Accepted Manuscript

Eliminating oxygen vacancies in SnO2 films via aerosol-assisted chemical vapour

deposition for perovskite solar cells and photoelectrochemical cells

Mohamad Firdaus Mohamad Noh, Nurul Affiqah Arzaee, Javad Safaei, Nurul Aida
Mohamed, Hyeong Pil Kim, Abd Rashid Mohd Yusoff, Jin Jang, Mohd Asri Mat Teridi
PII: S0925-8388(18)33525-4
DOI: 10.1016/j.jallcom.2018.09.273
Reference: JALCOM 47692

To appear in: Journal of Alloys and Compounds

Received Date: 29 July 2018

Revised Date: 17 September 2018
Accepted Date: 22 September 2018

Please cite this article as: M.F. Mohamad Noh, N.A. Arzaee, J. Safaei, N.A. Mohamed, H.P. Kim, A.R.
Mohd Yusoff, J. Jang, M.A. Mat Teridi, Eliminating oxygen vacancies in SnO2 films via aerosol-assisted
chemical vapour deposition for perovskite solar cells and photoelectrochemical cells, Journal of Alloys
and Compounds (2018), doi: https://doi.org/10.1016/j.jallcom.2018.09.273.

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 ACCEPTED MANUSCRIPT

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Eliminating Oxygen Vacancies in SnO2 Films via Aerosol-Assisted
Chemical Vapour Deposition for Perovskite Solar Cells and
Photoelectrochemical Cells

Mohamad Firdaus Mohamad Noha,*, Nurul Affiqah Arzaeeb, Javad Safaeia, Nurul Aida
Mohameda, Hyeong Pil Kimc, Abd Rashid Mohd Yusoffd, Jin Jangc, Mohd Asri Mat Teridia,*

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a
Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.

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b
Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.
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Advanced Display Research Center, Department of Information Display, Kyung Hee University, Dongdaemoon-

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14 gu, Seoul 130-701, South Korea.
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Department of Materials Science & Engineering, Yonsei University, Seoul 03722, South Korea

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*Corrresponding author: fir.noh@gmail.com (Mohamad Firdaus Mohamad Noh), Phone:+603-89118580
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asri@ukm.edu.my (Mohd Asri Mat Teridi), Phone:+603-89118580

Abstract
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Thin film deposition technologies are rapidly advancing especially in the field of solar energy
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storage and solar cells. Herein, spin coating and aerosol-assisted chemical vapour deposition
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(AACVD) are chosen to represent solution-based and vapour-based deposition routes,

respectively. SnO2 films processed at low temperature via the mentioned methods are applied
in photoelectrochemical (PEC) cell as active photoanode and perovskite solar cell (PSC) as
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electron transport layer. This study discovers that spin coated SnO2 film which consists of
greater amount of oxygen vacancy is beneficial for PEC cell but is detrimental towards the
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stability and hysteresis of PSC device. The improved PEC performance is majorly attributed
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to the enhanced light absorption of SnO2 caused by the reduction of its band gap energy.
Meanwhile, AACVD method successfully eliminates oxygen vacancy in SnO2 crystal lattice.
Although PEC cell shows very poor performance upon using AACVD-fabricated SnO2, the
employment of this layer greatly enhances the overall performance of PSC. The absence of
oxygen vacancy allows efficient charge transfer at SnO2/perovskite interface and renders
SnO2 less hydrophobic which prevents moisture-induced degradation of perovskite layer. Our
findings provide valuable information to understanding the film formation mechanism of
different fabrication technologies and their suitability for particular optoelectronic application.
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Keywords: Spin coating, aerosol-assisted chemical vapour deposition, perovskite solar cell,
photoelectrochemical water splitting, oxygen vacancy

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1. Introduction

Steady progress of thin film fabrication techniques since the last century have enabled a
plethora of technological breakthroughs in the field of microelectronics and nanotechnology
such as light emitting diodes, transistors, sensors, thin film batteries and solar cells, to name
but a few. The thin film deposition methods could be categorized into several groups

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depending on the processing protocols and film formation mechanism. For instance, solution-
phase techniques including spin coating, hydrothermal and chemical bath deposition refer to

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material deposition process from a solution of precursor.[1] Meanwhile, chemical vapour
deposition (CVD), electron-beam evaporation and thermal evaporation are classified as

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vapour-phase techniques[2] as the precursor involved in the film formation are in gaseous
state. A semiconducting layer that is produced from a particular fabrication technique will
show unique morphological, electrical and optical properties.

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Tin (IV) oxide (SnO2) is one of the most essential semiconducting material in thin film
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technologies including solar cell and photoelectrochemical (PEC) water splitting. The
relatively high bulk electron mobility (about 250 cm2 V-1 s-1) and a band gap value in the UV-
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range (about 3.95eV) have enabled SnO2 to be an excellent semiconductor.[3] In addition to

its chemical and thermal stability, SnO2 is also well-known to be environmental friendly.[4]
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The precursors that were typically used to synthesis SnO2 such as SnCl2 and SnCl4 are also
fairly cheap and easy to handle.[3] All of these features render SnO2 very attractive as one of
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the main component in opto-electronic devices.

