Solar Energy 197 (2020) 50–57

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

Suppressing recombination in perovskite solar cells via surface engineering T

of TiO2 ETL
⁎
Daniel Prochowicza,b, Mohammad Mahdi Tavakolic,d, , Małgorzata Wolska-Pietkiewicze,
Maria Jędrzejewskae, Suverna Trivedif, Manoj Kumarg, Shaik M. Zakeeruddina,
⁎
Janusz Lewińskib,e, Michael Graetzela, Pankaj Yadavh,
a
Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, School of Basic Sciences, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-
1015 Lausanne, Switzerland
b
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
c
Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
d
Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran, Iran
e
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
f
Department of Chemical Engineering, School of Technology, Pandit Deendayal Petroleum University, Gandhinagar 382 007, Gujarat, India
g
Department of Science, School of Technology, Pandit Deendayal Petroleum University, Gandhinagar 382 007, Gujarat, India
h
Department of Solar Energy, School of Technology, Pandit Deendayal Petroleum University, Gandhinagar 382 007, Gujarat, India

A R T I C LE I N FO A B S T R A C T

Keywords: Hybrid perovskite solar cells (PSCs) have gained significant attention owing to their excellent physicochemical
Perovskite solar cell and photovoltaic properties. PSCs typically consist of a perovskite light absorber sandwiched between two
ZnO nanocrystal carrier selective layers optimized with respect to optimal band alignment and low interfacial recombination. The
Interface engineering quality of the perovskite layer and interfaces play major roles in the fabrication of high-performance PSCs. In the
Recombination
present work, we systematically investigate the planar structure PSCs based on TiO2 and TiO2/ZnO electron
Impedance spectroscopy
transport layers (ETLs), which provide deeper insight into the charge recombination and accumulation me-
chanisms. We show that the double-layer structure of TiO2/ZnO ETL improves the optical and morphology
properties of perovskite film leading to superior device performance. From the ideality factor, EIS and IMVS
results, a suppressed recombination in TiO2/ZnO PSCs is achieved, which is due to improved grain size of
perovskite absorber layer grown on ZnO nanocrystals (NCs). Additionally, we find that the ZnO NCs improve the
shunt resistance and quality of the perovskite and suppress the recombination. The present study provides a
novel strategy to improve the device performance of PSCs along with a detail investigation procedure to un-
derstand the physical mechanism.

1. Introduction
The perovskite solar cells (PSCs) demonstrate a rapid and con-
tinuous growth of the power conversion efficiency (PCE) (Yang et al.,
2017; Jeon et al., 2018; Tavakoli et al., 2018b, 2018d), which now
exceeds 25% (For a recent certified value of PCE over 25%). This im-
provement is attributed to the excellent optoelectronic properties of
metal halide perovskites including high absorption coefficient (De Wolf
et al., 2014), long carrier diffusion length (Xing et al., 2013; Stranks
et al., 2013) and carrier mobility (D’Innocenzo et al., 2014; Marchioro
et al., 2014) as well as low trap state (Tavakoli et al., 2017). The high
photovoltaic performance of PSCs depend also on the type of materials
selected as the ETL in the device (Mohamad Noh et al., 2018). Gen-
erally, the ETL plays an important role in the extraction and transpor-
tation of photogenerated electrons in the PSCs and simultaneously
eliminates the electrical shunts between the transparent electrode and
perovskite layers. A thin compact TiO2 layer is typically used as ETL in
a planar heterojunction solar cells due to its suitable band alignment
with perovskite absorber layer and good transparency for visible light
(Jena et al., 2019). However, TiO2 ETLs suffer from the low con-
ductivity and high surface defect density that cause insufficient charge
separation at the interface with perovskite layer (Yang et al., 2016).
Hence, to overcome these issues, various modifications of the TiO2
surface have been proposed such as doping treatment with metal or

⁎
Corresponding authors at: Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA 02139, USA (M.M.
Tavakoli, P. Yadav).
E-mail addresses: mtavakol@mit.edu (M.M. Tavakoli), Pankaj.yadav@sse.pdpu.ac.in (P. Yadav).

