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Synergistic Engineering of Conduction Band, Conductivity, and

Interface of Bilayered Electron Transport Layers with Scalable TiO2
and SnO2 Nanoparticles for High-Efficiency Stable Perovskite Solar
Cells
Chien-Hung Chiang, Chun-Wei Kan, and Chun-Guey Wu*
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sı Supporting Information

ABSTRACT: A simple, synergistic engineering of the conduction band (CB),

conductivity, and interface of TiO2-based bilayered electron transport layers (ETLs)
via scalable TiO2 and SnO2 nanoparticles processed at low temperature (≤ 100 °C)
for regular planar perovskite solar cells (PSCs) was developed. The bottom layer (Lt-
TiO2:SnO2 nanocomposite film) was prepared by spin coating from the ethanol
suspension of small ground TiO2 nanoparticles with big ground SnO2 nanoparticles
as the additive. The top C-SnO2 layer (spin-coated from the concentrated
commercial SnO2 nanoparticles (C-SnO2 NPs, 20 wt %, 7 nm in size suspended
in H2O)) can be regarded as an interlayer between Lt-TiO2:SnO2 and perovskite
(Psk) absorbers. Bilayered Lt-TiO2:SnO2/C-SnO2 ETLs are dense films with a
cascade CB, good conductivity, facile electron extraction/transport ability, and a
highly hydrophilic surface for depositing high-quality Psk films. Regular planar PSCs
based on Lt-TiO2:SnO2/C-SnO2 ETLs combined with a
(FAI)0.90(PbI2)0.94(MABr)0.10(PbBr2)0.10 absorber and a spiro-OMeTAD hole
transporter achieved the highest power conversion efficiency of 22.04% with a negligible current hysteresis. The champion cell
lost less than 3% of the initial efficiency under continuous room lighting (1000 lux) for 1000 h (lost 10% after 2184 h) without
encapsulation under an inert atmosphere. Four related low-temperature-processed ETLs (Lt-TiO2/C-SnO2, Lt-C-SnO2, Lt-
TiO2:SnO2, and Lt-TiO2) were fabricated using the same metal oxide nanoparticle suspensions and studied simultaneously to reveal
the function of each metal oxide in the bilayered Lt-TiO2:SnO2/C-SnO2 ETLs. In the bottom Lt-TiO2:SnO2 layer, small TiO2
nanoparticles were needed for making a dense film, and highly conducting big SnO2 nanoparticles are used to increase the
conductivity of ETLs and a handy electron transport path for reducing the charge accumulation and series resistance of the cell. A
top C-SnO2 layer (regarded as an interlayer between Psk and Lt-TiO2:SnO2) was used to extract/transport electrons facilely, to form
a bilayered ETL with a cascade CB, and to create a hydrophilic surface to deposit high-quality Psk films to enhance the photovoltaic
performance of the PSCs. This study provides a blueprint for designing good-performance ETLs for high-efficiency, stable regular
planar PSCs using various sized nanoparticles prepared in a very simple and low-cost way.
KEYWORDS: perovskite, solar cell, electron transport, metal oxide nanocomposite, double layer, low temperature

■ INTRODUCTION
Organic−inorganic hybrid lead halide perovskites for photo-
they are also an abundant, nonexpensive, nontoxic material.3
Furthermore, PSCs based on a low (≤100 °C) temperature-
voltaic application have emerged about a decade ago.1 Now, processed (to save energy and reduce the fabrication cost as
the certified efficiency of perovskite solar cells (PSCs) is up to well as to be applied in organic polymer-based flexible
25.5%.2 The electron transport layer (ETL) that extracts and electrodes) TiO2 (Lt-TiO2) ETL were proved to have a high
power conversion efficiency (PCE) of over 17%.4 Nevertheless,
transports the photogenerated electrons and blocks the holes
a low-temperature-processed Lt-TiO2 ETL has a significant
from the perovskite (Psk) absorber plays an indispensable role
in the photovoltaic performance of a PSC. Searching for
suitable ETL materials and processes for PSCs has been a Received: January 31, 2021
significant effort in the PSC community.3−51 Titanium dioxide Accepted: April 29, 2021
(TiO2) films have been the most widely employed ETLs in Published: May 11, 2021
regular PSCs, because of their wide band gap, high chemical
stability, easy preparation, long electron lifetime, and frontier
orbital energy levels being compatible with Psk absorbers, and

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Table 1. Photovoltaic Parameters of the Regular Planar PSCsa Based on the Five ETLs and the HI of the Cells
ETL scan directionb Jsc (mA/cm2) Voc(V)
Lt-TiO2:SnO2/ C-SnO2 RS 26.00 1.13
FS 25.56 1.13
Lt-TiO2/C-SnO2 RS 25.96 1.12
FS 25.50 1.11
Lt-C-SnO2 RS 25.39 1.09
FS 24.72 1.09
Lt-TiO2:SnO2 RS 25.22 1.08
FS 24.10 0.93
Lt-TiO2 RS 24.74 1.06
FS 23.83 0.77
a
Cell architecture: FTO/ETL/ (FAI)0.90(PbI2)0.94(MABr)0.1(PbBr2)0.1/Spiro-OMeTAD/MoO3/Ag. bRS: reverse scan; FS: forward scan. cThe
average of 40 cells. dHysteresis index = (PCEreverse − PCEforward)/PCEforward.
