing the electron–hole recombina- The results showed that the ambient stability of the prepared
tion. This serves as an excellent insulating layer to separate perovskite solar cell was greatly improved without a signifi-
the cathode and anode [37]. Niu et  al. used aluminum as cant reduction in efficiency. Moreover, they used molecular
a post-modification material to investigate the stability of structure modeling to explain the degradation mechanisms
­CH3NH3PbI3 and the sensitized film under moisture and of organic/inorganic hybrid structures and they found that
sunlight. ­Al2O3 improved the stability and efficiency of per- the hydrogen bonding interactions between the inorganic
ovskite solar cells by protecting them from moisture and UV ­PbI3 unit and organic C ­ H3NH3 unit play an important role

Fig. 3  Schematic description of a energy level diagrams of the device (red), and compact-TiO2 (black) scaffold layers. d Schematic illus-
with post-modification by A­ l2O3, b the energy levels in the two solar tration, representing relaxation of photoexcited carriers in perovskite
cell interfaces and a model for the charge separation processes, c PL film [adopted from Ref. 33, 35, and 38]
spectra of the perovskite films on N ­ b2O5 (blue), mesoporous-TiO2

13
Journal of Solid State Electrochemistry (2022) 26:295–311 299

in determining the stability of ­CH3NH3PbI3 [34]. Bi et al. a higher electron extraction capability from the perovskite
examined synthesized ­ZrO2 and ­TiO2 as mesoporous lay- absorber layer interface to the ETL interface. Additionally,
ers for perovskite thin film solar cells using two-step and the fracture and pinhole between the FTO substrate and the
one-step deposition processes. When using the two-step perovskite interface/electrode were minimized.
and one-step approaches to compare the power conversion
efficiency of ­ZnO2 and ­TiO2. The two-step technique for Planar perovskite solar cells
­ZnO2 (PCE: 10.8% for ­ZnO2)-based solar cells outperforms
both the one-step and two-step techniques for T ­ iO2-based In typical planar perovskite solar cells, the perovskite active
solar cells (PCE: 9.8% for ­TiO2). As a result, the electron layer is the sandwich between the electron transport layer
lifetime in solar cells based on ­ZrO2 is longer than in solar and hole transport layer, forming both interfaces contacting
cells based on T ­ iO2 at the same voltage shown in Fig.  3b with charge transport layers. They are hot topic currently due
[35]. Inami et al. has been reported N
­ b2O5 as a scaffold layer to their unique advantages such as low cost, high efficiency,
(SL) and compared the electron-extraction capability at the easy processing, and low-temperature process [40]. James
perovskite/Nb2O5 and the perovskite/m-TiO2 interface. The M. Ball et al. proposed a low-temperature solution process
photoluminescence spectroscopy results revealed the higher technique for preparing planar thin-film architectural perovs-
electron-extraction capability at the perovskite/Nb2O5 inter- kite solar cells with power conversion efficiencies of about
face than the perovskite/m-TiO2 interface shown in Fig. 3c. 12.3% [41]. Traditional planar PSCs based on compact T ­ iO2,
They also proposed the relaxation of photoexcited carriers ZnO, or S ­ nO2 as well as inverted planar perovskite solar
in perovskite film shown in Fig. 3d. cells are included in the structure of planar perovskite solar
Also, it was revealed not only to functions as the efficient cells [42]. Each layer in planar perovskite solar cells has
electron transport layer but also to facilitate crystallization its own advantage for improving the device’s performance
of the overlying perovskite film, both of which are important [43]. As a result, there are a variety of methods for improv-
factors for high-performance perovskite solar cells. It was ing the performance of planar perovskite solar cells, includ-
also found that the perovskite layer on N ­ b2O5 shows fewer ing perovskite crystalline regulation [44], the design of new
pinhole defects than the perovskite/m-TiO2 film. There- perovskite components [45], surface morphology control
fore, the superior optoelectronic properties, better photo- [46], and modification of the charge carriers transport lay-
voltaic performance, and stability of mesoporous the per- ers and perovskite absorber layer interface [47]. Further-
ovskite solar cells [38]. In 2019, Tomulescu et al. revealed more, numerous studies have reported on the performance
mesoporous ­TiO2 layers with a high-roughness reticulated of planar perovskite solar cells using different techniques.
structure that can be applied to large surfaces using a spray- Recently, Zhu et al. used K and Cl ions at the ETL/perovs-
coating approach in the ambient atmosphere. These layers kite interface to passivation the ETL/perovskite contact and
are used as a mesoporous scaffold in PSCs with small and grain boundaries, demonstrating an increase in open-circuit
large active areas up to 1 ­cm2, and the average power con- voltage from 1.077 to 1.137 V and a 22.2% increase in power
versation efficiency was 10 to 12% higher than devices with conversion efficiency using ­SnO2-KCl composite ETL. As
a spin-coated smooth surface mesoporous scaffold. As a a result, defect passivation in the trap density will be low-
result, reducing charge losses within the solar cell’s most ered, and nonradiative recombination loss will be reduced
resistive component layer was beneficial for perovskite set- [48]. Lee Y and co-workers prepared ­SnO2 electron trans-
tlement, allowing the deposition of a thicker perovskite and port layer by using low-temperature atomic layer deposition
increasing the length of the interface between T ­ iO2 and per- (ALD) with excellent extraction and hole-blocking ability.
ovskite, as well as improving photogenerated charge collec- They found that the surface passivation of ­SnO2 is very cru-
tion and reducing hysteresis [29]. In 2020, Daneshvare Asl cial to reduce charge recombination at the perovskite and
et al. published a thin film containing mesoporous nanopar- ETL interface because of this the prepared planar perovskite
ticles, nanorods, and nanobranched nanorods as a scaffold solar cells exhibit high reproducibility, stability, and power
for perovskite solar cells. However, due to better optical conversion efficiency of 20% [49].
properties, nanobranched nanorods outperformed nanopar- They also recommended that the chemical and electrical
ticles and nanorods in photovoltaic performance, demon- properties of the ALD S ­ nO2 film were strongly associated
strating excellent electron transport properties and desired with deposition and postannealing temperature. However,
light-harvesting performance, which are desirable features the charge collection from perovskite to ­SnO2 can be less
for increasing the efficiency of perovskite solar cells [39]. influenced by the downward shift of conduction band maxi-
Overall, scaffold materials play an important role in perovs- mum and Fermi level of ­SnO2 film but, strongly affected
kite solar cells because they protect recombination electrons by crystallinity and proper surface passivation of the ­SnO2
from the electron transport layer interface and the perovs- layer. The microstructures from scanning electron micros-
kite absorber layer interface/electrode, as well as providing copy of the ALD ­SnO2 films deposited at 120 °C and the

13
300 Journal of Solid State Electrochemistry (2022) 26:295–311

complete perovskite device are displayed in Fig. 4 [49]. Sim- and carbon nanotubes (CNTs) which was prepared by simple
ilarly, Subbiah et al. used ALD method and prepared amor- thermal decomposing.
phous ­Nb2O5 with and without an interfacial passivation In this case, the addition of CNTs significantly improved
layer of phenyl-C61-butyric acid methyl ester (PCBM) as the conductivity of ­SnO2 films and reduced the trap-state
ETLs. The device performance exhibits superior behavior in density of ­SnO2 films, which benefits carrier transfer from
terms of hysteresis, scan rate dependency, and stability asso- the perovskite layer to the cathode. As a result, a high effi-
ciated with ETL–perovskite interactions and ALD-Nb2O5 ciency of 20.33% was achieved in the hysteresis-free PSC
fabricated using a PCBM interfacial layer. Their results also device, which showed 13.58% enhancement compared with
confirmed that ­Nb2O5 suitable for evaporated perovskite the conventional device [52]. In 2016, Anaraki et al. used a
absorbers with power conversation efficiency about 15.4% low-temperature solution process to prepare excellent S ­ nO2
[50]. The combined solution-processed and spin-coating ETL to fabricate highly efficient planar PSCs and achieved
techniques was employed to prepare ­Nb2O5 thin films by the power conversation efficiency of close to 21%. Moreover,
Shen et al. They used the prepared N­ b2O5 thin films for both the stability of the device retains more than 82% of the initial
mesoscopic and planar types of perovskite solar cells. They efficiency over 60 h [53]. Luo et al. came up with a strat-
obtained the power conversation efficiencies about 17.4 for egy to reduce nonradiative recombination for the inverted
mesoscopic while as high as 19.2% from planer perovskite devices, based on a simple solution-processed secondary
solar cells. Their results also reviled that the thickness of growth technique. This approach produced a wider band gap
­Nb2O5 thin films affects the quality of the device by reduc- top layer and a more n-type perovskite film, which mitigates
ing the charge recombination rate [31]. Another promising nonradiative recombination, leading to an increase in open-
composite-controlled ­SnO2 nanostructure was reported by circuit voltage (Voc) by up to 100 mV. They achieved a high
Singh and co-workers. The results showed that the ground Voc of 1.21 V without sacrificing photocurrent, correspond-
and compact composite ­SnO2 nanostructure formed a robust ing to a voltage deficit of 0.41 V at a band gap of 1.62 V.
ETL having efficient carrier transport properties; accord- This improvement led to a stabilized power output approach-
ingly, carrier recombination between the ETL and mixed ing 21% at the maximum power point [54]. Currently, planar
perovskite was inhibited. Moreover, the power conversion perovskite solar cells show relatively high PCEs between
efficiency of the device was reported about 21.09% with 20 and 21.4% [55]. However, the mesoporous perovskite
excellent long-term stability [51]. Tang et al. fabricated solar cells have greater PCEs than planar [56, 57]. Therefore,
hysteresis-free PSCs device based on a hybrid ETL of ­SnO2 planar PSCs do not reach world records yet; researchers are