https://doi.org/10.1016/j.solener.2019.12.070
Received 1 October 2019; Received in revised form 17 December 2019; Accepted 24 December 2019
Available online 06 January 2020
0038-092X/ © 2019 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
D. Prochowicz, et al.
non-metal ions (e.g. Y3+, (Zhou et al., 2014) Ru2+; (Xu et al., 2018)
Mg2+; (Wang et al., 2015) Nd3+; (Roose et al., 2016) La3+; (Gao et al.,
2016) Er3+; (Ren et al., 2018) Cl−; (Tan et al., 2017)) and passivation
using fullerene self-assembled monolayer (Wojciechowski et al., 2014;
Tao et al., 2015; Li et al., 2015) or reduced graphene oxide (Tavakoli
et al., 2016; Chung et al., 2017; Zibouche et al., 2018; Tavakoli et al.,
2019). Recently, the introduction of double-layered (Tavakoli et al.,
2018e; Song et al., 2017; Lee et al., 2017; Chavan et al., 2020) or
sandwich multilayers (Duan et al., 2016) ETL has been implemented to
improve its conductivity and the performance of planar perovskite solar
cells. For example, the modification of TiO2 surface by the SnO2 layer
efficiently enhanced the charge transport and retarded the charge re-
combination at the interface between the ETL and perovskite layer,
which contributes to higher Voc and PCE values of PSCs (Tavakoli et al.,
2018c). The recent works have demonstrated that the deposited ZnO
layer on the surface of TiO2 could efficiently increase electron transport
and retard the recombination reactions at the ZnO/perovskite absorber
interface (Xu et al., 2015; Yin et al., 2016). However, no systematic
study on the exact transport and charge collection mechanisms in TiO2-
and combined TiO2/ZnO-based planar PSCs is noted. Thus, it is crucial
to understand and determine the specific interfacial electronic proper-
ties between selective ETLs and the absorber layer.
Impedance spectroscopy is a widely used small-perturbation char-
acterization technique to probe the charge carrier dynamics from the
bulk and the interfaces of PSCs (Gottesman et al., 2016; Zarazúa et al.,
2017; Prochowicz et al., 2019). In turn, intensity-modulated photo-
current and photovoltage spectroscopy allow to identify and extract the
dynamic operating parameters of solar cells (Guillén et al., 2014;
Prochowicz et al., 2017). Recently, we have discussed the interfacial
characteristics of both planar and mesoporous PSCs providing a deeper
insight into the charge accumulation mechanism and the origin of open-
circuit voltage (Voc) (Prochowicz et al., 2018; Yadav et al., 2018;
Prochowicz et al., 2019a, 2019b, 2018).
Herein, we systematically study the interfacial and bulk character-
istics of the PSCs fabricated on TiO2 and TiO2/ZnO ETLs that provide a
deeper insight into the charge recombination and accumulation me-
chanisms. The effect of selected ETL on the performance of PSCs has
been investigated using impedance spectroscopy, intensity-modulated
photocurrent and photovoltage spectroscopy and Mott-Schottky ana-
lysis under dark and illumination conditions. Our analysis reveals that
the presence of ZnO on TiO2 layer improves the surface morphology
and optical property of perovskite absorber layer that leads to enhance
the device performance. A detailed analysis of the structure and optical
properties was carried out to explore the various physical phenomenon
related to this performance enhancement. The results of ideality factor,
EIS and IMVS measurement indicates that the grain size of the per-
ovskite film grown on the surface of ZnO NCs is increased, which results
in a suppressed recombination in the TiO2/ZnO-based PSCs. This work
presents a way to improve the device performance of PSCs along with a
detail investigation procedure for understanding the corresponding
physical mechanisms.
2. Results and discussions
To study the role of ETL on the performance of PSCs, planar devices
with compact TiO2 (reference) and TiO2/ZnO bilayer (optimum thick-
ness of ZnO: ~20 nm) were fabricated. ZnO nanocrystals (NCs) were
synthesized using a previously described an organometallic procedure
based on the controlled exposition of Et2Zn in DMSO to air (for the
fabrication procedures of both ETLs, see Experimental Section)
(Lewinski et al.). We intentionally used ZnO NCs derived from the
newly developed organometallic approach, as this type of NCs is stable