Recently, the rapid growth of global renewable energy sector has attracted
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considerable attention among scientific community to explore the potential of solar energy
storage by means of PEC water splitting. Compared to the conventional water splitting
technique (i.e. a system that consists of photovoltaic cells and an electrolyser), PEC cell
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allows direct conversion of solar energy to hydrogen with the aid of semiconducting
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materials.[5] As a result, PEC cell demonstrates higher solar-to-hydrogen conversion

efficiency and significantly lower capital cost.[5] However, the overall performance of PEC
cell not only relies on the intrinsic and morphological properties of the photoactive layer,[6,7]
but also on the chemical and photochemical stability of the material.[8] In the meantime,
introduction of crystallographic defects especially oxygen vacancy in the photoactive layer
has been recognized as a crucial factor that can enhance the PEC performance.[9–11] The
efficiency enhancement is ascribed to the increasing free carrier density and reduction of band

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gap energy which improves the light absorption ability, photoelectron generation and charge
separation efficiency.[9,10,12,13]
Perovskite solar cells (PSC) is another promising technologies among other types of
third generation photovoltaic technologies such as polymer solar cells and dye-sensitized solar
cells owing to outstanding efficiency, low-cost and facile fabrication process.[14] The current
solar power-to-current conversion efficiency (PCE) holds a record of 23.3% which is higher

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than other long-established thin-film solar cell technologies such as CIGS and CdTe.[15] In
spite of the outstanding PCE, it is well-known that the device still suffers from poor ambient

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air stability due to rapid degradation of perovskite material upon exposure to humidity.[16]
Several countermeasures have been taken to overcome this issue and one of it is the

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employment of hydrophobic electron and hole transport layers.[17,18] Currently, electron
transport layer (ETL) for PSC device either in form of compact or mesoporous layer is
dominated by TiO2.[3] Nevertheless, many groups have reported the unsuitability of TiO2 for

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PSC because TiO2 could negatively affect the performance and stability of the device.
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Leijtens et al.[19] claimed that TiO2 causes perovskite degradation in the presence of UV light
owing to the presence of oxygen vacancy in TiO2 and interaction with atmospheric oxygen.
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Zhang et al.[20] claimed that the oxygen vacancy in TiO2 could migrate during the
photocurrent-voltage (J-V) measurement due to the applied potential which in turn results in
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hysteresis effect. The presence of oxygen vacancy also deteriorates device efficiency due to
the increment of trap-assisted charge carrier recombination rate at the ETL/perovskite
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interface.[21] Therefore, several other inorganic and organic materials have been investigated
to replace TiO2 as ETL including ZnO[22], Nb2O5[23], and PCBM.[24] Another notable
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material that could challenge the performance of TiO2 as ETL is SnO2 where a PCE of up to
20.5% has been recorded for planar heterojunction PSC.[25] In addition to its magnificent
anti-reflection properties,[26] fabrication of SnO2 only requires low temperature heating
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which save the energy consumption.[27] Moreover, SnO2-based PSC indicated better stability
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against UV light and less severe hysteresis effect in comparison to TiO2-based

counterparts.[28]
In the present work, SnO2 thin films were fabricated at low temperature of 180°C via
two distinctive deposition methods namely spin coating and AACVD techniques which
represent the solution-based and vapour-based deposition process, respectively. It is known
that synthesis of SnO2 at low temperature usually lead to the formation of oxygen vacancy in
the SnO2 crystal lattice (e.g. SnO2-X or sometimes SnO phase).[29,30] However, different

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fabrication methods could alter the composition of SnO2 formed. Spin coating is one of the
most prominent technique used to fabricate thin film with thickness ranging from nanometers
to micrometers. The final film thickness is governed by several processing condition
including spin speed, spin time, dispense volume, solution viscosity and concentration of
precursor.[31] Meanwhile, aerosol-assisted chemical vapour deposition (AACVD) is a
modified method of conventional CVD which has been applied to fabricate numerous type of

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thin films such as NiO[32], BiVO4[33] and Fe2O3[34] for various applications. Instead of
using elevated temperature, AACVD employed ultrasonic atomizer to generate aerosol of

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precursors which are transferred to a reaction chamber with the help of carrier gas.[4] In
addition to reducing energy usage, AACVD allows easy control on the morphological

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properties of the fabricated thin film by changing several parameters during deposition. For
instance, film thickness can be increased by prolonging the deposition period.[4] Besides, the
roughness of the layer produced can be varied by regulating the deposition temperature and