drawback of low electron mobility (only about 10−4−10−6
cm2V−1 s−1) and, therefore, low conductivity. It was also found
that the surface of Lt-TiO2 is prone to have H2O/hydroxyl
groups, which interact with the CH3NH3+ in Psk, causing the
instability of the Psk layer and therefore the corresponding
cell.,5 Several strategies were used to improve the conductivity
of Lt-TiO2, such as doping7,8 or adding a conducting additive;9
nevertheless, how to avoid the degradation of Psk films by Lt-
TiO2 is still a key issue to commercialize PSCs. Moreover, the
light-soaking instability of PSCs was known to be mainly from
charge accumulation at the ETL/Psk interface.7−9 As a result,
ETLs in a planar PSC require a more efficient charge
separation and transport ability because the contact area
between the Psk and ETL is small. Therefore, insertion of a
layer of highly conducting films, such as fullerenes47,48 or
SnO249 between Psk and Lt-TiO2 to form a bilayered ETL to
improve the electron extraction and transport, had been
demonstrated successfully in several reports.47−49 Various
bilayered ETLs, such as TiO2/Mg-SnO2,41 SnO2/TiO2,42
TiO2/WO3,43 a-SnO2/c-TiO2,44 ZnO/SnO2,45 and gradient
F-doped SnO2 (Fx-SnO2/Fy-SnO2),46 were successfully used in
regular planar PSCs to achieve good efficiency and low current
hysteresis via interface engineering. Nevertheless, the PCEs of
the corresponding PSCs are still lower than that of the PSC
based on a high-temperature-processed mesoporous TiO2
ETL.39 Further improving the conductivity of the low-
temperature-processed ETL in a very simple and low-cost
way to enhance the charge extraction and transport is an
important step toward increasing the PCE of the regular planar
PSCs.
Recently, we used a simple ball-milling method to prepare an
anatase TiO2 nanoparticle (G-TiO2 NP) suspension in
isopropanol in a large quantity at temperature ∼30 °C from
bulk TiO2 powder without adding a surfactant.4 Regular PSCs
based on the low-temperature (≤100 °C)-processed Lt-TiO2
ETL prepared from G-TiO2 NPs exhibit the highest PCE of
17% but are electrically unstable (the efficiency decreases
significantly after repeated I−V scans under light illumination),
because of the low conductivity of the Lt-TiO2 ETL.
Furthermore, the conduction band (CB) of the Lt-TiO2 ETL
does not match well with the CB of the Psk absorber.4 To
improve the photovoltaic performance of the Lt-TiO2 ETL, in
this study, highly conducting SnO2 was used to increase the
conductivity and adjust the frontier orbital energy level of the
resulting Lt-TiO2:SnO2 ETLs. Moreover, the cascaded energy-
level alignment was known in natural photosynthetic processes
to minimize the energy loss within a bioreaction.40 Therefore,
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FF max PCE (%) average PCE (%)c hysteresis indexd
0.75 22.04 21.15 ± 0.50 <1%
0.76 21.96
0.73 21.22 20.10 ± 0.57 6.6%
0.70 19.81
0.72 19.92 19.30 ± 0.54 3.4%
0.71 19.13
0.72 19.61 19.16 ± 0.55 27%
0.64 14.34
0.71 18.62 17.92 ± 0.52 46%
0.55 10.03
a layer of highly conducting C-SnO2 film was coated on top of
Lt-TiO2:SnO2 to form a bilayered Lt-TiO2:SnO2/C-SnO2 ETL
with a cascade CB level and a hydrophilic surface for
depositing good-quality Psk films. A regular planar PSC
based on a bilayered Lt-TiO2:SnO2/C-SnO2 ETL achieved the
highest PCE of 22.04% with a negligible current hysteresis and
was very stable under an inert atmosphere.
■ RESULTS AND DISCUSSION
PSCs based on the Lt-TiO2 ETL prepared by spin coating
from the ground TiO2 nanoparticles (G-TiO2 NPs) at low
temperature (≤100 °C) have obvious advantages of being
simple and low cost.4 To simultaneously improve the
conductivity and tune the band structure of the Lt-TiO2
ETL, a conducting additive can be used.7,9,16 However, when
the commercialized SnO2 nanoparticles (C-SnO2 NPs, 5 nm in
size, suspended in H2O) were added into G-TiO2 NPs (in
ethanol, EtOH), particle aggregation occurs; as a consequence,
the resulting Lt-TiO2:SnO2 nanocomposite ETLs exhibit poor
photovoltaic performance. Therefore, a simple and economical
approach was developed in this study to prepare Lt-TiO2:SnO2
nanocomposite ETLs. TiO2 and SnO2 powders were mixed (in
EtOH having a total concentration of 1 wt % with various
TiO2:SnO2 weight ratios) and ground with a ball grinder.
During ball milling, the color of the particle suspension
changed, and the grinding process was stopped after 8 h when
the color of the suspension did not change further. The particle
size distribution of the ground TiO2:SnO2 mixtures with
various weight ratios (from 1:0 to 0:1) suspended in EtOH is
displayed in Figure S1, Supporting Information (SI). Under
the same grinding conditions, G-TiO2 NPs have an average
size of 20 nm versus 300 nm for the ground SnO 2
nanoparticles (G-SnO2 NPs), while the ground TiO2:SnO2
mixtures (G-TiO2:SnO2 NPs) show two distinguished particle
sizes: the majority small (20 nm in size) nanoparticles are TiO2
and the minor portion of the large (200 nm) particles is SnO2
(the large particles increase as the weight ratio of SnO2 in the
mixture increases but the particle size did not change). G-SnO2
NPs are smaller when SnO2 was ground with TiO2 compared
to the ground SnO2. The ground TiO2:SnO2 mixtures (G-
TiO2:SnO2 NPs) were better for fabricating Lt-TiO2:SnO2
nanocomposite ETLs than mixing G-TiO2 NPs and G-SnO2
NPs. Figure S2, SI illustrated the EtOH suspension of 1 wt %
G-TiO2 NPs and G-TiO2:SnO2 (4:1) NP mixture before and
after grinding.