and has well-passivated surface and ultra-long-lived electron-hole se-
paration (Grala et al., 2016; Wolska-Pietkiewicz et al., 2018). All these
properties make these ZnO NCs prospective for solar energy production
and photocatalysis (Cieślak et al., 2016, 2017; Pavliuk et al., 2017).
51
Solar Energy 197 (2020) 50–57
Moreover, state-of-the-art triple A-cation composition, Cs5(MA0.17
FA0.83)95Pb(I0.83 Br0.17)3 was used as an active layer and prepared ac-
cording to the recently published procedure (Tavakoli et al., 2019). The
device structure was completed using spiro-OmeTAD and Au as hole
transporting layer (HTL) and metal electrode, respectively. Fig. S1 il-
lustrates the top-view SEM images of perovskite absorber layers, de-
posited on top of TiO2 and TiO2/ZnO ETLs. These results indicate that
the perovskite film on TiO2/ZnO ETL is more uniform with larger
grains. The average grain size of perovskite film deposited on TiO2 and
TiO2/ZnO ETLs are 310 ± 120 nm and 680 ± 80 nm, respectively. In
order to find out the reason of enlarged perovskite crystallite size, we
performed the atomic force microscopy (AFM) measurement to study
the surface roughness of TiO2 and TiO2/ZnO films (Fig. S2). The TiO2/
ZnO sample shows smoother surface with lower root-mean-square
(RMS) roughness, which is beneficial for high-quality perovskite crystal
growth and for improving the interfacial contact between ETL and
perovskite absorber layer (Tavakoli et al., 2019). Fig. S3a shows the
UV–vis absorption spectra of the both perovskite films indicating a si-
milar absorption spectrum over the entire visible region. Moreover,
both samples display similar crystal structures with (1 1 0) and (2 0 2)
diffraction peaks centered at 14.07° and 31.7°, however, the intensity of
diffraction peaks become slightly stronger for the film on TiO2/ZnO ETL
compared with that of reference film, indicating its improved crystal-
linity (Fig. S3b). Notably, the perovskite film in both cases have the
same crystal structure. The above morphological and structural analysis
suggests that the presence of ZnO thin film on TiO2 ETL leads to the
growth of larger perovskite crystals with improved crystallinity.
Fig. 1a shows the current density–voltage (J-V) characteristic of
PSCs fabricated on TiO2 and TiO2/ZnO ETLs, measured under 100 mW
cm−2, AM1.5 illumination at 25 °C and reverse scan. The champion
reference device depicts a decent PCE of 17.51% with a Voc of 1.10 V, a
fill factor (FF) of 68.8% and a short circuit current density (Jsc) of 22.9
mA cm−2. In contrast, a superior photovoltaic performance is observed
for TiO2/ZnO bilayer-based PSC, which yields a maximum PCE of
18.77% with an improved Voc of 1.14 V, a FF of 71.2% and a Jsc of 22.8
mA cm−2. The statistic distributions of photovoltaic (PV) data for 10
devices are shown in Fig. S4. It is clear that the average PCE of TiO2/
ZnO-based PSCs are higher than that of the reference PSCs mainly due
to the improved Voc and FF. Fig. 1b shows the EQE response of both
devices with high photon to current conversion over 75%, leading to an
integrated Jsc of 22.9 mA cm−2 and 22.2 mA cm−2 for TiO2 and TiO2/
ZnO based PSCs, respectively.
Next, we investigate the influence of improved morphology and
different ETL/perovskite interfaces on the resulted solar cells perfor-
mance by using dark J-V, electrochemical impedance spectroscopy
(EIS), steady state photoluminescence and intensity modulated current
and voltage spectroscopy (IMPS and IMVS) measurements. The dark J-
V curves of the TiO2 and TiO2/ZnO based PSCs under reverse scan in
the log scale as a function of applied bias are shown in Fig. 2a. The
various regions of a dark J-V in PSCs were discussed in detail in our
previous works (Albadri et al., 2017; Tress et al., 2018). The obtained
plots for both devices show a similar trend in the high and mid forward
bias regions with a comparable magnitude. In the low forward bias
region (from 0 V to 0.2 V), the observed lower value of dark current in
TiO2/ZnO-based device compared with TiO2-based device is due to its
higher shunt resistance or low leakage current. In general, shunt re-
sistance is in parallel with the junction of solar cells, determining the
extent of leakage current. A higher value of the shunt resistance in solar
cells causes lower leakage current. Our dark current characterization