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precursor concentration.[26] Since two distinctive techniques are used in this study, the
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resulting SnO2 thin films have different composition of oxygen vacancies which influence
optical and electrical behaviour and eventually lead to different device performance.
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Even though high temperature processing of SnO2 could improve the performance of
PEC cell[26], focus was given to low temperature-based SnO2 since this kind of layer is very
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favourable to enhance the performance of PSC device.[26,27] The structural, electrical and
optical properties of each SnO2 thin film was thoroughly investigated. Both SnO2 thin films
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were then employed as photoanode in PEC cells as well as ETL in PSC device. Astoundingly,
the spin coated SnO2 layer is beneficial as photoanode in PEC technology compared to
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AACVD-based SnO2. On the other hand, PSC device based on SnO2 ETL prepared through
AACVD exhibited higher efficiency and improved stability in contrary to spin coated-based
SnO2 device counterpart. The inverse behaviour of both thin films is discussed in details in
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this study.
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2. Experimental

2.1. Materials

Fluorine-doped tin oxide (FTO) glass (sheet resistance 15 Ω sq-1) was bought from Pilkington.
Tin (II) chloride (SnCl2, 98%), lead (II) iodide (PbI2, 99%), lithium

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bis(trifluoromethanesulfonyl)imide (Li-TFSI, 99%), 4-tert-butylpyridine (tBP, 96%), γ-
Butyrolactone (GBL, 99%), dimethylsulfoxide (DMSO, 99.9%) and anhydrous acetonitrile
(99.8%) was purchased from Sigma Aldrich. Methylammonium iodide (MAI) from Dyesol
was used. Phenyl-C71-butyric acid methyl ester (PC70BM) was obtained from Ossila.
2,2’,7,7’-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluorene (spiro-OMeTAD,
99.5%) from Luminescence Technology Corporation was used. Absolute ethanol and

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chlorobenzene (99%) was purchased from VWR International Limited and R&M Chemicals,
respectively.

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2.2. SnO2 film fabrication

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FTO substrates were cleaned using acetone, methanol and isopropanol in ultrasonic bath for
10 min each. Then, the substrates were washed with deionized water and dried using N2 flow.

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For solution-based technique, 0.1M SnCl2 dissolved in ethanol was spin coated on the pre-
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cleaned FTO at 2000 rpm for 30 s. Afterwards, the layer was annealed at 180°C for 1 hour in
ambient atmosphere.
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For vapour-based technique, SnO2 layer was deposited on FTO using a homemade
AACVD system as described in our previous work (Fig. S1).[26] In brief, the pre-aged
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solution of SnCl2 in ethanol (0.01M) was atomized using a piezoelectric transducer operated
at full power, so that the aerosol created achieved the maximum dew point in the container. In
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other words, the aerosol generated fully filled the precursor container such that the generation
rate of aerosol from the precursor solution is equal to the condensation rate of aerosol back
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into the solution. By using purified air as carrier gas with volume flow rate of 280 cm3 min-1,
the generated aerosol was transferred into the filtration chamber where the aerosol droplets
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were screened (large-sized droplets precipitate while small-sized droplets travel further). In
filtration chamber, purified air with volume flow rate of 1530 cm3 min-1 was added to reduce
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the concentration of aerosol. The flow of aerosol was directed to a reaction chamber where
thin SnO2 layer will form on FTO substrate that was placed on a pre-heated hotplate with
temperature of 180°C. The deposition period was set to 15 min. To avoid disturbance of the
flow of gas-vapour mixture, a small gap was made under the reaction chamber to allow the
evaporated solvent, by-products of the reaction and excess air to leave the chamber.

2.3. Perovskite solar cell fabrication

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For the application in PSC, the prepared SnO2 samples were transferred into a glovebox.
Then, PCBM layer (10 mg mL-1 in chlorobenzene) was spin coated on the ETL at 2000 rpm
for 30 s before annealed at 100°C for 10 min. The sample was left to cool down to room
temperature before coating next layer. The perovskite film was prepared by spin coating
perovskite precursor solution containing 462 mg PbI2 and 159 mg MAI dissolved in 700 µL

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GBL and 300 µL DMSO at 1000 rpm for 10 s and 4000 rpm for another 30 s. 15 s before the
second spin program ended, 500 µL chlorobenzene was dropped onto the perovskite layer and

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followed by annealing at 100°C for 30 min. After cooling down, HTM solution consisting of
1 mL spiro-OMeTAD solution (72.3 mg in 1 mL chlorobenzene), 17.5 µL Li-TFSI solution

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(520 mg Li-TFSI in 1 mL acetonitrile) and 28.8 µL tBP was spin coated at 4000 rpm for 20 s.
Finally, silver contact was deposited via thermal evaporation. The active area of cell was 0.07
cm2.