Lt-TiO2:SnO2 (with the TiO2:SnO2 ratios from 1:0 to 0:1)
ETLs were fabricated simply by spin coating from the ground
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nanoparticle EtOH suspensions (G-TiO2 NPs, G-SnO2 NPs,

and G-TiO2:SnO2 NPs) and then heated at 100 °C for 20 min.
We first screened the optimal G-TiO2:G-SnO2 weight ratio to
be the nanocomposite ETL and found that when the
TiO2:SnO2 weight ratio in G-TiO2:SnO2 NPs is equal to 4:1,
the corresponding PSCs have the highest PCE of 18.31%. To
prepare the bilayered Lt-SnO2:TiO2/C-SnO2 ETL, a layer of
C-SnO2 (from C-SnO2 NPs with concentrations from 5 to 30
wt %) was spin-coated on top of the Lt-TiO2:SnO2 (4:1) film,
and the highest PCE of 19.30% was obtained when the
concentration of the C-SnO2 NP suspension is 20 wt %.
To explore the effects of each layer and the components of
the bilayered Lt-TiO2:SnO2/C-SnO2 ETLs on the photovoltaic
performance of the corresponding cells, PSCs based on the
other four related ETLs (bilayered Lt-TiO2/C-SnO2, mono-
layered Lt-TiO2, Lt-TiO2:SnO2, and Lt-C-SnO2 (prepared
from C-SnO2 NP water suspension)) were fabricated from the
same metal-oxide stock suspensions and studied simulta-
neously. At the same time, the cells were further optimized
using a higher light harvesting
(FAI)0.90(PbI2)0.94(MABr)0.10(PbBr2)0.1050 (compared to the
(FAI)0.85 (PbI2)0.89(MABr)0.15(PbBr2)0.15) absorber, and a
layer (approximately 100 nm) of NaF was deposited (by
sputtering coating) on the back of FTO glass as an
antireflection coating to increase the light reaching the Psk
absorber. Table 1 lists the photovoltaic parameters and the
hysteresis index (HI, defined as (PCEreverse − PCEforward)/
PCEreverse) of the PSCs based on the five types of ETLs, and
the corresponding I−V curves (both forward and reverse
scans) are displayed in Figure S3, SI. The optimized PSCs
based on the Lt-TiO2:SnO2/C-SnO2 bilayer ETLs achieved the
highest PCE of 22.04% against 18.48% for the optimized cell
using monolayered Lt-TiO2 as an ETL. Figure 1 depicts the I−
V curves obtained from both forward and reverse scans, the
incident photon-to-electron conversion efficiency (IPCE)
curve, and the steady-state output of the champion cell
based on the Lt-TiO2:SnO2/C-SnO2 ETL. The nonzero
spectral response of the cell spanned from the UV, visible to
near-infrared region (ca. 300−820 nm) with the peak IPCE of
approximately 93% at ∼550 nm. The Jsc integrated from the
IPCE curve (Figure 1c) is ∼92% of the Jsc obtained from the
I−V measurement, suggesting that the short-circuit current
density was not overestimated. The steady-state output was
very stable for 250 s under continuous one-sun illumination in
a glovebox.
The photovoltaic data listed in Table 1 show clearly that
adding SnO2 into TiO2 (Lt-TiO2:SnO2 vs Lt-TiO2) or
inserting a layer of SnO2 between Psk and ETL (Lt-TiO2
and Lt-TiO 2 :SnO 2 versus Lt-TiO 2 /C-SnO 2 and Lt-
TiO2:SnO2/C-SnO2, respectively) can not only increase the
PCE but also reduce the current hysteresis of the PSCs. The Figure 1. (a) I−V curves (scanning forward and reverse and delay
cell based on Lt-TiO2:SnO2/C-SnO2 ETL has almost time 0.01 s), (b) IPCE curve and integrated current, and (c) steady-
negligible (∼1%) current hysteresis; alternatively, significant state output of the champion PSC based on the Lt-TiO2:SnO2/C-
current hysteresis was observed on the cells with Lt-TiO2:SnO2 SnO2 ETL.
and Lt-TiO2 (27 and 46%, respectively) as ETLs. The current
hysteresis phenomenon was widely observed in the early effective method to reduce the current hysteresis, probably via
development of planar regular PSCs. Nonradiative recombi- reducing the charge accumulation near the Psk/ETL interface.
nation and charge accumulation near the Psk/CTL (carrier Therefore, the bilayered Lt-TiO2:SnO2/C-SnO2 ETL designed
transport layer) interface are the two critical reasons.51−55 The in this study has at least two advantages: using a good
decrease in current hysteresis can be attributed (at least conducting top C-SnO2 layer to facilely extract the excited
partially) to the improvement in the charge extraction as well electrons from Psk and using large G-SnO2 NPs in the bottom
as charge transportation of the ETL. Adding highly conducting TiO2:SnO2 layer as the handy path to transport electrons
SnO2 inside TiO2 or on top of TiO2 has demonstrated to be an quickly to the cathode.