Fig. 4  Planar-type perovskite solar cells with ALD ­SnO2 ETLs. a minescence emission spectra of the perovskite films formed on the
SEM images of the ALD SnO films and the complete perovskite solar ALD ­SnO2 and c-TiO2 substrates. e J–V curve change according to
cell. b Transmittance of the ALD S ­ nO2, FTO, and c-TiO2, films. c postannealing of ALD ­SnO2 films [ adopted from Ref. 50]
J–V curves with ­SnO2 and c-TiO2 films. d Absorbance and photolu-

13
Journal of Solid State Electrochemistry (2022) 26:295–311 301

less willing to switch from meso to planar, even though it is mechanisms (iv and v) within PSCs. These kinetic processes
industrially more preferable [58]. and influences factor have a significant impact on device
performance. The schematic representation of the PSC work
mechanism and a review of the parameters that influence the
Electron transport materials in perovskite solar cells function of ETLs are extremely useful in determining the
underlying causes of PSC solar performance improvement
The electron transport layer in perovskite solar cells prevents through ETL optimization [63]. To obtain efficient photo-
the hole from migrating to the counter electrode by captur- voltaic perovskite solar cells, the presence of ETL is crucial
ing and conveying the excited photogenerated electron from requirement to extract and transport excited the photogen-
the perovskite absorber layer [59]. In addition, to improve erated electron from perovskite absorber layer to its counter
carrier separation and reduce electron–hole recombination at electrodes [64].
the interface. ETL features such as charge mobility, energy Although different groups claimed to obtain power con-
level alignment, trap states, interface, and surface morphol- version efficiency of more than 13% for ETL free devices but
ogy all contribute to the efficiency of perovskite solar cells. still dominant efficiency and stability of the devices with the
As a result, high charge mobility ETL is the most important incorporation of electron transport layers [65, 66]. There-
factor for effective perovskite solar cells, as it leads to effi- fore, the selection of proper electron transport layers must
cient charge collection and transportation while suppressing fulfill the following criteria such as good electron mobility,
charge recombination at the interface [60, 61]. Another ele- wide band gap, and compatible energy level [67]. Wide band
ment that improves the efficiency of perovskite solar cells gap inorganic semiconductors are excellent ETL candidates
is energy level alignment. When ETL is better aligned with and have been utilized extensively to fabricate highly effi-
the perovskite absorber layers, electron extraction and trans- cient PSCs due to their low cost and considerable charge
portation become much easier. This means increasing the mobility. So far, binary and ternary metallic oxides and some
device’s short-current density (­ Jsc), fill factor (FF), and open- chalcogenides materials used as ETLs. Their band structures
circuit voltage (­ Voc). Other significant factors in defining and electron mobilities are listed in Fig. 5b [68]. Among
high-efficiency photovoltaic perovskite solar cells are charge them, until now T ­ iO2 is a widely used ETL and higher PCE
extraction, transport, and recombination at the interface. than others, but the electron recombination rates are very
One of the most critical factors in the ETL is trap states, high due to low conductivity and electron mobility which are
which influence charge extraction and transport, indicating unfavorable for electron collection and transport properties.
a high recombination rate at the interface. One technique to Moreover, they have defects such as oxygen vacancies and
improve the electron transport layer and the performance of metal interstitials at the surface and grain boundaries that
photovoltaic perovskite solar cells is to use interface engi- make less efficient and poor stability PSCs [69]. As a result,
neering. The device performance can also be improved by different studies have been conducted in order to improve the
improving the ETL’s surface morphologies. As a result, all performance and stability of photovoltaic perovskite solar
elements play a role in determining the device’s attributes cells. To improve the qualities of electron transport layers,
[61, 62]. Figure 5 a shows some charge carrier injection there are two essential aspects (ETLs). The first method
(i and iii), transport and collection (ii), and recombination involves doping additional elements into the ETL structure,

Fig. 5  a Charge transfer mechanism in the ETLs. b Electron mobility and band structure of various electron transport materials [adopted from
Refs. 61 and 70]

13
302 Journal of Solid State Electrochemistry (2022) 26:295–311

while the second method involves using bilayer materials for solution-processed method. The results revealed that the
electron transport layers [70, 71]. Al dopant in ­SnO2 enhanced the charge transport behav-
ior of planar PSCs and increased the current density of the
With doping and undoped electron transport material devices, compared with the undoped S ­ nO2 ETLs. Moreover,
in PSCs the enhanced electrical property also improved the fill fac-
tors and power conversion efficiency of the solar cells. Thus,
Doping is one way of improving the conductivity of ETLs the optimized cell based on Al-SnO2 exhibited a higher effi-
and optimizes the energy level matching between ETLs ciency of 12.10% than that using ­SnO2 (9.02%) as ETLs. The
and the perovskite film, leading to increasing the conduc- prepared low-temperature solution-processed Al-SnO2 pla-
tion band edge which can efficiently decrease the charge nar device structure and SEM images are shown in Fig. 6a–c
recombination process. Therefore, the electron transport lay- [74]. Similarly, Liu et al. studied the effect of tantalum dop-
ers have high conductivity, high electron extraction, lower ing on ­SnO2 (Ta-SnO2) electron transport layer prepared via
trap-state density, high electron mobility, and transportation chemical bath deposition method for perovskite solar cells.
process, resulting in enhanced performance of the perovskite The results confirmed that, in contrast to undoped ­SnO2, the
solar cell devices, reduced hysteresis, and improved stabil- I-V curve and transmittance spectra showed a significant
ity [72]. Different research has been developed with differ- conductivity improvement of Ta-SnO2 without declining the
ent doping materials; for instance, Wang et al. reported the light transmittance property. The results further revealed that
results obtained from poly-vinylpyrrolidone (PVP) doped Ta doping could accelerate the electron transfer and decrease
and undoped S ­ nO2 as ETLs. The PVP doped S ­ nO2 thin film the recombination probability at the ­SnO2/perovskite inter-
exhibits improved electron transport over the undoped one. face, as well as passivated the electron traps, leading to the
At the same time, the perovskite grown on PVP-SnO2 shows improvement in the PSC performance. The optimized device
more uniform crystalline grains, higher electron mobility, showed a power conversion efficiency of 20.80%, with an
and lower defect density than the control sample grown on open-circuit voltage of 1.161 V, a short-circuit current den-
the pure S­ nO2. The optimized device based on PVP doped sity of 22.79 mA/cm2 and a fill factor of 0.786. The device
­SnO2 exhibited an improved power conversion efficiency of structure and its performance are shown in Fig. 6d–g [75].
19.42% compared with the control PSC based on undoped Li-doped ­TiO2 layer was proposed as a solution to reduce
­SnO2. Furthermore, the PVP doped S ­ nO2-based devices the solar power loss of ETL conductance by Teimouri et al.
showed reduced hysteresis and better stability without any The doped ­TiO2 films have shown significantly improved
encapsulation [73]. Recently, Chen et al. proposed an effec- characteristics by increasing conductivity and providing
tive approach for producing planar PSCs with A ­ l3+ doped faster electron transport. A planar PSC device consists
­SnO2 ETLs which was prepared by using a low-temperature of an ETL with 0.3 M Li-doped ­TiO2 resulted in a power

Fig. 6  a Top-view SEM image of ­SnO2 on FTO. b Schematic of the measured under reverse and forward voltage scanning. f EQE of the
PSCs grown on Al-SnO2. c Cross-sectional SEM image of the planar ­ nO2 and Ta-SnO2 ETLs. g Stabilized PCEs for
devices deposited on S
perovskite solar cell based on Al-SnO2 [adopted from Ref. 76, open the ­SnO2- and Ta-SnO2-based devices [adopted from Ref. 75]
access]. d A typical planar PSC structure. e J-V curves of c PSCs