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2.4. Thin film characterization
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For determining the morphology of the films, ZEISS Merlin field emission scanning electron
microscopy (FESEM) and Nanosurf Easyscan2 atomic force microscopy (AFM) were
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utilized. Energy dispersive spetroscopy (EDX) was also performed using Zeiss Merlin. The
photograph of water contact angle of the films were acquired using Kruss Drop Shape
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Analyzer – DSA100 contact angle meter. Transmittance and absorption spectra were recorded
on Lambda 35 Perkin Elmer UV-visible spectrophotometer.
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2.5. Photoelectrochemical cell characterization

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The performance of each SnO2 sample in PEC cell was analysed by means of linear sweep
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voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS)

using Metrohm Autolab electrochemical workstation under simulated one sun illumination
and dark condition. The PEC properties was investigated using three-electrode configuration
where SnO2 film coated on FTO substrate was used as working electrode, Pt electrode was
applied as counter electrode and Ag/AgCl was used as reference electrode. The electrolyte
used was 0.5M Na2SO4 solution in deionized water and the active area of the photoanode was
1.0 cm2. In LSV analysis, the voltage was swept in the range of -1.0 to 1.0 V vs. Ag/AgCl at a

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rate of 10 mV s-1. To check the stability of the photoanode, chronoamperometry measurement
was carried out for 5 min under bias voltage of 0.0V vs. Ag/AgCl. For EIS measurement, a
frequency in the range of 105 to 0.1 Hz and bias voltage of 0.0 V vs. Ag/AgCl was applied.

2.6. Perovskite solar cell characterization

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Current density-voltage (J-V) characteristics was recorded using a Keithley 2400 source meter
under AM 1.5G solar illumination with a calibrated intensity of 100 mW cm-2 as determined

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by a standard silicon reference cell (Daystar Meter). J-V sweeps were performed from VOC to
JSC and vice versa at a scan rate of 0.1 V s-1. The steady-state photoluminescence spectra were

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collected by using a florescence spectrometer instrument (FLS920, Edinburgh Instuments) at
excitation wavelength of 515 nm.

3. Results and Discussion

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3.1. SnO2 film properties
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SnO2 thin films were fabricated using spin coating and AACVD techniques on FTO substrate
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at low temperature of 180°C. The crystallinity of SnO2 deposited via AACVD (denoted as
AACVD-SnO2) and spin coating (denoted as SC-SnO2) techniques were determined using
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XRD (Fig. S2). As expected, AACVD-SnO2 sample exhibited no specific diffraction peak
while SC-SnO2 showed very low degree of crystallinity. This indicate that deposition of SnO2
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at low temperature tend to form amorphous SnO2 structure regardless of the fabrication
technique used which is consistent with the previous reports.[26,27] To confirm that the
samples prepared are SnO2, EDX spectra was taken (Fig. 1 (a)-(b)). The AACVD-SnO2 films
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showed almost perfect tin to oxygen molar ratio of 1 to 2 which indicate that the AACVD
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technique completely converted SnCl2 to SnO2. On the other hand, the atomic percentage of
oxygen in SC-SnO2 sample was slightly lower compared to that found in AACVD-SnO2
counterpart. Such phenomenon signifies the existence of oxygen vacancy both on the surface
and in crystal lattice of the spin coated film.

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Fig. 1. (a, b) EDX spectra, (c, d) FESEM images (e, f) AFM images and (g, h) water contact
angle measurement of SnO2 layers fabricated on FTO at 180°C using AACVD and spin
coating technique. All figures on the left belong to AACVD-SnO2 and all figures on the right
belong to SC-SnO2.

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Topographical information of the prepared thin films were obtained from FESEM
images. From Fig. 1 (c), it was observed that SnO2 layer formed from AACVD method has
small particles evenly distributed throughout the FTO surface and the particles showed no
specific growing orientation. On the other hand, spin coated SnO2 layer indicated very smooth
surface that covers the whole FTO layer (Fig. 1(d)). However, the structure of the underlying
FTO layer is still visible as spin coated SnO2 layer not only cover the FTO surface but also

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filled in the grooves of FTO. The morphology of both SnO2 thin films were further confirmed
using atomic force microscopy (AFM) as displayed in Fig. 1 (e)-(f). Based on AFM analysis,

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root-mean-square (RMS) roughness of 5.3 nm and 2.8 nm was acquired for film deposited
using AACVD and spin coating, respectively. The slightly rougher surface of AACVD-SnO2

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layer is due to the presence of small SnO2 nanoparticles.
To investigate the wettability of each SnO2 surface, water contact angle (WCA)
measurement was carried out. Astoundingly, it was discovered that AACVD-SnO2 layer

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demonstrated higher contact angle value (93.9°) compared to SC-SnO2 counterpart (63.3°),
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although both SnO2 layers were prepared from similar precursor solution (i.e SnCl2 in
ethanol), as can be seen in Fig. 1 (g)-(h). This indicate that AACVD-SnO2 layer is more
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hydrophobic than SC-SnO2 which is attributed to the low interfacial tension between water
and AACVD-SnO2 surface. The difference in wettability of the respective SnO2 film could be
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attributed to two major factors namely surface roughness and oxygen vacancy on the surface
of the thin films.[35,36] From the viewpoint of surface roughness, rougher film would lead to
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improved hydrophobicity and higher contact angle.[37,38] This is in good agreement with our
AFM analysis where AACVD-SnO2 has higher RMS roughness than SC-SnO2. However, it
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must be noted that the wetting property of a solid surface could be described either by Wenzel
model or Cassie-Baxter model.[39] According to Wenzel model, the water droplet penetrates
into the grooves of the film, forming intimate contact between water and the film surface. In
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some circumstances, the water may suspend on the grooves and trap small air pockets
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underneath the water. This situation is referred as Cassie-Baxter model. In our case, it is
rather difficult to tell which model dominates the wetting behaviour of the samples. Yet, we
anticipate that Wenzel model is more relevant in this study as this model can properly explain
our findings on the higher performance of AACVD-SnO2-based perovskite device which will
be discussed in more detail in next section.
Meanwhile, higher amount of oxygen vacancy on SnO2 surface could also promote
wettability.[35] Similar phenomenon has also been observed for TiO2, ZnO and