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The long-term stability of the cells based on five types of
ETLs is displayed in Figure 2. By storing the cells in a glovebox
Figure 2. Long-term stability of the regular planar PSCs based on the
five ETLs (a) stored in a glovebox and (b) exposed under an ambient
atmosphere without encapsulation.
for 2184 h under continuous room lighting (approximately
1000 lux), cells based on Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-
SnO2, and Lt-C-SnO2 ETLs retained ca. 90% of their initial
efficiency. On the other hand, PSCs with the Lt-TiO2:SnO2 or
Lt-TiO2 ETL lost approximately 26% of their initial PCE. The
results showed that the charge accumulation near the Psk/ETL
interface would be the major reason for the degradation of the
cell under an inert atmosphere. Without encapsulation, cells
based on all five ETLs are very unstable by standing in air
(25−30 °C, 40−50% humidity) under room lighting, but the
stability of PSCs based on Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-
SnO2, and Lt-C-SnO2 ETLs is also better than that of PSCs
using Lt-TiO2:SnO2 or Lt-TiO2 as an ETL (see Figure 2(b)).
It was known that the degradation of the PSC in air is mainly
due to the decomposition of the Psk absorber by moisture and
oxygen. The difference in the long-term stability displayed in
Figure 2(b) suggests that the quality of the Psk films deposited
on those ETLs may also differ. The photovoltaic performance
of a PSC depends on several factors, such as the conductivity
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of each layer (of the whole cell), the energy offset between the
CTLs and Psk absorber, the nonradiative recombination
pathways, the interface defects of the cell, the quality of the
Psk layer, and so forth. To resolve the function of each layer
and components in the bilayered ETL and show the merit of
the designed bilayered Lt-TiO2:SnO2/C-SnO2 ETL reported
in this study, the physicochemical properties of the five low-
temperature-processed ETLs, Lt-TiO2:SnO2/C-SnO2, Lt-
TiO2/C-SnO2, Lt-C-SnO2, Lt-TiO2:SnO2, and Lt-TiO2, were
studied in detail simultaneously.
The optimal ETL thickness as well as the conductivity
(calculated from the dark I−V curves displayed in Figure S4, SI
of the devices with an ITO/ETL/Au architecture) of the five
ETLs is listed under Figure S4, SI. The data clearly revealed
that the Lt-C-SnO2 ETL has higher conductivity than the Lt-
TiO2 ETL, and adding SnO2 either inside or on top of the
TiO2 film increases the conductivity of the ETL. The higher
conductivity of the ETL facilitates not only the electron
extraction/transfer at the Psk/ETL interface but also electron
transport in the bulk ETL, reducing the charge accumulation at
the ETL/Psk interface and within ETL,56 resulting in better
photovoltaic performance. Nevertheless, the order in ETLs’
conductivity is not the same as the order of any photovoltaic
parameters of the corresponding PSCs. This result indicates
that the conductivity of the five ETLs is not the only
parameter, which affects the photovoltaic performance of the
corresponding regular planar PSCs.
UV/Vis/NIR transmission spectra of the ETLs on FTO
substrates are displayed in Figure 3, and the optical band gap
Figure 3. UV/Vis transmission spectra of the five ETLs.
(Eg) of the ETLs estimated from the Tauc plots (see Figure
S5, SI) of the absorption spectra was 4.24, 4.25, 4.32, 4.23, and
4.23 for Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-SnO2, Lt-C-SnO2,
Lt-TiO2:SnO2, and Lt-TiO2, respectively. All ETLs have a
similar optical band gap except the Lt-C-SnO2 film, which has
a slightly larger Eg than the other four ETLs. The optical band
gaps of the five ETLs also suggest that adding a layer C-SnO2
on Lt-TiO2:SnO2 or Lt-TiO2 did not change the band gap of
the ETLs significantly but increased slightly the transparence at
350 ∼ 450 nm, probably because of the antireflection effect of
the C-SnO2 film.30,57 The increasing in the light transmission
between 350 and 450 nm also reflects on the IPCE curves as
the data displayed in Figure S6, SI. However, the improvement
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in the IPCE value did not affect significantly the Jsc of the cell
because the intensity at 350−450 nm of the AM 1.5G sunlight
is very weak.
The valence band (VB) edges (or work function) of the five
ETLs were measured with the ultraviolet photoelectron spectra
(UPS) as shown in Figure S7, SI. The primary photoelectron
(upper emission) cut-off energies (Ef) and the secondary
photoelectron (lower emission) onset (cut-on) energies (Ei)
were used to calculate the work function using eq 1.58,59
ϕ = hν − (Ef − Ei) (1)
where ϕ is the VB energy and hν (= 21.2 eV) is the incident
photon energy of He(I) used for the UPS measurement.
The VB energies for Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-
SnO2, Lt-C-SnO2, Lt-TiO2:SnO2, and Lt-TiO2 were 8.45, 8.47,
8.46, 8.62, and 8.72 eV, respectively. CB levels were estimated
by subtracting Eg from the VB to be 4.21, 4.22, 4.14, 4.29, and Figure 5. SEM images of the five ETLs on FTO.
4.39 eV, respectively. The resulting band structures of the five
ETLs as well as the (FAI)0.90(PbI2)0.94 (MABr)0.10(PbBr2)0.10 that the monolayered C-SnO2 film is very flat but not dense,
absorber are depicted in Figure 4. Bilayered ETLs do show a maybe because of the poor interface compatibility between
FTO and the C-SnO2 NP water suspension. The discontin-
uous film morphology is the major reason that the Voc of the
PSC based on the Lt-C-SnO2 ETL is lower than the Voc of
those with bilayered Lt-TiO2:SnO2/C-SnO2 and Lt-TiO2/C-
SnO2 ETLs although Lt-C-SnO2 has the highest conductivity
and the CB energy offset between Lt-C-SnO2 and the Psk
absorber is the smallest among the five ETLs.