13
Journal of Solid State Electrochemistry (2022) 26:295–311 303

conversion efficiency of 24.23% which demonstrated 1.97% Single‑layer and bilayer electron transport materials
improvement compared to the one without doping [76]. Yin in PSCs
G and co-workers prepared Nb-doped ­TiO2 thin films by
simple one-port chemical bath process at low temperature Monolayer (single) charge transport layers have defects and
and applied as a high-quality ETL for planar PSCs. Com- pinholes at the interface; they provide the direct pathways
pared with pure ­TiO2, the Nb-doped ­TiO2 is more efficient between the perovskite absorber layer and the fluorine-
for photogenerated electron injected and extraction showing doped tin oxide (FTO)/ITO, which can increase the risk
higher conductivity, higher mobility, and low-state density. of the recombination between the photogenerated elec-
A PSC with 1% Nb-doped T ­ iO2 gives a power conversion trons and holes. Besides, they increase the energy loss at
efficiency of more than 19% with 1200-h stability in air [77]. the perovskite absorber layer with the interface of both
Similarly, a better electron extraction and transport, lower the transparent electrode and ETL [82]. Also, they reduce
trap-state density, and higher conductivity with power con- the blocking effect of electron transport layers, reducing
version efficiency about 17.2% are observed in Sn-doped the performance and lifetime of the perovskite solar cell.
­TiO2 compared with pristine ­TiO2 [78]. For the first time, However, the electron transport bilayer is the most efficient
Mahmood et al. reported highly porous indium-doped ZnO electron transport layer in perovskite solar cells that prevent
nanofibers by using electro-spinning rout as ETLs in PSCs. trapping electrons and the direct contact between perovs-
The high porosity and high crystallinity of the nanofibers kite absorber interface and FTO/ITO substrate. Besides,
give a better infiltration of the absorber and rapid charge it is important to remove the pinholes and cracks of the
transport characteristics due to indium (In) doping. This fea- surface of charge transport layers. Therefore, the uniform
ture of the material leads to highly efficient and hysteresis- and compact bilayer can effectively avoid charge accumu-
free PSCs with a best power conversion efficiency of 17.18% lation to reduce the charge recombination at the interface
at optimal thickness. Moreover, the incorporation of poly- and back electron transfer from ETLs to perovskite layers
mer polyethyleneimine coated with In-doped ZnO nanofiber also increasing the blocking effect of ETLs then increase
ETLs used in PSCs enhanced the power conversion efficiency open-circuit voltage, short current density, fill factor, and
to 18.69% with free hysteresis. Also, it reduced the work enhanced the performance of the perovskite solar cells [83].
function and the energy barrier, leading to high electron For example, different research has improved the interface
extraction, high conductivity, and good charge transportation between ETLs/perovskite active layer/FTO/ITO substrate
[79]. Jeong et al. reported alkali metal carbonates ­(Li2CO3, by using electron transport bilayer. However, a double-
­Na2CO3, ­K2CO3, and ­Cs2CO3) doped ZnO nanoparticles as layer ­TiO2/WO3 synthesized by spin coating and atomic
ETLs for the fabrication of planar heterojunction perovskite layer deposition (ALD) technology can avoid the defect of
solar cells. They used low-temperature solution-processed interfaces between ETLs/perovskite active layers/fluorine-
techniques to tune the energy band structure of ZnO ETLs doped tin oxide. This indicates that the minimum loss at the
with various alkali metal carbonates. Their results confirmed interface of ETLs/perovskite absorber layer/FTO substrate
that the power conversion efficiency of 27% is improved due and electron–hole recombination. Therefore, it has higher
to the incorporation of alkali carbonates in ETLs. recombination resistance and lower contact resistance [84].
This is due to the formation of deeper conduction bands It has a lower valence band maximum, and the energy level
in metal carbonates doped ZnO ETLs which leads the structure can efficiently block the holes than pristine ­WO3
electrons can easily transported from the perovskite active and ­TiO2, as shown in Fig. 3. Also fast electron transfer
layer to the cathode electrode. As alternatives to ­TiO2 and and an efficient electron extraction at interface perovskite
n-type metal oxides, electron transport materials consisting absorber layer and bilayer ETLs. In addition, one most
of doped ZnO nanoparticles are feasible ETLs for efficient important to enhance the performance of perovskite solar
n-i-p planar heterojunction solar cells, and they can be used cells is controlling the thickness of T
­ iO2. The PCE for pla-
on flexible substrates via roll-to-roll processing. The sche- nar perovskite solar cells exhibited about 20.14% as well as
matic diagram of the PSC device and band structure of the an average PCE of 18.19%, which is better than single ­TiO2
metal carbonates doped ZnO is shown in Fig. 7a–c [80]. In or ­WO3 of PCE 16.99% or 17.04% reported by You Y and
general, doing is one of the most important strategies for co-workers [84]. In 2018, Yi et al. reported bilayer S ­ nO2 as
enhancing intrinsic electronic properties of charge transport an efficient ETL in ­MAPbI3-based perovskite solar cell by a
layer in perovskite solar cell device. Therefore, increasing low-temperature solution-processed method. This bilayer of
the conductivity of the materials ETLs, which is reduced the ­SnO2 ETLs synthesized using S ­ nO2 nanoparticle incorpo-
series resistance contact at the interface of ETLs/ Perovskite rating with a thin layer S
­ nO2 sol–gel method a uniform and
absorber layer / electrode also the formation of ohmic con- pin-hole free has been formed. Therefore, bilayer S ­ nO2 ETL
tacts to the external electrode, which enhances the fill factor devices have lower contact series resistance which implies
in the perovskite solar cells [81]. increasing conductivity of ­SnO2 ETLs and charge extraction

13
304 Journal of Solid State Electrochemistry (2022) 26:295–311

Fig. 7  a Schematic diagram of device. b SEM cross section images of the conventional planar perovskite solar cell with doped ZnO. c Energy
band diagram of ZnO doped with various alkali metal carbonate materials [adopted from Ref. 82]

properties at the perovskite/ETL interface. Also, the fewer results verified that the T
­ iO2 bilayer-based perovskite solar
defects indicate lower recombination of electron–hole at cells were highly efficient in carrier extraction, recombina-
the interface that give higher current density and fill fac- tion suppression, and defect passivation, and thus demon-
tors and average power conversion efficiency from 12.97 strate champion efficiencies up to 16.5%, presenting almost
to 16.84% [85]. Martínez-Denegri et al. synthesized ­SnO2/ 50% enhancement compared to the ­TiO2 single-layer-based
TiO2 nanoparticle at low-temperature and spin-coating counterparts [87]. F-doped S ­ nO2 nanocrystals using facile
method as ETL bilayers. They demonstrated that a few low-temperature solution-processed method as bilayer ETL
tens of nanometers thick bilayer can perform as a robust. planar heterojunction perovskite solar cells was reported by
Aside from boosting the average efficiency of planar opaque Gong et al. They found that a gradual substitution of ­F− into
devices, the proposed method allowed them to preserve the the ­SnO2 ETL can effectively reduce the band offset and
main photovoltaic characteristics when thinner active lay- result in a substantial increase in device open-circuit volt-
ers, usually exhibiting a noncontinuous morphology, were age. As a result, a power conversion efficiency of 20.2% was
integrated for semitransparent cells. The bilayers of ETL achieved for planar hetrojunction PSCs using F-doped S ­ nO2
power conversion efficiency exhibited from 14.9 to 15.2% as bilayer ETL. Furthermore, reduced the charge accumula-
and short-circuit photocurrent and fill factor values which tion of at the interface between ETLs and perovskite active
are higher than that of monolayer [86]. Lu H and co-workers layer leads reducing energy loss due to high charge extrac-
successfully designed a novel T ­ iO2 bilayer with type II tion and transport at interface [88]. Li et al. introduced a
band alignment at different Fermi energy levels by combing low-temperature solution method to deposit a ­TiO2/SnO2
atomic layer deposition and spin-coating technique. Their bilayer for an efficient ETL. The results demonstrated that