shows the better shunt resistance in TiO2/ZnO ETL/perovskite PSCs.
Fig. 2b depicts the plots of ideality factor with respect to the applied
bias. It is worth pointing out that the PSCs quality not only depends on
the shunt resistance, but also on the device parameters such as ideality
factor, charge accumulation and recombination (Prochowicz et al.,
2019). Both PSCs show the similar curves with difference in their
magnitude. The ideality factor values in the range of 1.92 and 1.86
D. Prochowicz, et al.
Fig. 1. (a) Current density–voltage (J-V) characteristic of PSCs fabricated on TiO2 and TiO2/ZnO ETLs, measured under 100 mW cm−2, AM1.5 illumination at 25 °C
and reverse scan, and (b) EQE responses of PSCs fabricated on TiO2 and TiO2/ZnO ETLs.
k T dlnJ (V ) −1
were obtained using equation nID (V ) = Be dV ( )
for TiO2 and
TiO2/ZnO-based PSCs, respectively. Previously, we explained the role
series resistance (Rs) on the magnitude of the ideality factor (Tress
et al., 2018). Briefly, the value of ideality factor is valid only in the
exponential region (0.85–0.95 V) of J-V characteristics, whereas it is
often found that the J-V curve is dominated by shunt and series re-
sistances. In general, the recombination in the bulk of perovskite layer
and the surface recombination at both selective contacts were found to
be the main recombination centres in the PSCs (Yadav et al., 2017). The
ideality factor with the value of 1 suggests that band to band re-
combination occurred, whereas the value of 2 indicates that the re-
combination is occurred in the space charge region, close to the surface
contact (Prochowicz et al., 2017). In this study, the resulted values of
ideality factor (above 1.5) suggest that the recombination at space
charge region is mainly dominant in both PSCs.
To further analyse the recombination mechanism in the resulted
devices, EIS measurements under dark and light as a function of applied
bias were performed. Fig. 3a shows the Nyquist spectra of TiO2 and
TiO2/ZnO based PSC at a bias close to the knee voltage of 0.8 V. The
result depicts two fully resolved semicircles in the low and high fre-
quency regions, which are consistent with the literature (Ravishankar
et al., 2018, 2019). In general, the low frequency arc is related to the
Fig. 2. (a) The dark J-V curves of the TiO2 and TiO2/ZnO based PSCs under reverse scan in the log scale as a function of applied bias, and (b) ideality factor with
respect to the applied bias for TiO2 and TiO2/ZnO based PSCs.
52
Solar Energy 197 (2020) 50–57
charge accumulation and ionic motion at interfaces (ETL/perovskite
and perovskite/HTL), whereas the high frequency arc corresponds to
the recombination in PSCs (Contreras-Bernal et al., 2019; Wang et al.,
2019). We note that the fabrication process of both solar cells was
carried out at a same time to maintain the same experimental condi-
tions. Consequently, the observed significant differences in the high
frequency arcs are stem from difference in the recombination. Fig. 3b
shows the electrical equivalent circuit used for fitting the obtained
Nyquist spectra, where Rs represents the series resistance, associated
with the connecting terminals, RHF and CHF represent the high fre-
quency resistance (recombination resistance) and capacitance (geome-
trical capacitance), and RLF and CLH represent the low frequency re-
sistance and capacitance associated with charge accumulation and ion
motion. The value of Rs for both PSCs was calculated from the intercept
of complex impedance in the real axis. The values of 18 Ω and 21 Ω are
estimated for TiO2 and TiO2/ZnO-based PSCs, respectively. Fig. 3c
depicts the trend of RHF for both PSCs as a function of applied bias
extracted from the Nyquist spectra using the equivalent circuit shown in
Fig. 3b. The obtained plots follow the exponential behaviour with a
similar trend, while their absolute values are different. The behaviour
of RHF is described by the equation of RHF = R 0 exp(−βqV / KB T ) , where,
T is absolute temperature, kB is Boltzmann constant, q is elementary
D. Prochowicz, et al.
Fig. 3. (a) Nyquist spectra of the TiO2- and TiO2/ZnO based PSC at a bias corresponding to the knee voltage of 0.8 V, (b) electrical equivalent circuit used for fitting