SEM topographic and cross-sectional images of the perov-
skite ((FAI)0.90(PbI2)0.94(MABr)0.10 (PbBr2)0.10) films coated
on the five ETLs are shown in Figure 6. Dense Psk films
Figure 4. Energy-level diagram of the five ETLs as well as FTO and
the Psk absorber ((FAI)0.90(PbI2)0.94(MABr)0.10(PbBr2)0.10).

cascade lowest unoccupied molecular orbital (LUMO) level,

and comparing the CB level of the ETLs with the Voc values of
the corresponding cells listed in Table 1, the PSC based on the
ETL with a cascade LUMO level has higher Voc. The LUMO
of Lt-C-SnO2 matched better with that of the Psk absorber, but
the Lt-C-SnO2-based cell has lower Voc, probably because the
Lt-C-SnO2 film has a poor morphology, which will be revealed
in the following paragraph.
Scanning electron microscopy (SEM) images of the 5 ETLs
are displayed in Figure 5. The surface morphology of the
bilayered Lt-TiO2:SnO2/C-SnO2 and Lt-TiO2/C-SnO2 films is
similar: both are very flat and dense and composed of very
small nanoparticles. On the other hand, both Lt-TiO2:SnO2
and Lt-TiO2 films have a very rough surface, and few big grains
were also observed in the Lt-TiO2:SnO2 film. The particle
distribution curves displayed in Figure S1, SI indicated that
some SnO2 particles having the size over 200 nm existed in the
G-TiO2:SnO2 NPs. The big grains in the Lt-TiO2:SnO2 film
may come from SnO2 in the G-TiO2:SnO2 NPs. It was shown
that the roughness of the high-temperature-processed TiO2
ETL affects the quality of Psk films and therefore the
photovoltaic performance of the corresponding cells.4 In this
study, a layer of C-SnO2 (composed of 7 nm particles) was
added to change the surface morphology of low-temperature-
processed Lt-TiO2:SnO2 and Lt-TiO2 films. The dense and flat
surface morphology of bilayered Lt-TiO2:SnO2/C-SnO2 and
Lt-TiO2/C-SnO2 films comes from the small SnO2 nano-
particles that fill the valleys of the bottom film and at the same
time form a thin layer of pure C-SnO2 film. It is noted here
23610
Figure 6. SEM topographic and cross-sectional images of Psk films
deposited on the five ETLs.
formed on top of all ETLs, and the average grain sizes and
thickness of Psk films on bilayered Lt-TiO2:SnO2/C-SnO2 and
Lt-TiO2/C-SnO2 are very close. Nevertheless, PSCs based on
the Lt-TiO2:SnO2/C-SnO2 ETL have slightly higher Voc and
FF values compared to those with Lt-TiO2/C-SnO2 as an ETL,
which is probably because Lt-TiO2:SnO2/C-SnO2 has higher
conductivity compared to Lt-TiO2/C-SnO2 (see Figure S4,
SI). These data supported that improving the bulk conductivity
of ETLs is also important for enhancing the photovoltaic
performance of PSCs. Psk films coated on bilayered ETLs have
a grain size up to 1000 nm. On the other hand, the grain size of
the Psk films deposited on Lt-TiO2:SnO2 and Lt-TiO2 falls
between 200 and 700 nm, very close to the size reported
previously when Psk films were deposited on the low-
temperature TiO2 ETL,60,61 but significantly smaller than
those of Psk on bilayered ETLs. The smaller grain size of the
Psk film would be one of the reasons that PSCs based on Lt-
TiO2:SnO2 and Lt-TiO2 ETLs exhibited poor photovoltaic
performance and long-term stability. It is interesting to note
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here that the grain size and thickness of Psk films coated on Lt- Therefore, one of the advantages of using C-SnO2 as a top
C-SnO2 are very close to those of the ones deposited on Lt- layer of bilayered (not a single Lt-C-SnO2 layer) ETL is to
TiO2:SnO2/C-SnO2 and Lt-TiO2/C-SnO2 (all having the C- create a high hydrophilic surface for depositing big Psk grains
SnO2 film in contact with Psk), and the conductivity of Lt-C- with high crystallinity without the drawback of direct contact
SnO2 is even higher than that of Lt-TiO2:SnO2/C-SnO2 and between Psk and the partially exposed FTO substrate.
Lt-TiO2/C-SnO2 films (see Figure S4, SI). Nevertheless, the Photoluminescence (PL) behaviors were generally used for
Lt-C-SnO2 ETL showed poor photovoltaic performance exploring the charge recombination in bulk Psk and at the Psk/
compared to Lt-TiO2:SnO2/C-SnO2 and Lt-TiO2/C-SnO2 CTL interfaces. The nonradiative processes through mainly the
ETLs, which is because Lt-C-SnO2 is not a dense film (see Shockley−Read−Hall recombination of the Psk film (coated
the SEM images displayed in Figure 5) and Psk may directly on an inert substrate such as FTO with no charge transport
come in contact with the FTO electrode. ability) occur within the Psk grains and at grain boundaries.62
X-ray diffraction (XRD) patterns of the Psk films coated on Therefore, the PL intensity can be used to probe the quality of
the five ETLs are illustrated in Figure S8, SI. The diffraction the Psk film: Psk with fewer defects has stronger PL intensity.