13
Journal of Solid State Electrochemistry (2022) 26:295–311 305

the ­TiO2/SnO2 ETL has an enhanced charge extraction from 13.2 to 17.2% [83]. Similarly, Kumari et al. synthe-
ability and a suppressed carrier recombination at the ETL/ sized ­TiO2/ZnO by spray pyrolysis technique method as
perovskite interface, which gives a better photogenerated ETLs for perovskite solar cells. This bilayer helps in high
carrier separation and transport for T
­ iO2/SnO2 bilayer ETL. electron extraction and low interfacial recombination due
As a result, PSCs with ­TiO2/SnO2 bilayer ETLs present to high charge collection and transportation, therefore lower
higher photovoltaic performance of the baseline cells com- charge accumulation at the interface between ETLs and per-
pared with their ­TiO2 and S ­ nO2 single-layer ETL counter- ovskite active layer.
parts. The optimized PSC device has a power conversion In addition by using 4-tert-butylpyridine (TBP) increase
efficiency of 19.11% with an open-circuit voltage of 1.15 V, in the contact angle of prepared films reduces the of deg-
a short-circuit current density of 22.77 mA ­cm−2, and a fill radation of perovskite film into ­PbI2 under moisture. This
factor of 72.38% shown in Fig. 8a [85]. Due to the suit- enhanced the stability of perovskite solar cells. Moreover,
able band alignment Fig. 8b of the ­TiO2/SnO2 ETL in the controlling the effect of precursor concentration, thickness,
device, a high open-circuit voltage of 1.18 V is achieved. substrate temperature, and solution flow rate is important to
The obtained J-V values, band gap alignment, and PL spec- determine optimization condition of ­TiO2 film. The highest
tra are depicted in Fig. 8a–d [89]. In another work, Xu et al. power conversion efficiency of about 7.39% was found for
prepared ­TiO2/ZnO bilayer by employing a sol–gel method the device with TBP [90]. For the first time, Wang et al.
as ETLs for perovskite solar cells. These bilayers improved reported the highest open-circuit voltage around 1.15 V
the interfacial layer by avoiding the direct contact between for ZnO/SnO2 double layer as ETLs with a power conver-
the FTO substrate and perovskite active layer. Moreover, sion efficiency 18% [91]. The benefits of low-temperature
this bilayer, together with perovskite absorber, forms a type processed fullerene/SnO2 bilayers as ETLs for efficient pla-
II energy band structure benefiting high charge extraction nar perovskite solar cells were investigated by Chen Y and
and transport leading to lower electron–hole recombination co-worker. The results show that the existence of ­PC60BM
in the cells and improved final power conversion efficiency could enhance the crystalline quality and grain boundary

Fig. 8  a The J-V curves of the PSC based on T­ iO2/SnO2 bilayer ETL. b Band alignment for different ETLs: T ­ iO2/SnO2. c PL
­ iO2, ­SnO2, and T
spectra and d time-resolved PL curves of perovskite film deposited on different ETLs: T
­ iO2, ­SnO2, and ­TiO2/SnO2 [adopted from Ref. 91]

13
306 Journal of Solid State Electrochemistry (2022) 26:295–311

integration in perovskite films. The J-V analysis and other efficiency, but the stability is greatly enhanced and hyster-
experimental results revealed that both the light harvesting esis of the films are reduced [103]. Recently, a fullerene
of perovskite films and carrier extraction from perovskite derivative pyrrolidinofullerene C60-substituted phenol
films to ­PC60BM/SnO2 bilayer have been enhanced. The (NPC60-OH) was introduced to modify the surface ­SnO2
device performance shows a higher average PCE 15.03% ETLs, which reduced the energy band gap between ETL
and also improved short-circuit current density about and the perovskite film due to the suitable work function
21.05 mA·cm−2 [92]. Corresponding, different researcher of ­SnO2/NPC60-OH. Therefore, high conductivity of ETL
has been enhanced the performance of the perovskite solar leads to high charge mobility and transportation, hence
cells were used a bilayer as the electron transport layer in suppresses charge recombination and lower trap-stat den-
perovskite film. Hence improved the interface between elec- sity at interface. However, the electrical parameter of Voc,
tron transport layer/perovskite active layer / FTO substrate ­Jsc, and FF are enhanced and the power conversion effi-
and prevent direct contact of them also improved the charge ciency has reached 21.39% but lower hysteresis and more
extraction and transportation indicate reduce charge accu- stable device than pure S ­ nO2 [104]. Modify the surface of
mulation, energy loss and trap-state density also suppressed ZnO ETL with methoxybenzoic acid derivatives (3,4,5-
electron hole recombination such as ZnO-PCBM [93], ­SnO2/ trimethoxybenzoic acid) (TMBA) which made a larger
ZnO [94], PCBM/CeOx [95], ZnO/AZO [96], ­TiO2/SnO2 work function shift of ZnO ETL and high charge extrac-
[97]. tion and transfer due to improved conductivity. Moreover,
reduced electron–hole recombination, lower trap-state
Interface engineering density, and hysteresis, which is higher open-circuit volt-
age than the power conversion efficiency has been found
Interface engineering for conventional PSCs from 1.44 to 13.75% [105]. A self-assembled monolayer
of γ-mercaptopropyltrimethoxysilane (γ-MPTS) was used
SAMs  Self-assembled monolayers (SAMs) were utilized to modify the interface between the meso-TiO2 surface
to change the dielectric and drain electrode surfaces of ETLs and the perovskite layer which leads to minimized
electron-selective transfer layers made of metal oxide. trap-state density and improved the carrier transport per-
Thermodynamically, self-assembly of molecules on the formance. Also, the electron–hole recombination and the
surface is a process in which molecules interact with one power conversion efficiencies were achieved from 14.36
another to produce structured structures. Surface passiva- to 16.50% which less hysteresis, hence better performed
tion dielectrics such as S­ iO2 or ­Al2O3 are the most often than unmodified T ­ iO2 [106]. Modified the surface of W
­ Ox
used [98]. SAMs improve the shape and crystal quality of layer with SAM layer used a low-temperature process, the
the perovskite layer by improving crystallinity, increasing Jsc, Voc, FF, and PCE were improved. Therefore, power
grain size, and lowering the degree of defects at the sur- conversion efficiency was reached to 14.9% without any
face. Furthermore, fine-tuning the polarity of molecules hysteresis [107].
to manage the interfacial dipole moment in relation to the
normal surface indicates a change in the work function Window layer passivation  Improving the interface between
[99]. As a result, changing the surface morphology of per- ETLs and the perovskite absorber layer is an effective
ovskite solar cells reduces charge carrier traps and energy method for suppressing the charge recombination. There-
loss at the interface, resulting in improved charge extrac- fore, using a wide layer controlling the charge recombi-
tion and transportation from the active layer of the per- nation at the surface of ­TiO2, ­SnO2, ZnO, and ­WO3. The
ovskite. As a result, reducing charge accumulation at the interface between the ­TiO2 layer and the perovskite layer
interface causes charge recombination to be suppressed was modified by an ultrathin MgO nanolayer. This MgO-
and hysteresis to be reduced [100]. This is modified by the coated ­TiO2 film suppresses charge recombination at the
surface energy of dielectric materials. The modification ­TiO2/CH3NH3PbI3 surface, which leads to the improve-
of electron transport layer interface and perovskite active ment in both ­Voc and FF; therefore, an increase of PCE
layer with functional SAMs has been causing improve- from 11.4 to 12.7% was demonstrated [108]. An ultrathin
ment in electrical parameters which can contribute to ­Zn2SnO4 (ZTO) layer was coated onto ZnO nanocone via a
increasing the efficiency of perovskite solar cell device solution-processed method to modify the interface between
[101, 102]. The combination of SAMs with metal oxide the ZnO layer and the perovskite layer. This ZTO-coated
such as ­TiO2, ZnO, and S ­ nO2 further improves the inter- ZnO film could retard the charge recombination at ZnO/
face properties of perovskite solar cells. Modifying the perovskite active layer surface. This combination showed
surfaces of noninverted ­(SnO2) and inverted ­(NiOx) films an improvement in all PV parameters with power conver-
with ethylphosphonic acid (EPA) and 4-bromobenzoic sion efficiency about 18.3% [109]. The surface modifica-
acid (BBA) SAMs does not necessarily lead to enhanced tion of ZnO covered the ultrathin ­Nb2O5 passivation layer