the Nyquist spectra, (c) plot of RHF for both PSCs as a function of applied bias extracted from the Nyquist spectra using the equivalent circuit and (d) PL spectra of the
perovskite layer deposited on TiO2 and TiO2/ZnO ETLs.
1
charge, β (β = ideality factor ) is the recombination parameter, V is applied
voltage and Ro is the resistance at zero bias. A lower value of RHF for the
TiO2-based PSC compared with TiO2/ZnO-based PSC signifies its higher
recombination. The value of β, which defines the recombination in
PSCs, was calculated as 0.47 and 0.55 for TiO2 and TiO2/ZnO-based
PSCs, respectively. The higher value of β in TiO2/ZnO-based PSC is
attributed to the lower recombination, which is due to the improved
morphology and larger grain size of the perovskite absorber layer (Tress
et al., 2018; Yadav et al., 2017; Ravishankar et al., 2018). The obtained
EIS results are consistent with the finding of ideality factor.
Photoluminescence (PL) measurements were performed to under-
stand the transport properties of perovskite films deposited on different
ETLs and shown in Fig. 3d. The PL peak of the perovskite film on TiO2/
ZnO ETL exhibits much stronger quenching effect as compared to the
TiO2-based perovskite. These results suggest that TiO2/ZnO ETL has
better charge extraction properties at ETL/perovskite interface as
compared to the TiO2 ETL.
The capacitance versus frequency (C-F) plots for both devices under
illumination and dark conditions at zero applied bias are shown in
Fig. 4a. In both conditions, the C-F plots of the investigated devices
reveal similar behaviour with a significant difference in absolute values.
We found that under illumination the generated charges and ions are
accumulated at the ETL/perovskite interface leading to a higher value
of capacitance at low frequency region compared with the device
measured under dark (Yadav et al., 2017). The different plateaus in the
C-F plots represent a difference in polarization step, where the high
frequency plateau is due to the dielectric response of the perovskite
layer and the low frequency plateau is associated with the charges and
ions accumulation. From the obtained C-F plots in both PSCs, we con-
clude that the presence of ZnO layer does not play significant role on
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Solar Energy 197 (2020) 50–57
the charge and ion accumulation dynamics.
Next, we performed the Mott-Schottky analysis on the corre-
sponding devices under dark condition to further look into the charge
carrier concentration. The carrier concentration and built-in-potential
are calculated by considering the slope and intercept at X-axis, re-
spectively (Fig. S5). The carrier concentrations of 3.13 × 1018 and
2.20 × 1018 cm−3 and built-in-potentials of 1 V and 1.1 V were esti-
mated for TiO2 and TiO2/ZnO based PSCs, respectively. An almost si-
milar value for built-in-potential is expected for both PSCs due to slight
change in the ETL/perovskite interface.
To further study about TiO2 and TiO2/ZnO based PSCs, intensity
modulated photocurrent and photovoltage spectroscopy (IMPS and
IMVS) were performed (Fig. 5). The IMPS responses of both PSCs in the
frequency domain depicts the well-separated two maxima peaks at low
and high frequencies, which well coincides with each other. As reported
previously (Prochowicz et al., 2017), the time response associated with
the high frequency is related to the product of Rs and geometrical ca-
pacitance. On the other hand, the time response associated with the low
frequency (high time constant) corresponds to the ionic movements. It
is to be noted here that IMPS measurements were performed at short
circuit condition, where net terminal voltage across PSCs are close to
zero. Under this situation it is expected that ionic motions are not in-
itiated and a similar time response is observed for both the PSCs.
Moreover, in case of IMVS measurement, performed at Voc of device,
one can expect the bias initiated ion motion.
Fig. 5b shows the IMVS responses for both PSCs in the frequency
domain, which illustrates the similar trend with two well-separated
maxima peaks in the low and high frequency spectra regions. In both
solar cells, the low frequency peaks correspond to the time constants of
0.05 sec and 1 sec, while the high frequency peaks correspond to the
D. Prochowicz, et al. Solar Energy 197 (2020) 50–57