intensity of (100) planes and the corresponding crystalline Nevertheless, the steady-state PL of the Psk film on the CTL
domain sizes calculated from the (100) plane using the was also commonly used to probe the charge extraction and
Scherrer equation are listed in the Table under Figure S8, SI. transport efficiency of the CTL. The steady-state PL spectra of
Psk films deposited on Lt-SnO2:TiO2/C-SnO2, Lt-TiO2/C- Psk films on the five ETLs are displayed in Figure 7(a). Psk
SnO2, and C-SnO2 ETLs have higher crystallinity and a larger
crystalline domain size than those coated on Lt-SnO2:TiO2
and Lt-TiO2. The XRD data obviously reveal that the
crystallinity (the intensity of the (100) diffraction) of Psk
films is better when the ETL surface has more SnO2 content
(even in the monolayered ETLs). Psk films deposited on
bilayered Lt-TiO2/C-SnO2 and monolayered Lt-C-SnO2 have
a similar average grain size, crystallinity, and crystalline
domain. Nevertheless, the photovoltaic performance of the
PSCs based on the Lt-TiO2/C-SnO2 ETL is better than that of
the one with the Lt-C-SnO2 ETL even though the conductivity
of the Lt-C-SnO2 film is higher than that of the Lt-TiO2/C-
SnO2 film. This is because C-SnO2 NPs (H2O suspension)
cannot form a dense and continuous Lt-C-SnO2 film on the
FTO substrate (see the SEM images displayed in Figure 5).
Another dense and conducting layer underneath can remedy
the disadvantage of Lt-C-SnO2 to be an ETL for the regular
planar PSCs. The results reveal the merit of the designed
bilayered ETL with a TiO2:SnO2 bottom layer and a SnO2 top
layer for the regular planar PSCs.
The quality of Psk films depends not only on the
components/concentrations of their precursor solutions and
preparation conditions but also on the surface properties of the
substrate. It was reported that Psk coated on the more
hydrophilic surface has bigger grains and a higher thickness,
probably because the Psk precursor solution (Psk/(DMF +
DSMO)) can spread more evenly on the more hydrophilic
surface; therefore, thicker Psk films with larger grains were
obtained after dripping an antisolvent.9 To study the surface
hydrophilicity of the five ETLs, water contact angles were
measured to be 4.7, 5.5, 6.9, 19.6, 21.4, and 50.3 degree for Lt-
TiO 2 :SnO 2 /C-SnO 2 , Lt-TiO 2 /C-SnO 2 , Lt-C-SnO 2 , Lt-
TiO2:SnO2, Lt-TiO2, and FTO substrate, respectively (see Figure 7. (a) Static state and (b) TRPL spectra of Psk films deposited
Figure S9, SI). Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-SnO2, and on the five ETLs.
Lt-C-SnO2 films have a close water contact angle, which is
much smaller than those of Lt-TiO2:SnO2 and Lt-TiO2 films films on Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-SnO2, and Lt-C-
because SnO2 is a more hydrophilic substance compared to SnO2 have almost the same PL intensity, which is weaker than
TiO2. Notably, the water contact angle of the Lt-C-SnO2 film is those coated on Lt-SnO2:TiO2 and Lt-TiO2 films. Psk films
slightly larger than those of Lt-TiO2:SnO2/C-SnO2 and Lt- deposited on Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-SnO2, and
TiO2/C-SnO2 films probably because the former film was Lt-C-SnO2 have a larger average grain size (from the SEM
deposited loosely on the most hydrophobic FTO surface (the images illustrated in Figure 6) as well as higher crystallinity and
contact angle of FTO is also displayed in Figure S9, SI). The a bigger crystalline domain (obtained from the XRD patterns
contact angle of FTO/Lt-C-SnO2 was contributed by both displayed in Figure S7, SI) compared to those coated on Lt-
hydrophobic FTO and hydrophilic Lt-C-SnO2. The contact TiO2:SnO2 and Lt-TiO2. It is hard to find a reason to support
angle data also confirmed that the Lt-C-SnO2 film did not that Psk films with bigger grains, higher crystallinity, and a
cover FTO totally as revealed with SEM images (Figure 5). larger crystalline domain will have more nonradiative
23611 https://doi.org/10.1021/acsami.1c02105
ACS Appl. Mater. Interfaces 2021, 13, 23606−23615
ACS Applied Materials & Interfaces
recombination sites. Therefore, the lower PL intensity of Psk/
ETL is because the ETL has higher electron extraction and
transport efficiency as observed in other studies.9,63,64 In other
words, Lt-TiO2:SnO2/C-SnO2, Lt-TiO2/C-SnO2, and Lt-C-
SnO2 ETLs have higher electron extraction and transport
ability than Lt-TiO2:SnO2 and Lt-TiO2 ETLs. The significantly
smaller current hysteresis of the PSCs based on Lt-TiO2:SnO2/
C-SnO2, Lt-TiO2/C-SnO2, and Lt-C-SnO2 ETLs compared to
those with Lt-SnO2:TiO2 or Lt-TiO2 as an ETL further
supported this conclusion.