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SrTiO3.[36,40,41] As can be seen from EDX analysis, SC-SnO2 sample has greater number of
oxygen vacancy. The presence of oxygen vacancy in SC-SnO2 induce dissociative adsorption
of water at the vacancy sites. The sole oxygen atom of water heals the vacancy while the other
two hydrogen atoms bind to the oxygen atoms on the surface of SnO2 to form hydroxyl
groups.[35,36] The polar hydroxyls groups that was created on the film surface can form
oxygen bonds with the subsequent water molecules which eventually enhance the surface

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hydrophilicity of SC-SnO2. Another well-known factor that could influence the wettability of
SnO2 surface is the surface free energy which is to some extent caused by the crystal facets of

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SnO2.[42] Nevertheless, since both SnO2 samples prepared in this study exhibited almost
identical amorphous nature as shown in XRD spectra, we inferred that surface free energy

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induced by crystal facets is not the main factor that determine the wettability.

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Fig. 2. (a) Transmittance and (b) absorbance spectra of AACVD-SnO2 and SC-SnO2 on FTO
substrate. Inset of (b) is Tauc Plot for band gap determination.
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High transparency and low absorption of SnO2 is preferable to improve the efficiency
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of a PSC device as this feature could enhance the light absorption ability of active perovskite
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layer. In contrary, high light absorption of SnO2 layer itself is highly desired to enhance the
PEC performance for solar water splitting process. As represented in Fig. 2 (a), both SnO2-
coated FTO glasses exhibited light transmittance of more than 75% in the visible light region,
but AACVD-SnO2 sample has slightly superior transparency compared to SC-SnO2
counterpart. In addition, both SnO2-coated FTO samples showed better light transmittance
than bare FTO at certain wavelength. This is due to the fact that low temperature-processed
SnO2 reduced the light scattering effect appeared at the surface of FTO and allow the light to
travel in straight path.[26,27] The impressive light transmittance property is also attributed to

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the wide band gap of SnO2. The Tauc plot that was derived from absorbance spectra (Fig.
2(b)) suggests that different fabrication techniques could affect the band gap energies of SnO2
layers. It is noted that the corresponding onset absorption of both SnO2 samples fall in the UV
regime. Still, SC-SnO2 showed red-shift in absorbance spectra in comparison to AACVD-
SnO2. The approximated band gap values of AACVD-SnO2 and SC-SnO2 are 3.67 eV and
3.58 eV, respectively, which is in good agreement with the values reported previously.[43]

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The bandgap narrowing of SC-SnO2 could be ascribed to the high percentage of surface
defects (i.e. oxygen vacancy) in crystal lattice.[44,45] Furthermore, SC-SnO2 obviously

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demonstrated extended absorption tail into visible light region up to wavelength of
approximately 425 nm. Although this feature is also observable in AACVD-SnO2, it should

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be emphasized that the extended tail is more apparent in SC-SnO2. The extended tail is
principally stemmed from the electron transitions associated with surface oxygen vacancy-
induced electronic states near the band edge.[29,46] In other words, oxygen vacancy

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introduced new energy level in the band gap near the band edge of SnO2 which allow
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excitation of electron by lower energy photons from the intrinsic defect site. The greater
amount of oxygen vacancy, the greater number of low energy photon that can be absorbed.
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Therefore, it can be concluded that spin coating technique resulted in greater amount of
oxygen vacancy in SnO2 layer compared to AACVD.
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The formation process of SnO2 in spin coating and AACVD under low temperature
condition can be described as follows. Since the standard enthalpy of formation (∆Hf°) of
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SnO2 (∆Hf° ≈ -578 kJ mol-1)[47] is lower than that of SnCl2 (∆Hf° ≈ -336 kJ mol-1)[48], the
formation of SnO2 from SnCl2 is thermodynamically favourable, but the chemical reaction
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could appear either via direct or indirect route. Direct route refers to a straightforward reaction
between SnCl2 and O2 molecules in air to form SnO2 nanoparticles.[49] Nonetheless, this
reaction mechanism is less likely to occur in low temperature processing methods because the
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formation of SnO2 films from a SnCl2 precursor through direct route requires a large amount
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of energy.[50] This is due to the fact that Sn and Cl atoms in SnCl2 are held together by ionic
bonds and hence, the forces that held the atoms together are relatively strong.[50] Even
though the direct reaction route was reported to show low apparent activation energy (about
58 kJ mol-1),[51] Oldershaw et. al. showed that the dissociation energy of Cl-Sn-Cl bond is
still high (approximately 370 kJ mol-1).[52] Therefore, we postulate that the SnO2 films
prepared via both techniques were formed majorly through indirect reaction pathway where
Sn-based intermediates such as Sn(OH)2 are initially formed due to the reaction with ethanol