Fig. 4. The capacitance versus frequency (C-F) plots for both devices at zero applied bias (a) under illumination and (b) dark conditions.

time constants of 2 µs and 4 µs for TiO2 and TiO2/ZnO based PSCs,

respectively. We note that the time response in order of µs calculated
from the high frequency peak is related to the charge recombination
(Albadri et al., 2017). The longer time response in TiO2/ZnO based PSC
is consistent with the higher value of RHF obtained from the EIS mea-
surement. Based on the results from EIS, J-V Dark, IMPS and IMVS, we
conclude that the combination of TiO2/ZnO ETL improves the proper-
ties of perovskite layer and enhances the device performance via sup-
press the device recombination.
From the above measurements and analysis, it is concluded that
when the TiO2 and TiO2/ZnO-based PSCs are measured under illumi-
nation, the following steps are possibly happened (Fig. 6). Under illu-
mination in Cs5(MA0.17 FA0.83)95Pb(I0.83 Br0.17)3 electron-hole pair are
generated (step 1). To generate the photocurrent, the holes move to-
wards Au contacts via HTM (step 2), at a same time electron move
towards FTO via TiO2 or TiO2/ZnO layers (step 3). The electrons in
TiO2 or TiO2/ZnO layers and holes in HTM layers can leak as a shunt
current (step 4). The shunt current is generally depended on the quality
of perovskite absorber layer. In this work, the employment of ZnO NCs
layer on top of TiO2 ETL is significantly improved the grain size (Fig. Fig. 6. Energy band diagram (illustrative) of PSCs under illumination with
S1), which eventually reduces the grain boundaries and improve the possible sequence of events.

Fig. 5. Intensity modulated (a) photocurrent and (b) photovoltage spectroscopy (IMPS and IMVS) of TiO2 and TiO2/ZnO based PSCs measured as a function of
frequency.