For a more quantitative examination of the interfacial
electron transfer kinetics, time-resolved photoluminescence
(TRPL) measurements of Psk/ETLs were performed, and the
results are displayed in Figure 7(b). The information from the
TRPL data (just like that from the PL spectra) can be used to
evaluate the efficiency of the electron extraction and transport
by ETLs. The charge recombination lifetimes of the Psk
excitons resolved by fitting the normalized TRPL spectra are
1.5, 1.7, 1.7, 10.4, and 15.7 ns for Psk deposited on Lt-
TiO 2 :SnO 2 /C-SnO 2 , Lt-TiO 2 /C-SnO 2 , Lt-C-SnO 2 , Lt-
TiO2:SnO2, and Lt-TiO2, respectively. It is known that in a
PSC the electrons produced by the exciting light will diffuse
quickly to the Psk/ETL interface and be transferred to the
ETL within several tens of nanoseconds. A good ETL can
extract electrons quickly to significantly reduce the radiative
recombination within the Psk film, and therefore, the PL
quenches rapidly. The much weaker PL intensity and
remarkably faster PL decay immediately after the exciting
pulse stops for Psk films deposited on Lt-TiO2:SnO2/C-SnO2
and Lt-TiO2/C-SnO2 than those on Lt-TiO2:SnO2 and Lt-
TiO2, respectively, support that depositing an extra C-SnO2
layer can facilitate the electron extraction, leading to the
improvement in the photovoltaic performance of the ETLs.
■
CONCLUSIONS
A simple, synergistic engineering of the CB, conductivity, and
surface of the low-temperature-processed bilayered Lt-
TiO2:SnO2/C-SnO2 ETLs for regular planar PSCs was
reported. A ground TiO2:SnO2 nanoparticle (G-TiO2:SnO2
NP) suspension (in EtOH) used for fabricating a TiO2:SnO2
nanocomposite bottom layer was prepared simply by ball
grinding of the TiO2 and SnO2 powder mixture in ethanol at
room temperature without adding any surfactant. The top C-
SnO 2 layer was spin-coated from a commercial SnO 2
nanoparticle water suspension to be a highly conducting
interfacial layer between the Psk and Lt-TiO2:SnO2 ETL, at
the same time to create a bilayered ETL with a cascade CB
level, good conductivity, and hydrophilic surface. Four related
ETLs were prepared (from the same metal oxide nanoparticle
suspensions) and investigated simultaneously to reveal the
function of each layer and the components of the bilayered Lt-
TiO2:SnO2/C-SnO2 ETL when applied to the regular planar
PSCs. It was shown that in the Lt-TiO2:SnO2 bottom layer
small TiO2 nanoparticles are necessary for making a dense film
to avoid the short-circuit, and large SnO2 particles were used to
increase the conductivity and adjust the CB level as well as be a
handy path for transporting the electron to the cathode. The
C-SnO2 top layer is responsible, besides to form the cascade
CB with TiO2:SnO2, for improving the electron extraction and
transport of the ETL as well as creating a hydrophilic surface
for depositing high-quality Psk films to enhance the Jsc of the
PSC. The bilayered Lt-TiO2:SnO2/C-SnO2 ETL possesses a
cascade CB, and its CB levels matched well with those of the
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www.acsami.org Research Article
Psk absorber to reduce the Voc loss during the electron
transport process, beneficial for the Voc. As a result, regular
planar PSCs based on the low-temperature-processed Lt-
TiO2:SnO2/C-SnO2 bilayer ETLs achieve the highest PCE of
22.04% with a negligible current hysteresis and are very stable
under an inert atmosphere (glovebox). The concept of
bilayered ETL design reported here can pave a new path for
the research and development of low-cost and scalable ETLs
for high-efficiency and stable regular planar PSCs.
■
EXPERIMENTAL SECTION
Chemicals and Physicochemical Studies. Anatase titanium
dioxide (TiO2) powder (Degussa P90) was purchased from
Nanostructured and Amorphous Material, Los Alamos, New Mexico,
USA. Both SnO2 powder (10 μm in size) and 5 nm SnO2 water
suspension (15 wt %) were acquired from Alfa Aesar, USA. Zirconium
dioxide (ZrO2) beads (density: 5.95 g cm−3; size: 100 μm) were
obtained from Oriental Cera TEC., Taiwan. FTO/glass (TEC-7) was
obtained from MTI, USA, and patterned in our laboratory. Lead
iodide, lead bromide (PbI2, PbBr2; Alfa Aesar, USA), methyl
ammonium bromide (MABr) and formamidinium iodide (FAI;
Ossila Co., UK), 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amino)-
9,9′-spirobifluorene (spiro-MeOTAD, Luminescence Technology,
Taiwan), bis-(trifluoro-methane)-sulfonimide lithium salt (Li-TFSI,
99%, Ossila Co., UK), MoO3 (Aldrich, USA), and other compounds
used in this study were purchased from the commercial resources. All
chemicals, unless specified, were used as received without further
purification.
Grazing incidence XRD data were collected in the 2θ range of 5−
50 degree on a Bruker powder diffractometer (D8 Discover) using Cu
Kα1 radiation equipped with a 2D detector. UPS and X-ray
photoelectron spectroscopy spectra were obtained from a Thermo
VG-Scientific/VG-Sigma Probe spectrometer. UV/Vis and PL spectra
were recorded using a Cary 300 Bio spectrometer and a Hitachi F-
7000 fluorescence spectrophotometer, respectively, at room temper-
ature. The nanosecond TRPL spectra were recorded with an optical-
microscope-based system (UniRAM, Protrustech with the custom
designed light path). The average power, wavelength, pulse duration,
and repetition rate of the excitation are 20 μW, 405 nm, 150 ps, and
20 MHz, respectively. SEM was performed with a Hitachi S-800
microscope at 15 KV. Samples for SEM imaging were mounted on a
metal stub with a piece of conducting tape and then coated with a thin
layer of gold film to avoid charging. The cross-sectional SEM image
was used for estimating the film thickness and observing the interface
contact between each layer of the cell. The contact angle was
measured with a home-made set-up (Grandhand Ctag01, Taiwan)
using water as a probe solvent. The contact angle is determined using
the image of a sessile drop at the points of the intersection between
the drop contour and the projection of the surface. The particle size
distribution of the TiO2 and SnO2 particles was measured with a
dynamic light scattering meter (Microtrac Nanotrac wave, Japan).