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solvent. Then, these intermediates react further to form SnO and eventually convert to
SnO2.[53] The following Eq. 1-3 represent indirect route of reaction of SnCl2.[53]

 + 2 
 →

  + 2    (Eq. 1)


  →

+ 
(Eq. 2)



+
 →

 (Eq. 3)


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Fig. 3. (a) Deposition process and (b) film formation mechanism of SnO2 via spin coating
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technique. (c) Deposition process and (d) film formation mechanism of SnO2 via AACVD
technique.
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The deposition process and possible formation mechanism of SnO2 through spin
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coating and AACVD methods are visualize in Fig. 3. In spin coating process, SnCl2 dissolved
in ethanol was dropped on the substrate, spun at certain rotation per minute (rpm) and
annealed on a hot plate at 180°C (Fig. 3 (a)). As the substrate was spinning, the excess
precursor solution was thrown away due to the inertia of the solution which progressively
reduce the thickness with prolonging spinning time.[31] During annealing process, solvent
(C2H5OH) and by-product (C2H5Cl) evaporate which subsequently leave the Sn(OH)2
intermediates on the surface of FTO (Fig. 3(b)). The continuous heat energy supplied also

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induces the conversion of Sn(OH)2 to SnO. Then, O2 molecules in air start to oxidize SnO to
form SnO2 particles. However, the O2 molecules could penetrate only from the surface (top-
side) of the layer which is directly exposed to air.[21] This lead to incomplete conversion of
SnO to SnO2 especially at the bottom of the layer near FTO and as a result, greater amount of
oxygen vacancy is created.
Meanwhile, in AACVD process, the vaporized precursor solution is blown into a hot

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reaction chamber (Fig. 3(c)). The solvent and by-products start to evaporate once the vapour
carrying the precursors enters the reaction chamber. The remaining precursors flow towards

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the FTO substrate. Then, O2 particles in the air react with the precursors as annealing
treatment continues. We postulate that the entire chemical reaction most probably occurs at

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the FTO surface rather than in the gas phase because the deposition temperature used in this
study is quite low.[26] The growth of SnO2 layer proceeds through the chemisorption of
precursors to the growing SnO2 grains, and subsequent reaction with the adsorbed O2

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molecules (Fig. 3(d)). As O2 reacts with the precursor right after the chemisorption process,
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the formation of oxygen vacancy sites in the growing SnO2 layer is prevented.
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3.2. Performance of PEC cells

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Fig. 4. Photoelectrochemical performance measured via linear sweep voltammetry. (a) SC-
SnO2 and AACVD-SnO2 photoanodes under one sun illumination, (b) SC-SnO2 and AACVD-
SnO2 photoanodes under chopping condition, (c) SC-SnO2 photoanode illuminated from front
and back as well as under dark condition and (d) AACVD-SnO2 photoanode illuminated from
front and back as well as under dark condition.

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In order to further approve that number of oxygen vacancy in SC-SnO2 layer is greater
than in AACVD-SnO2 counterpart, the thin films were employed as photoanode in

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photoelectrochemical (PEC) cell. In this system, SnO2 layer itself absorbs light which results
in the formation of photoexcited electrons and holes in its valence and conduction bands,

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respectively. The holes are transferred to water molecules, which causes oxidation of H2O to
O2 and H+ while electrons are transported to FTO and subsequently to the cathode through
external circuit where H+ ions are reduced to H2 gas. This means that photoanode that

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generates larger amount of electron-hole pair and successfully separate the charges will
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display higher photocurrent density in LSV analysis. As shown in Fig. 4 (a), both SnO2
samples exhibited photocurrent density in the range of µA cm-2 due to the low crystallinity
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and wide band gap of SnO2 which reduce their light absorption ability. However, SC-SnO2
possessed greater photocurrent density compared to AACVD-SnO2 as the voltage was swept
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from -1.0 to 1.0 V vs. Ag/AgCl which directly reflects the ability of SC-SnO2 to absorb more
light and form larger number of excitons. As explained earlier, oxygen vacancy in SC-SnO2
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create new energy level in the band gap which reduce the amount of energy per time required
to activate the photoelectrons. Oxygen vacancy also acts as electron donor enhancing the
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photocurrent density.[54] Besides that, the existence of oxygen vacancy also causes a
significant cathodic shift of onset potential for SC-SnO2 where the value decreases by about
0.27 V with respect to AACVD-SnO2. In other words, oxygen vacancy beneficially reduces
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water oxidation overpotential and increases overall PEC efficiency.[55,56]