54
D. Prochowicz, et al.
shunt resistance of the TiO2/ZnO-based PSCs. In the literature, it is
well-known that under the illumination and bias, the ionic defects such
as I− (interstitial) can accumulate at ETL/perovskite interface (step 5).
These ions can also generate the traps levels, where photo-generated
holes accumulate and accelerate the recombination. However, from the
ideality factor, EIS and IMVS analysis, a suppressed recombination in
TiO2/ZnO-based PSCs is achieved due to the improved grain size in the
perovskite absorber layer grown on ZnO NCs. Additionally, the ZnO
NCs improve the shunt resistance as well as the perovskite crystallinity
and suppress the recombination in the device. Besides, ZnO has deeper
conduction band (CB) as compared to TiO2 ETL with respect to the CB
of triple-A cation perovskite film (Fig. S6). As seen, there is a small
barrier for transferring the electrons from CB of the perovskite film to
the TiO2 ETL. By using ZnO at the interface with slightly deeper CB than
that of perovskite film, we could adjust the band alignment in the de-
vice and thus facilitate the charge transfer and reduce the recombina-
tion.
3. Conclusions
In summary, we studied the charge recombination and accumula-
tion mechanisms in planar PSCs based on compact TiO2 and bilayer
TiO2/ZnO ETLs. The effect of selected ETLs on the performance of PSCs
was investigated using impedance spectroscopy, intensity-modulated
photocurrent and photovoltage spectroscopy as well as Mott-Schottky
analysis under dark and illumination conditions. We found that TiO2/
ZnO PSCs have higher Voc and FF, which lead to a higher PCE.
Interestingly, the morphology of perovskite film deposited on top of
TiO2/ZnO ETL shows larger grain size with better crystallinity as
compared to the perovskite on TiO2 ETL, resulting in lower grain
boundaries and thus reduced the shunt leakage current. Moreover, the
lower grain boundaries also reduce the recombination centers, which
results in lower ideality factor and higher Voc. These results explain
higher efficiency of PSCs fabricated on TiO2/ZnO ETL and present a
comprehensive study on the PSCs modified by the ZnO NCs interface
layer, which is valuable for understanding the working mechanisms in
the PSCs.
4. Experimental section
4.1. Device fabrication
4.1.1. Substrate preparation
Nippon Sheet Glass 10 Ω/sq was cleaned by sonication in 2%
Hellmanex water solution for 30 min. After rinsing with deionised
water and ethanol for 15 min, the FTO substrates were further cleaned
with UV ozone treatment for 15 min.
4.1.2. ETLs preparation
A compact thick TiO2 layer was deposited by spray pyrolysis of 9 mL
ethanol solution containing 0.6 mL titanium diisopropoxide bis(acet-
ylacetonate) solution (75% in 2-propanol, Sigma-Aldrich) and 0.4 mL
acetylacetone at 450 °C in air. After the spraying, the substrates were
left at 450 °C for 30 min and left to cool down to room temperature.
ZnO nanoparticles for ZnO ETL was prepared by a recently reported
method (Lewinski et al.). Briefly, Et2Zn (1,77 mL of a 2.26 M solution in
hexane, 4 mmol) was added dropwise to DMSO (20 mL) at room tem-
perature. Then, the resulting mixture was exposed to air and stirred for
additional 48 h at ambient conditions. After this time ZnO nano-
particles (~5 nm in diameter) were separated from the parent DMSO
colloidal suspension by using acetone and rewashed several times. The
ZnO nanoparticles were dissolve in anhydrous DMSO at a concentration
of ~5 mg/ml. The solution was then spin-coated on TiO2-based sub-
strates at 3000 rpm for 20 s followed by short baking at 150 °C for
5 min. This procedure was repeated one times and finally annealed at
150 °C for 1 h. The thickness of the optimized ZnO layer was estimated
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Solar Energy 197 (2020) 50–57
as 20 nm using LSE-MS profilometer.
4.1.3. Perovskite precursor solution and deposition
Perovskite solution containing FAI (1 M), PbI2 (1.1 M), MABr
(0.2 M) and PbBr2 (0.2 M) was first prepared in a mixed solvent of
DMF:DMSO = 4:1 v/v. Then, a 5 vol% of 1.5 M CsI solution in DMSO
was added into the perovskite solution in order to have a triple cation
perovskite composition, as reported elsewhere (Tavakoli et al., 2018a).
The perovskite solution was spin-coated using conditions such as
1000 rpm for 10 sec and, continuously at 6000 rpm for 20 sec. During
the second phase, 100 μL of chlorobenzene was dropped on top film 10
sec before end of spinning. The film was further annealed at 100 °C for
50 min in a dry box.
4.1.4. Hole transporting layer preparation and deposition
Hole transporting material (HTM) solution was prepared by dis-
solving 100 mg spiro-MeOTAD in 1.094 mL chlorobenzene and ad-
ditionally mixing it with 23 µL of lithium bis(trifluoromethylsulphonyl)
imide (stock solution Li-TFSI 520 mg·mL−1 in acetonitrile), 39 µL tert-
butylpyridine. HTM was deposited on top of the perovskite layer by
spin coating at 4000 rpm for 20 sec. Finally, Au electrode (80 nm) was
thermally evaporated under high vacuum.
4.2. Device characterization
The J-V characteristics of the devices were measured under
100 mW/cm2 conditions using a 450 W Xenon lamp (Oriel), as a light
source, equipped with a Schott K113 Tempax sunlight filter (Praezisions
Glas & Optik GmbH) to match the emission spectra to the AM1.5G
standard in the region of 350–750 nm. The current–voltage character-
istics of the devices were obtained by applying external potential bias to
the cell while recording the generated photocurrent using a Keithley
(Model 2400) digital source meter and also with a temperature-con-
trolled probe station from LASC. The J–V curves of all devices were
measured by masking the active area with a metal mask of area
0.16 cm2. AC measurements were performed using a potentiostat
Biologic SP300 equipped with a frequency response analyser. EIS
measurements were performed in the DC bias range of 0 to open circuit
voltage with an AC perturbation signal of 20 mV in the frequency range
of 100 mHz to 100 kHz. IMVS and IMPS measurements were done by a
frequency response analyzer (FRA) connected with Bio-Logic SP300
potentiostat.
4.3. Thin film characterizations
The powder X-ray diffraction spectrometer (Rigaku, Japan) with a
Cu k line of 1.5410 °A was used to determine phase and crystallinity.
The surface SEM measurements were carried out using a field emission
scanning electron microscope (FE-SEM; S-4700, Hitachi). UV–VIS
measurements were performed on a Varian Cary 5. Photoluminescence
(PL) spectra were analyzed using a photoluminescence spectrometer
(f = 0.5 m, Acton Research Co., Spectrograph 500i. USA), and an in-
tensified CCD(PI-MAX3) (Princeton Instrument Co., IRY124, USA).
AFM images were collected using XE-100 Advanced Scanning Probe
Microscope (Park System).
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
D. P. acknowledges the financial support from the HOMING pro-
gramme of the Foundation for Polish Science co-financed by the
D. Prochowicz, et al.
European Union under the European Regional Development Fund
(POIR.04.04.00-00-5EE7/18-00). P. Y. acknowledges the ORSP of
Pandit Deendayal Petroleum University for financial support and the
financial support from DST SERB (CRG/2018/000714) and DST Nano
Mission (DST/NM/NT/2018/174).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.solener.2019.12.070.
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