Preparation of ETLs for Regular Planar PSCs. There are five
types of ETLs: Lt-TiO2:SnO2/SnO2, Lt-TiO2/SnO2, Lt-C-SnO2, Lt-
TiO2:SnO2, and Lt-TiO2 were prepared and studied in this paper. The
first two ETLs are bilayer, and the following three ETLs are
monolayer. Three stock solutions for making ETLs were prepared as
follows: Ground TiO2 (G-TiO2 NPs, ca. 20 nm in size) suspended in
EtOH was prepared with a ball-milling method similar to our previous
report.4 Ground TiO2:SnO2 (G-TiO2:SnO2 NPs, ca. 20 and 200 nm
in size) or SnO2 (G-SnO2 NPs, ca. 300 nm in size) suspension was
prepared by mixing TiO2 (15 μm) and SnO2 (10 μm) powders
together or SnO2 powders along in EtOH, and then they were ground
for 8 h at room temperature with a ball grinder until the color of the
suspensions did not change. The rotation speed of the ball grinder is
2000 rpm. The SnO2 nanoparticle water suspension (C-SnO2 NPs, 15
wt %, size: 5 nm) was purchased from Alfa Aesar, UK (other
concentrations of C-SnO2 nanoparticles were diluted or concentrated
from 15 wt % suspension, and the particle size slightly increases when
https://doi.org/10.1021/acsami.1c02105
ACS Appl. Mater. Interfaces 2021, 13, 23606−23615
ACS Applied Materials & Interfaces
the suspension was concentrated ex 7 nm for 20 wt % suspension). To
deposit a monolayered ETL on clean patterned FTO glass, 100 μL
(G-TiO2:SnO2 NPs or G-TiO2 NPs or 20 wt % C-SnO2 NPs)
suspension was spin-coated on the cleaned FTO glass using a spin
rate of 5000−10,000 rpm for 30 s and then heated at 100 °C for 20
min. For fabricating bilayered Lt-TiO2/C-SnO2 and Lt-TiO2:SnO2/C-
SnO2 ETLs, 100 μL of 20 wt % C-SnO2 NPs was spin-coated on top
of TiO2 or TiO2:SnO2-coated FTO at a spin rate of 1000 rpm for 30 s
and then heated at 100oC for 20 min.
Device Fabrication and Characterization. A Psk absorber layer
was deposited on top of the ETL using a one-step, antisolvent
dripping method from its precursor solution. The Psk precursor
solution was prepared by well mixing FAI, MAI, PbI2, and PbBr2 in
DMF/DMSO (6:4, V/V) to form 1.3 M (based on Pb) precursor
solution with the stoichiometry of the Psk as
(FAI)0.85(PbI2)0.89(MAPbBr3)0.15 or (FAI)0.90
(PbI2)0.94(MABr)0.10(PbBr2)0.10.50 Psk precursor solution (40 μL)
was coated on the ETL with the spin program of 1000 rpm for 10 s,
then 7000 rpm for 15 s, and finally 3 s; 60 μL of chlorobenzene was
dripped on the wet film as an antisolvent. The resulting Psk film was
heated at 150 °C for 10 min, and a then spiro-OMeTAD hole
transport layer (HTL) was spin-coated on Psk followed by the
vacuum deposition of MoO3 as an electron blocking layer and Ag as
an electrode.29 The deposition of the Psk active layer and HTL was
performed under a N2-filled glovebox. The highest-efficiency cells
were further optimized by depositing ca. 100 nm NaF film on the
back of FTO glass as an antireflection coating. The physicochemical
property and photovoltaic performance measurements of the PSCs
were carried out using the same methods as reported previously.9
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c02105.
Particle size distribution of the TiO2, SnO2, and TiO2/
SnO2 mixture powders before and after grinding for 8
hours in ethanol, I−V curves of the PSCs, I−V curves of
the devices, Tauc plots of the absorption spectra, IPCE
curves and integral current density, UPS spectra, XRD
patterns, and water contact angles (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Chun-Guey Wu − Department of Chemistry, National Central
University, Chung-Li 32001, Taiwan; Research Center for
New Generation Light Driven Photovoltaic Modules,
National Central University, Chung-Li 32001, Taiwan;
orcid.org/0000-0001-8540-5602; Email: t610002@
cc.ncu.edu.tw
Authors
Chien-Hung Chiang − Department of Chemistry, National
Central University, Chung-Li 32001, Taiwan; Research
Center for New Generation Light Driven Photovoltaic
Modules, National Central University, Chung-Li 32001,
Taiwan
Chun-Wei Kan − Department of Chemistry, National Central
University, Chung-Li 32001, Taiwan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c02105
Notes
The authors declare no competing financial interest.
23613
■
www.acsami.org Research Article
ACKNOWLEDGMENTS
Financial support from the Ministry of Science and
Technology (MOST), Taiwan, ROC (Grand number:
MOST 107-2113-M-008-006-MY3) was gratefully acknowl-
edged. The device fabrication was carried out in the Advanced
Laboratory of Accommodation and Research for Organic
Photovoltaics, MOST, Taiwan, ROC.
■
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