13
Journal of Solid State Electrochemistry (2022) 26:295–311 307

synthesized by the sol–gel method, which could reduce Conclusion and future perspective
ZnO surface defects and also improved the morphology
of ­CH3NH3PbI3 perovskite film. The ultrathin ­Nb2O5 pas- Charge transport layers in perovskite solar cells may serve
sivation layer effectively prevents direct contact between as n-type to couple the half in a p–n junction, reduce sur-
the ZnO and perovskite and prevents the decomposition of face recombination at the interface, conduct the current
the perovskite light absorber coated over ZnO. to the metal electrode, and allow the incoming light to
Therefore, an efficient charge transport layer leads pass the maximum portion through and reach the absorber
suppress charge recombination and improved power con- layer. Therefore, in this review, we have presented efforts
version efficiency to 14.57% [110]. Fullerene derivative that have been made to improve the PCE using a single
pyrrolidinofullerene ­C60-substituted phenol (­ NPC60-OH) layer and bilayer of ETL, the interface between the ETL,
modified surface of S ­ nO2 ETLs reduce the charge recom- and the perovskite absorber layer. The effects of doping
bination and trap-state density indications enhance the on the properties of ETL in perovskite solar cells were
electron mobility and transportation of perovskite solar thoroughly discussed. Various metal oxides such as ­TiO2,
cells. Furthermore, The ­NPC60-OH-based devices showed ZnO, ­SnO2, ­WOx, and fullerene and their derivatives as
a reduced energy band gap between ETL and the per- ETLs have been researched and applied to perovskite solar
ovskite film due to the suitable WF of S ­ nO2/NPC60-OH, cells. The charge collection efficiency of single ETL of
which contributed to the high open-circuit voltage and the ­TiO2-based ETL has been improved by using bilayers
improved power conversion efficiency [104]. such as ­TiO2/SnO2, ­TiO2/ZnO, ­TiO2/WO3, and appropri-
ate substitution of cation doping such as Nb, Sn, and Li.
The improved charge collection performance using bilayer
Stability and performance of perovskite solar cells and doped ETL may arise due to the reduction of charge
carrier recombination at the surface, enhancing the current
Perovskite solar cells’ long-term stability is a significant conduction ability of the layers. It also noted that the inter-
consideration for commercial use. As a result, a variety face between the charge transport layers and perovskite
of factors affecting perovskite solar cell stability, such active layer modifications with functional self-assembled
as moisture, oxygen, temperature, and UV radiation monolayers (SAMs) is important for enhancing charge
stability, must be carefully evaluated [111, 114]. Dif- extraction and transportation. Besides, suppressing charge
ferent researchers have focused on improving the stabil- recombination indicates enhanced performance and stabil-
ity of PSCs by introducing moisture, oxygen, UV light, ity in perovskite solar cell devices. Therefore, to harness
and thermal-resistant layers. For example, Wang et al. the widest portion of visible light-generated charge carri-
reported that polyethylene glycol (PEG) into the methyl- ers using perovskite solar cells needs careful design of the
ammonium lead trihalide ­( MAPbI 3) precursor solution, ETL and interfaces. It possibly boosts the efficiency, and a
with ­TiO 2-ZrO 2 mesoporous scaffold as ETLS in PSCs hysteresis-free perovskite solar cell device was constructed
with carbon electrode and the hole-conductor-free. The for commercial application. Therefore, bilayers ETL will
hygroscopic PEG protects the perovskite film from mois- improve the PCE of perovskite solar cells by improving the
ture which leads exhibit superior stability and enhanced current conduction through them to the metal electrode,
the power conversion efficiency of 11.62% [100]. Cesium enhancing the amount of light passing through to the pho-
iodide doped in methylammonium lead iodide perovskite ton active layer, and reducing charge carrier recombination
­(CsxMA1-xPbI3) as light absorber layer with carbon coun- at the surface and interface.
ter electrode and hole-conductors-free perovskite solar
cell were fabricated under a high humidity air environ-
ment. The results revealed that the presence of cesium
and carbon improved the moisture-resistant of the perovs- References
kite solar cell devices with high stability and enhanced
power conversion efficiency [112]. Modifying the inter- 1. Kojima A, Teshima K, Shirai Y, Miyasaka T (2009) Organometal
face between mesoporous ­T iO 2 /perovskite layer were halide perovskites as visible-light sensitizers for photovoltaic
cells. J Am Chem Soc 131(17):6050–6051
used both aminocaproic acid [­ H2NCH2(CH2)4COOH] and 2. Tang G, You P, Tai Q, Yang A, Cao J, Zheng F, Zhou Z, Zhao J,
caproic acid [­ CH 3(CH 2) 4COOH], leading to significant Chan P-K-L, Yan F (2019) Solution-phase epitaxial growth of
enhancement in both the efficiency and stability of PSCs. perovskite films on 2D material flakes for high-performance solar
This modified mesoporous T ­ iO2/perovskite layer of power cells. Adv Mater 31(24):1807689
3. Ahn N, Son D-Y, Jang I-H, Kang S-M, Choi M, Park N-G (2015)
conversion efficiency was found 18.2% and improving Highly reproducible perovskite solar cells with average efficiency
the stability of PSCs under 50 ± 5% relative humidity in of 18.3% and best efficiency of 19.7% fabricated via Lewis base
the air [113]. adduct of lead (II) iodide. J Am Chem Soc. 137(27):8696–8699.