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To validate the result, several samples were prepared and the corresponding LSV
curves are displayed in Fig. S3. From the result, similar trend was observed where SC-
SnO2 samples have higher PEC performance compared to AACVD-SnO2 which confirms
that the former owns greater number of oxygen vacancy than the latter. In the meantime,
based on Fig. 4(b), drastic change of photocurrent under chopped light illumination implies
that both samples are highly responsive towards the presence and absence of light. On top of
that, small photocurrent spikes were detected for SC-SnO2 photoanode right after the light is

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switched on. This effect can be explained as follows. When the light is turned on, electron-
hole pairs are instantaneously excited and separated in the light active SnO2 layer. Holes
diffuse to the surface of SnO2 whereas electrons are simultaneously transported to the
cathode. Nonetheless, the rate of water oxidation by holes depends on the rate of charge
transfer at SnO2/electrolyte interface. Since, the existence of oxygen vacancy species of SnO2
(i.e. SnO) in spin coated sample reduces the charge transfer process, it slows down the water

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oxidation kinetics. Consequently, holes start to accumulate at SnO2/electrolyte interface. As
the rate of holes arrival at the surface and the rate of charge transfer and recombination reach

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equilibrium, the photocurrent generation eventually stabilizes.[57] As for AACVD-SnO2
sample, since the amount of photoexcited electron-hole pairs is rather low and the holes are

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effectively separated at SnO2/electrolyte interface, no photocurrent spikes can be observed.
The effect of light illumination from front-side (i.e. SnO2-side) and back-side (i.e.
glass-side) was also investigated as shown in Fig. 4 (c)-(d). It can be seen that much lower

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photocurrent was detected for back-illuminated samples which could be attributed to either (i)
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increased light reflection and scattering caused by glass substrate and FTO layer or (ii) poor
charge transport and separation property of active layer which elevates the charge
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recombination rate.[58,59] To approve the first hypothesis, we measured the light absorption
of front- and back illuminated samples through UV-Vis spectroscopy. However, almost no
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difference can be observed from the absorption spectra (results not shown) indicating that the
second hypothesis is the dominating factor that determines the performance of PEC cell. We
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also noted that back-illuminated AACVD-SnO2 photoanode exhibited extremely low

photocurrent (almost same to dark current) as a consequence of high recombination rate of
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photogenerated charges at the SnO2/FTO interface. We believe that this behaviour mainly
originates from the difference of oxygen vacancy within both samples but further
investigation is still ongoing in our lab to explain this phenomenon thoroughly.
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Fig. 5. Nyquist plot of EIS spectra of SnO2 photoanode fabricated via spin coating and
AACVD and their corresponding fitted curves. Inset is the equivalent circuit used for curve
fitting.
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EIS analysis was also performed to comprehend the charge transfer properties of SnO2
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photoanode in PEC cell. The analysis was carried under one sun light illumination at bias
voltage of 0.0 V with frequency ranging from 105 to 0.1Hz. The EIS curves in Nyquist plot
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for both samples were best fitted using the Voight circuit as displayed in the inset of Fig. 5.
The equivalent circuit was chosen by considering a very small chi-squared (χ2) value
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(approximately 10-5) from the curve fitting software (ZSimpWin) which is associated with the
variation in fitted and experimental data.[60] RS represents the series resistance that exist in
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the circuit owing to the sheet resistance of FTO, ion movement in electrolyte and external
circuit connection.[61,62] This value is obtained from the x-intercept of the fitted curves.
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Meanwhile, each R-Q parallel component represents an incomplete semicircle where the first
component is ascribed to the charge transfer resistance (R1) and capacitance (Q1) at the
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electrolyte/SnO2 photoanode interface whereas the second component is attributed to the

charge transfer resistance (R2) and capacitance (Q2) within the bulk of SnO2. Smaller radius of
the semicircle signifies a faster charge transfer process and vice versa.[62,63] The value of all
parameters of the fitted curves are tabulated in Table S1. Usually, photoanode that has faster
charge transfer rate would also exhibit high photocurrent density in LSV measurement.
Nonetheless, we discovered that the R1 and R2 values of SC-SnO2 photoanode is higher
compared to that value of AACVD-SnO2 counterpart, in spite of the fact that the SC-SnO2

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demonstrated superior photocurrent density in LSV analysis. The slightly poor R1 and R2
observed in SC-SnO2 are influenced by the existence of oxygen vacancy species of SnO2 (i.e.
SnO) at the surface and in bulk of photoanode. Since SnO is highly resistive,[64] it acts like
an insulator[65] preventing or slowing down the charge transfer process at
photoanode/electrolyte interface. EIS analysis is in good agreement with the photocurrent
spike observed in the chopped LSV curves. Nevertheless, the improved performance of SC-

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SnO2 photoanode in PEC cell as analysed via LSV is to a great extent contributed by the
reduced band gap of SnO2 (Fig. 2(b)) owing to the existence of oxygen vacancy which in turn

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boosted the light absorption ability. As a consequence, considerable amount of photoelectron
is generated in SC-SnO2 photoanode which compensated the sluggish charge transfer process.

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Furthermore, amperometric I-t curve in Fig. S4 shows that SC-SnO2 sample has better
stability compared to AACVD-SnO2 counterpart which indicate the suitability of spin
coating technique for the preparation of photoanode in solar water splitting technology.