13
308 Journal of Solid State Electrochemistry (2022) 26:295–311

4. Chen W, Wu Y, Yue Y, Liu J, Zhang W, Yang X, Chen H, Bi E, deposition strategy boosts efficiency of perovskite solar cells to
Ashraful I, Grätzel M, Han L (2015) Efficient and stable large- 20%. Adv Mater 30(28):1801935
area perovskite solar cells with inorganic charge extraction lay- 21. Guo Q, Wu J, Yang Y, Liu X, Sun W, Wei Y, Lan Z, Lin J, Huang
ers. SCi 350(6263):944–948 M, Chen H, Huang Y (2020) Low-temperature processed rare-
5. Liu X, Zhao W, Cui H, Wang Y, Xu T, Huang F (2015) Cor- earth doped brookite ­TiO2 scaffold for UV stable, hysteresis-
rection: Organic–inorganic halide perovskite based solar cells– free and high-performance perovskite solar cells. Nano Energy.
revolutionary progress in photovoltaics. Inorg Chem Front 77:105183
2(6):584–584 22. Şahin Ç, Diker H, Sygkridou D, Varlikli C, Stathatos E (2020)
6. Kojima A, Teshima K, Miyasaka T, Shirai Y (2006) Novel pho- Enhancing the efficiency of mixed halide mesoporous perovskite
toelectrochemical cell with mesoscopic electrodes sensitized by solar cells by introducing amine modified graphene oxide buffer
lead-halide compounds (2). ECS Meeting Abstract, Meet Abstr layer. Renew Energy 146:1659–1666
MA. 2006–02: 397 23. Dagar J, Castro-Hermosa S, Gasbarri M, Palma A-L, Cina L,
7. Im J-H, Lee C-R, Lee J-W, Park S-W, Park N-G ( 2011) 6.5% Matteocci F, Calabrò E, Di Carlo A, Brown T-M (2018) Efficient
efficient perovskite quantum-dot-sensitized solar cell. Nanoscale. fully laser-patterned flexible perovskite modules and solar cells
3(10):4088–4093. based on low-temperature solution-processed S ­ nO2/mesoporous-
8. Kim H-S, Lee C-R, Im J-H, Lee K-B, Moehl T, Marchioro A, TiO2 electron transport layers. Nano Res 11(5):2669–2681
Moon S-J, Humphry-Baker R, Yum J-H, Moser J-E, Grätzel M 24. Ye W, Xiang J, Huang F, Zhong D (2018) Towards large-area
(2012) Lead iodide perovskite sensitized all-solid-state submi- perovskite solar cells: the influence of compact and mesoporous
cron thin film mesoscopic solar cell with efficiency exceeding ­TiO2 electron transport layers. Mater Res Express. 5(8):085506
9%. Sci Rep 2(1):1–7 25. Shen D, Zhang W, Xie F, Li Y, Abate A, Wei M (2018) Graphene
9. Liu M, Johnston M-B, Snaith H-J (2013) Efficient planar het- quantum dots decorated T ­ iO2 mesoporous film as an efficient
erojunction perovskite solar cells by vapour deposition. Nature electron transport layer for high-performance perovskite solar
501(7467):395–398 cells. J Power Sources 402:320–326
10. Lee M-M, Teuscher J, MiyasakaT M-N, Snaith H-J (2012) Effi- 26. Yang M, Zhang Y, Du J, Yang L, Fan L, Sui Y, Wang F (2019)
cient hybrid solar cells based on meso-superstructured organo- Engineering the mesoporous T ­ iO2 layer by a facile method to
metal halide perovskites. SCi 338(6107):643–647 improve the performance of perovskite solar cells. Electrochim
11. Yang G, Tao H, Qin P, Ke W, Fang G (2016) Recent progress Acta 318:83–90
in electron transport layers for efficient perovskite solar cells. J 27. Wang Z, Fang J, Mi Y, Zhu X, Ren H, Liu X, Yan Y (2018)
Mater Chem A 4(11):3970–3990 Enhanced performance of perovskite solar cells by ultraviolet-
12. Agha D-N- Q, Algwari Q- T (2021) The influence of the interface ozone treatment of mesoporous ­TiO2. Appl Surf Sci 436:596–602
layer between the electron transport layer and absorber on the 28. Wang D, Chen Q, Mo H, Jacobs J, Thomas A, Liu Z (2020) A
performance of perovskite solar cells. In IOP Conference Series: bilayer ­TiO2/Al2O3 as the mesoporous scaffold for enhanced air
Mater Sci Eng. (Vol. 1152, No. 1, p. 012033). IOP Publishing stability of ambient-processed perovskite solar cells. Adv Mater
13. Ke W, Fang G, Liu Q, Xiong L, Qin P, Tao H, Wang J, Lei H, Li 1(6):2057–2067
B, Wan J, Yang G (2015) Low-temperature solution-processed 29. Tomulescu A-G, Stancu V, Beşleagă C, Enculescu M, Nemneş
tin oxide as an alternative electron transporting layer for efficient G-A, Florea M, Dumitru V, Pintilie L, Pintilie I, Leonat L (2020)
perovskite solar cells. J Am Chem Soc 137(21):6730–6733 Reticulated Mesoporous ­TiO2 Scaffold, Fabricated by Spray
14. Ahn N, Son D-Y, Jang I-H, Kang S-M, Choi M, Park N-G (2015) Coating, for Large-Area Perovskite Solar Cells. Energy Technol
Highly reproducible perovskite solar cells with average efficiency 8(1):1900922
of 18.3% and best efficiency of 19.7% fabricated via Lewis base 30. Dong G, Xia D, Yang Y, Zhang W, Fan R, Sui L, Li Y (2020).
adduct of lead (II) iodide. J Am Chem Soc. 137(27):8696–8699 In-situ passivation of T­ iO2 mesoporous scaffold with nano-sized
15. Pham H-D, Yang T-C-J, Jain S-M, Wilson G-J, Sonar P (2020) heteropolyacid for boosting the efficiency of the perovskite solar
Development of dopant-free organic hole transporting materials cells. Electrochim Acta. 332:135427
for perovskite solar cells. Adv Energy Mater 10(13):1903326 31. Shen D, Zhang W, Li Y, Abate A, Wei M (2018) Facile depo-
16. Parida B, Singh A, Oh M, Jeon M, Kang J- W, Kim H, (2019) sition of N ­ b2O5 thin film as an electron-transporting layer for
Effect of compact T ­ iO2 layer on structural, optical, and per- highly efficient perovskite solar cells. ACS Appl Nano Mater
formance characteristics of mesoporous perovskite solar cells. 1(8):4101–4109
Mater Today Commun 18:176–183 32. Hwang S-H, Roh J, Lee J, Ryu J, Yun J, Jang J (2014) Size-
17. Thambidurai M, Dewi H-A, Harikesh P-C, Foo S, Muhammed controlled ­SiO2 nanoparticles as scaffold layers in thin-film per-
Salim, K-M, Mathews N, Dang C(2018). Highly efficient per- ovskite solar cells. J Mater Chem A 2(39):16429–16433
ovskite solar cells with Ba (OH)2 interface modification of 33. Niu G, Li W, Meng F, Wang L, Dong H, Qiu Y (2014) Study on the
mesoporous ­TiO2 electron transport layer. ACS Appl Energy stability of C­ H3NH3PbI3 films and the effect of post-modification
Mater 1(11):5847–5852 by aluminum oxide in all-solid-state hybrid solar cells. J Mater
18. Zhang B, Zhang B, Wang S, Yao S, Bala H, Sun G, Zhang Chem A 2(3):705–710
Z(2020) Applying neoteric ­MgTiO3-coated ­TiO2nanoparticulate 34. Dong X, Fang X, Lv M, Lin B, Zhang S, Ding J, Yuan N (2015)
films as scaffold layers in perovskite solar cells based on carbon Improvement of the humidity stability of organic–inorganic
counter electrode for retarding charge recombination. Electro- perovskite solar cells using ultrathin ­Al2O3 layers prepared by
chim Acta. 338:135884 atomic layer deposition. J Mater Chem A 3(10):5360–5367
19. Xiong L, Qin M, Chen C, Wen J, Yang G, Guo Y, Ma J, Zhang 35. Bi D, Moon S-J, Häggman L, Boschloo G, Yang L, Johansson
Q, Qin P, Li S, Fang G (2018) Fully high-temperature processed E-M, Nazeeruddin M-K, Grätzel M, Hagfeldt A (2013) Using a
­SnO2 as blocking layer and scaffold for efficient, stable, and hys- two-step deposition technique to prepare perovskite (­ CH3NH3PbI3)
teresis free mesoporous perovskite solar cells. Adv Funct Mater for thin film solar cells based on Z­ rO2 and T
­ iO2 mesostructures.
28(10):1706276 RSC Adv 3(41):18762–18766
20. Sun H, Deng K, Zhu Y, Liao M, Xiong J, Li Y, Li L (2018) 36. Qiang Y, Xie Y, Qi Y, Wei P, Shi H, Geng C, Liu H (2020)
A novel conductive mesoporous layer with a dynamic two-step Enhanced performance of carbon-based perovskite solar cells

13
Journal of Solid State Electrochemistry (2022) 26:295–311 309

with a L­ i+-doped ­SnO2 electron transport layer and A ­ l2O3 scaf- 53. Anaraki E-H, Kermanpur A, Steier L, Domanski K, Matsui T,
fold layer. Sol Energy 201:523–529 Tress W, Saliba M, Abate A, Grätzel M, Hagfeldt A, Correa-
37. Xiong Y, Zhu X, Mei A, Qin F, Liu S, Zhang S, Jiang Y, Zhou Baena J-P (2016) Highly efficient and stable planar perovskite
Y, Han H (2018) Bifunctional ­Al2O3 interlayer leads to enhanced solar cells by solution-processed tin oxide. Energy Environ Sci
open-circuit voltage for hole-conductor-free carbon-based per- 9(10):3128–3134
ovskite solar cells. Sol RRL 2(5):1800002 54. Luo D, Yang W, Wang Z, Sadhanala A, Hu Q, Su R, Shivanna
38. Inami E, Ishigaki T, Ogata H (2019) Sol-gel processed niobium R, Trindade G-F, Watts J-F, Xu Z, Liu T (2018) Enhanced pho-
oxide thin-film for a scaffold layer in perovskite solar cells. Thin tovoltage for inverted planar heterojunction perovskite solar
Solid Films 674:7–11 cells. Sci 360(6396):1442–1446
39. e Asl S-D Zarenezhad H, Askari M, Halali M, Sadrnezhaad S-K 55. Saliba M, Correa-Baena J-P, Wolff C-M, Stolterfoht M, Phung
(2020) Efficient light harvesting in perovskite layer via three- N, Albrecht S, Neher D, Abate A (2018) How to make over
dimensional ­TiO2 nanobranched nanorod scaffold. Nano Express. 20% efficient perovskite solar cells in regular (n–i–p) and
1(3) p.030017 inverted (p–i–n) architectures. Chem Mater 30(13):4193–4201
40. Matsui T, Seo J-Y, Saliba M, Zakeeruddin S-M, Grätzel M 56. Wu Y, Yang X, Chen W, Yue Y, Cai M, Xie F, Bi E, Islam A,
(2017) Room-temperature formation of highly crystalline mul- Han L (2016) Perovskite solar cells with 18.21% efficiency and
tication perovskites for efficient, low-cost solar cells. Adv Mater area over 1 c­ m2 fabricated by heterojunction engineering. Nat
29(15):1606258 Energy. 1(11):1–7
41. Ball J-M, Lee M-M, Hey A, Snaith H-J (2013) Low-temperature 57. You J, Meng L, Song T-B, Guo T-F, Yang Y-M, Chang W-H,
processed meso-superstructured to thin-film perovskite solar Hong Z, Chen H, Zhou H, Chen Q, Liu Y (2016) Improved air
cells. Energy Environ Sci 6(6):1739–1743 stability of perovskite solar cells via solution-processed metal
42. Heo J-H, Song D-H, Han H-J, Kim S-Y, Kim J-H, Kim, D, oxide transport layers. Nat Nanotechnol 11(1):75–81
Shin H-W, Ahn T-K, Wolf C, Lee T-W, Im S-H (2015) Planar 58. Park I-J, Kang G, Park M-A, Kim J-S, Seo S-W, Kim D-H,
­CH3NH3PbI3 perovskite solar cells with constant 17.2% average Zhu K, Park T, Kim J-Y (2017) Highly efficient and uni-
power conversion efficiency irrespective of the scan rate. Adv form 1cm2 perovskite solar cells with an electrochemically
Mater. 27(22):3424–3430 deposited NiOx hole-extraction layer. Chem Sus Chem
43. Cai Y, Zhang Z, Zhou Y, Liu H, Qin Q, Lu X, Gao X, Shui L, 10(12):2660–2667
Wu S, Liu J (2018) Enhancing the efficiency of low-temperature 59. Kim T, Lim J, Song S (2020) Recent progress and challenges of
planar perovskite solar cells by modifying the interface between electron transport layers in organic–inorganic perovskite solar
perovskite and hole transport layer with polymers. Electrochim cells. Energies 13(21):5572
Acta 261:445–453 60. Pan H, Zhao X, Gong X, Li H, Ladi N- H, Zhang X- L, Fu Y,
44. Dong H, Wu Z, Xi J, Xu X, Zuo L, Lei T, Zhao X, Zhang L, (2020) Advances in design engineering and merits of elec-
Hou X, Jen A-K-Y (2018) Pseudohalide-induced recrystallization tron transporting layers in perovskite solar cells. Mater Horiz
engineering for C ­ H3NH3PbI3 film and its application in highly 7(9):2276–2291
efficient inverted planar heterojunction perovskite solar cells. 61. Yu M, Guo Y, Yuan S, Zhao J-S, Qin Y, Ai X-C (2020) The
Adv Funct Mater 28(2):1704836 influence of the electron transport layer on charge dynamics
45. Xie F, Chen C-C, Wu Y, Li X, Cai M, Liu X, Yang X, Han L and trap-state properties in planar perovskite solar cells. RSC
(2017) Vertical recrystallization for highly efficient and stable Adv 10(21):12347–12353
formamidinium-based inverted-structure perovskite solar cells. 62. Chen J, Park N-G (2020) Materials and methods for interface
Energy Environ Sci 10(9):1942–1949 engineering toward stable and efficient perovskite solar cells.
46. Zheng Y, Kong J, Huang D, Shi W, McMillon-Brown L, Katz ACS Energy Lett 5(8):2742–2786
H-E, Yu J, Taylor A-D (2018) Spray coating of the PCBM elec- 63. Zhou D, Zhou T, Tian Y, Zhu X, Tu, Y (2018) Perovskite-based
tron transport layer significantly improves the efficiency of pin solar cells: materials, methods, and future perspectives. Journal
planar perovskite solar cells. Nanoscale 10(24):11342–11348 of Nanomaterials, 2018.
47. Zheng Y, Shi W, Kong J, Huang D, Katz H-E, Yu J, Taylor A-D 64. Hu A, Levis S, Meehl G-A, Han W, Washington W-M, Oleson
(2017) A Cytop insulating tunneling layer for efficient perovskite K-W, Van Ruijven B-J, He M, Strand W-G (2016) Impact of
solar cells. Small Methods 1:1700244 solar panels on global climate. Nat Clim Chang 6(3):290–294
48. Zhu P, Gu S, Luo X, Gao Y, Li S, Zhu J, Tan H (2020) Simultane- 65. Ke W, Fang G, Wan Tao J-H, Liu Q, Xiong L, Qin P, Wang
ous Contact and Grain-Boundary Passivation in Planar Perovs- J, Lei H, Yang G, Qin M, X. Zhao X, Yan Y, (2015) Efficient
kite Solar Cells Using ­SnO2-KCl Composite Electron Transport hole-blocking layer-free planar halide perovskite thin-film
Layer. Adv Energy Mater 10(3):1903083 solar cells. Nat Commun 6:6700
49. LeeY LS, Seo G, Paek S, Cho K-T, Huckaba A-J, Calizzi M, 66. Noh M-F-M, Teh C-H, Daik R, Lim E-L, Yap C- C, Ibrahim
Park C-W, J-S, Lee D, Lee H-J, (2018) Efficient planar perovskite M- A Teridi, M-A- M (2018) The architecture of the electron
solar cells using passivated tin oxide as an electron transport transport layer for a perovskite solar cell. J Mater Chem C
layer. Adv Sci 5(6):1800130 6(4):682–712
50. Subbiah A-S, Dhara A-K, Mahuli N, Banerjee S, Sarkar S-K 67. Zhu L, Ye J, Zhang X, Zheng H, Liu G, Pan X, S. Dai S (2017)
(2020) Ultra-thin atomic layer deposited–Nb2O5 as electron Performance enhancement of perovskite solar cells using a
transport layer for co-evaporated ­MAPbI3 planar perovskite solar La-doped ­BaSnO3 electron transport layer. J Mater Chem A
cells. Energy Technol 8(4):1900878 5:3675
51. Singh M, Ng A, Ren Z, Hu H, Lin H-C, Chu C-W, Li G (2019) 68. Wang K, Olthof S, Subhani W-S, Jiang X, Cao Y, Duan L, Liu
Facile synthesis of composite tin oxide nanostructures for S- F (2020) Novel inorganic electron transport layers for planar
high-performance planar perovskite solar cells. Nano Energy perovskite solar cells: Progress and prospective. Nano Energy.
60:275–284 68:104289
52. Tang H, Cao Q, He Z, Wang S, Han J, Li T, Gao B, Yang J, Deng 69. Kim D-H, Han G-S, Seong W-M, Lee J-W, Kim B-J, Park N-G,
D, Li X (2020) ­SnO2–Carbon Nanotubes Hybrid Electron Trans- Hong K-S, Lee S, Jung H-S (2015) Niobium doping effects on
port Layer for Efficient and Hysteresis-Free Planar Perovskite ­TiO2 mesoscopic electron transport layer based perovskite solar
Solar Cells. Sol RRL 4(1):1900415 cells. Chemsuschem 8(14):2392–2398

13
310 Journal of Solid State Electrochemistry (2022) 26:295–311

70. Li N, Yan J, Ai Y, Jiang E, Lin L, Shou C, Ye J (2020) A 87. Lu H, Tian W, Gu B, Zhu Y, Li L (2017) T ­ iO2 electron transport
low-temperature ­TiO2/SnO2 electron transport layer for high- bilayer for highly efficient planar perovskite solar cell. Small
performance planar perovskite solar cells. Sci China Mater 13(38):1701535
63(2):207–215 88. Gong X, Sun Q, Liu S, Liao P, Shen Y, Grätzel C, Zakeeruddin
71. Zhou N, Cheng Q, Li L, Zhou H (2018) Doping effects in S ­ nO2 S-M, Grätzel M, Wang M (2018) Highly efficient perovskite solar
transport material for high performance planar perovskite solar cells with gradient bilayer electron transport materials. Nano Lett
cells. J Phys D: Appl Phys. 51(39):394001 18(6):3969–3977
72. Chiang C-H, Kan C-W, Wu C- G, (2021) Synergistic engineering 89. Li N, Yan J, Ai Y, Jiang E, Lin L, Shou C, Yan B, Sheng J, Ye J
of conduction band, conductivity, and interface of bilayered elec- (2020) A low-temperature T ­ iO2/SnO2 electron transport layer for
tron transport layers with scalable ­TiO2 and S ­ nO2 nanoparticles high-performance planar perovskite solar cells. Sci China Mater
for high-efficiency stable perovskite solar cells. ACS Appl Mater 63(2):207–215
Interfaces 13(20):23606–23615 90. Kumari N, Gohel J-V, Patel S-R (2018) Optimization of ­TiO2/
73. Wang D, Chen S-C, Zheng Q (2019) Poly (vinyl-pyrrolidone)- ZnO bilayer electron transport layer to enhance efficiency of per-
doped ­S nO 2 as an electron transport layer for perovskite ovskite solar cell. Mater Sci Semicond Process 75:149–156
solar cells with improved performance. J Mater Chem C 91. Wang D, Wu C, Luo W, Guo X, Qu B, Xiao L, Chen Z (2018)
7(39):12204–12210 ZnO/SnO2 double electron transport layer guides improved open
74. Chen H, Liu D, Wang Y, Wang C, Zhang T, Zhang P, Sarvari H, circuit voltage for highly efficient ­CH3NH3PbI3-based planar per-
Chen Z, Li S (2017) Enhanced performance of planar perovskite ovskite solar cells. ACS Appl Energy Mater 1(5):2215–2221
solar cells using low-temperature solution-processed Al-doped 92. Chen Y, Xu C, Xiong J, Zhang Z, Zhang X, Yang J, Xue X,
­SnO2 as electron transport layers. Nanoscale Res Lett 12(1):1–6 Yang D, Zhang J (2018) Benefits of fullerene/SnO2 bilayers as
75. Liu Q, Zhang X, Li C, Lu H, Weng Z, Pan Y, Chen W, Hang X-C, electron transport layer for efficient planar perovskite solar cells.
Sun Z, Zhan Y (2019) Effect of tantalum doping on S ­ nO2 elec- Org Electron 58:294–300
tron transport layer via low temperature process for perovskite 93. Zhang J, Tan C-H, Du T, Morbidoni M, Lin C-T, Xu S, Durrant
solar cells. Appl Phys Lett. 115(14):143903 J-R, McLachlan M-A (2018) ZnO-PCBM bilayers as electron
76. Teimouri R, Heydari Z, Ghaziani M-P, Madani M, Abdy H, transport layers in low-temperature processed perovskite solar
Kolahdouz M, Asl-Soleimani E (2020) Synthesizing Li doped cells. Sci Bull 63(6):343–348
­TiO2 electron transport layers for highly efficient planar perovs- 94. Noh Y-W, Jin I-S, Kim K-S, Park S-H, Jung J-W (2020) Reduced
kite solar cell. Superlattices Microstruct. 145:106627 energy loss in S­ nO2/ZnO bilayer electron transport layer-based
77. Yin G, Ma J, Jiang H, Li J, Yang D, Gao F, Zeng J, Liu Z, Liu perovskite solar cells for achieving high efficiencies in outdoor/
S-F (2017) Enhancing efficiency and stability of perovskite solar indoor environments. J Mater Chem A 8(33):17163–17173
cells through Nb-doping of T ­ iO2 at low temperature. ACS Appl 95. Fang R, Wu S, Chen W, Liu Z, Zhang S, Chen R, Yue Y, Deng
Mater Interfaces 9(12):10752–10758 L, Cheng Y-B, Han L, Chen W (2018) [6, 6]-phenyl-C61-butyric
78. Cai Q, Zhang Y, Liang C, Li P, Gu H, Liu X, Wang J, Shentu Z, acid methyl ester/cerium oxide bilayer structure as efficient and
Fan J, Shao G (2018) Enhancing efficiency of planar structure stable electron transport layer for inverted perovskite solar cells.
perovskite solar cells using Sn-doped ­TiO2 as electron transport ACS Nano 12(3):2403–2414
layer at low temperature. Electrochim Acta 261:227–235 96. Wu S-H, Lin M-Y, Chang S-H, Tu W-C, Chu C-W, Chang Y-C
79. Mahmood K, Khalid A, Ahmad S-W, Mehran M-T (2018) (2018) A Design based on a charge-transfer bilayer as an electron
Indium-doped ZnO mesoporous nanofibers as efficient electron transport layer for improving the performance and stability in
transporting materials for perovskite solar cells. Surf Coat Tech- planar perovskite solar cells. J Phys Chem C 122(1):236–244
nol 352:231–237 97. Liu Z, Sun B, Liu X, Han J, Ye H, Tu Y, Chen C, Shi T, Tang Z,
80. Jeong J, Kim H, Yoon Y-J, Walker B, Song S, Heo J, Park S-Y, Liao G (2018) 15% efficient carbon based planar-heterojunction
Kim J-W, Kim G-H, Kim J-Y (2018) Formamidinium-based pla- perovskite solar cells using a ­TiO2/SnO2 bilayer as the electron
nar heterojunction perovskite solar cells with alkali carbonate- transport layer. J Mater Chem A 6(17):7409–7419
doped zinc oxide layer. RSC Adv 8(43):24110–24115 98. Ma H, Yip H-L, Huang F, Jen A-K-Y (2010) Interface engineer-
81. Avila J, Gil-Escrig L, Boix P-P, Sessolo M, Albrecht S, Bolink ing for organic electronics. Adv Funct Mater 20(9):1371–1388
H-J (2018) Influence of doped charge transport layers on efficient 99. Kim S-Y, Cho S-J, Byeon S-E, He X, Yoon H-J (2020) Self-
perovskite solar cells. Sustain Energy Fuels 2(11):2429–2434 assembled monolayers as interface engineering nanomaterials
82. Yi H, Wang D, Mahmud M- A, Haque F, Upama M- B, Xu C, in perovskite solar cells. Adv Funct Mater 10(44):2002606
Uddin A, (2018) Bilayer S ­ nO2 as electron transport layer for 100. Wang S, Li H, Zhang B, Guo Z-A, Bala H, Yao S, Zhang J, Chen
highly efficient perovskite solar cells. ACS Appl Energy Mater C, Fu W, Cao J, Sun G (2020) Perovskite solar cells based on
1(11):6027–6039 the synergy between carbon electrodes and polyethylene glycol
83. Xu X, Zhang H, Shi J, Dong J, Luo Y, Li D, Meng Q (2015) additive with excellent stability. Org Electron. 83:105734
Highly efficient planar perovskite solar cells with a ­TiO2/ZnO 101. Han F, Hao G, Wan Z, Luo J, Xia J, Jia C (2019) Bifunctional
electron transport bilayer. J Mater Chem A 3(38):19288–19293 electron transporting layer/perovskite interface linker for highly
84. You Y, Tian W, Min L, Cao F, Deng K, Li L (2020) ­TiO2/WO3 efficient perovskite solar cells. Electrochim Acta 296:75–81
bilayer as electron transport layer for efficient planar perovskite 102. Zhao M, Wu W, Su B (2018) pH-controlled drug release by dif-
solar cell with efficiency exceeding 20%. Adv Mater Interfaces fusion through silica nanochannel membranes. ACS Appl Mater
7(1):1901406 Interfaces 10(40):33986–33992
85. Yi H, Wang D, Mahmud M-A, Haque F, Upama M-B, Xu C, 103. Anizelli H, David T-W, Tyagi P, Laureto E, Kettle J (2020)
Duan L, Uddin A (2018) Bilayer ­SnO2 as electron transport Enhancing the stability of perovskite solar cells through func-
layer for highly efficient perovskite solar cells. ACS Appl Energy tionalisation of metal oxide transport layers with self-assembled
Mater 1(11):6027–6039 monolayers. Sol Energy 203:157–163
86. Martínez-Denegri G, Colodrero S, Kramarenko M, Martorell J 104. Cao T, Chen K, Chen Q, Zhou Y, Chen N, Li Y (2019) Fullerene
(2018) All-nanoparticle S ­ nO2/TiO2 electron-transporting layers derivative-modified ­SnO2 electron transport layer for highly effi-
processed at low temperature for efficient thin-film perovskite cient perovskite solar cells with efficiency over 21%. ACS Appl
solar cells. ACS Appl Energy Mater 1(10):5548–5556 Mater Interfaces 11(37):33825–33834

13
Journal of Solid State Electrochemistry (2022) 26:295–311 311

105. Han J, Kwon H, Kim E, Kim D-W, Son H-J, Kim D-H (2020) 110. Zhang P, Yang F, Kapil G, Shen Q, Toyoda T, Yoshino K, Minemoto
Interfacial engineering of a ZnO electron transporting layer using T, Pandey S-S, Ma T, Hayase S (2018) Enhanced performance of
self-assembled monolayers for high performance and stable per- ZnO based perovskite solar cells by ­Nb2O5 surface passivation. Org
ovskite solar cells. J Mater Chem A 8(4):2105–2113 Electro 62:615–620
106. Lu H, Zhuang J, Ma Z, Deng Y, Wang Q, Guo Z, Zhao S, Li H 111. Wang R, Mujahid M, Duan Y, Wang Z- K, Xue J, Yang Y, (2019)
(2019) γ-MPTS-SAM modified meso-TiO2 surface to enhance A review of perovskites solar cell stability. Adv Funct Mater
performance in perovskite solar cell. Mater Sci Semicond Pro- 29(47):1808843
cess 97:21–28 112. Wang S, Liu H, Bala H, Zong B, Huang L, Guo Z-A, Fu W,
107. Hou Y, Quiroz C-O-R, Scheiner S, Chen W, Stubhan T, Hirsch Zhang B, Sun G, Cao J, Zhang Z (2020) A highly stable hole-
A, Halik M, Brabec C-J (2015) Low temperature and hyster- conductor-free ­CsxMA1-xPbI3 perovskite solar cell based on car-
esis free electron transporting layers for efficient, regular, and bon counter electrode. Electrochim Acta. 335:135686
planar structure perovskite solar cells. Adv Energy Mater 113. Chen R, Cao J, Wu Y, Jing X, Wu B, Zheng N (2017) Improving
5(20):1501056 efficiency and stability of perovskite solar cells by modifying
108. Han G-S, Chung H-S, Kim B-J, Kim D-H, Lee J-W, Swain B-S, mesoporous ­TiO2–perovskite interfaces with both aminocaproic
Mahmood K, Yoo J-S, Park N-G, Lee J-H, Jung H-S (2015) and caproic acids. Adv Mater Interfaces 4(23):1700897
Retarding charge recombination in perovskite solar cells using 114. Meng L, Zhang F, Ma W, Zhao Y, Zhao P, Fu H, Guo X (2018)
ultrathin MgO-coated T ­ iO2 nanoparticulate films. J Mater Chem Improving photovoltaic stability and performance of perovskite
A 3(17):9160–9164 solar cells by molecular interface engineering. J Phys Chem C
109. Tai M, Zhao X, Shen H, Guo Y, Zhang M, Zhou Y, Li X, Yao Z, 123(2):1219–1225
Yin X, Han J, Lin H (2019) Ultrathin Z ­ n2SnO4 (ZTO) passivated
ZnO nanocone arrays for efficient and stable perovskite solar Publisher's Note Springer Nature remains neutral with regard to
cells. Chem Eng J 361:60–66 jurisdictional claims in published maps and institutional affiliations.

13