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3.3. Performance of perovskite solar cells
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Fig. 6. (a) Schematic diagram of device structure. (b) Energy band alignment of the cell. (c)
Current density-voltage curves for PSC based on SC-SnO2 and AACVD-SnO2 with PCBM
interlayer. RS = reverse scan, FS = forward scan. (d) Steady state PL spectra of CH3NH3PbI3
films on blank substrate, SC-SnO2 and AACVD-SnO2 layers.

The fabricated SnO2 thin films were further employed as ETL in PSC device. The

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perovskite and hole transporting layer were prepared in ambient air with relative humidity of
approximately 40%. Fig. S5 shows the J-V curves of the best devices and Table S2 tabulates

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the J-V characteristic for the respective devices. PSC that used AACVD-SnO2 layer as ETL
achieved a maximum PCE of 6.4% which is derived from JSC, VOC and FF values of 11.7 mA
cm-2, 0.89 V and 61.37%. Meanwhile, SC-SnO2 based PSC showed JSC, VOC and FF values of

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8.9 mA cm-2, 0.77 V and 63.03% which led to a PCE of merely 4.3%. In order to improve the
performance of PSC, PC70BM passivation layer was introduced between SnO2 ETL and

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perovskite light harvesting layer. The device structure and their corresponding band gap
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energy level are represented in Fig. 6(a) and (b), respectively. The existence of PC70BM
interlayer enhanced all J-V characteristics of both devices except for FF value of SC-SnO2
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sample. As a result, device efficiency measured in reverse direction was increased to 6.7%
and 10.2% for SC-SnO2 and AACVD-SnO2, respectively. This could be attributed to the
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better electron extraction properties of PC70BM compared to SnO2 which avoids charge
accumulation and recombination at the perovskite/SnO2 interface.[66] Introduction of
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PC70BM also reduced the hysteresis behaviour in the device due to the same reason. Average
PCE was also calculated by taking into account the PCE obtained from reverse scan of several
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devices fabricated via particular condition. It was observed that all photovoltaic parameters
especially VOC value of AACVD-SnO2 is greater than that of SC-SnO2. Previously, we have
proven that high amount of free charge carrier in ETL is detrimental for device performance
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as it could increase the charge recombination rate.[26] In this work, it can be seen from PEC
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application (Fig. 4) that SC-SnO2 has higher PEC performance which in turn reflect the
greater number of photoexcited electron-hole pairs. The generated charge carriers in SC-SnO2
would cause non-radiative recombination between electron in ETL and holes in perovskite
layer which eventually decrease the device efficiency.

 !"#$%
  = 
(Eq. 4)

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Hysteresis index is also calculated using Eq. 4.[67] It can be seen that devices
employing SC-SnO2 either with or without PC70BM interlayer displayed more severe
hysteresis than that device counterparts employing AACVD-SnO2 (Fig. 6(c) and Table 1).
The reasons behind the difference in the performance of devices based on AACVD-SnO2 and
SC-SnO2 are associated with oxygen vacancy presented in SnO2 layer.[19–21,68,69]

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Table 1 Current density-voltage curves parameters for PSC based on SC-SnO2 and AACVD-
SnO2 with PCBM interlayer.

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JSC VOC FF PCE Hysteresis Average
Sample 2
(mA/cm ) (V) (%) (%) index PCE (%)
SC-SnO2/PCBM (RS) 12.5 0.85 62.69 6.7

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0.224 5.8
SC-SnO2/PCBM (FS) 10.8 0.86 56.46 5.2
AACVD-SnO2/PCBM (RS) 14.7 1.03 67.51 10.2
0.147 9.5
AACVD-SnO2/PCBM (FS) 14.4 1.02 58.99 8.7
*RS = reverse scan, FS = forward scan.

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To further approve this phenomenon, photoluminescence (PL) spectra of perovskite
layers deposited on the blank glass, glass/SC-SnO2 and glass/AACVD-SnO2 substrates were
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investigated (Fig. 6(d)). As seen from PL peak centred at 768 nm, the intensity of the peak is
quenched upon introduction of SnO2 layer as ETL. This behaviour indicates that the
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photoexcited electrons are collected efficiently at the interface. Besides, the quenching effect
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is much stronger for AACVD-SnO2 in comparison to SC-SnO2 sample which reflect the
enhanced electron extraction efficiency by AACVD-SnO2.[67,70] The slower charge
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extraction rate of SC-SnO2 sample could be attributed to the presence of oxygen vacancy
species of SnO2 (i.e. SnO phase) at the interface. The high resistivity of SnO[64] hampers the
charge transfer process at SnO2/perovskite interface which lead to charge accumulation and
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recombination at the interface. Thus, the existence of oxygen vacancy is the main reason for
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reduced performance and increasing hysteresis in SC-SnO2-based device. The PL analysis is

in good agreement with the result observed from EIS study earlier.

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Fig. 7. Top-view of FESEM images of perovskite layer prepared in ambient air (RH 40%) on
(a) AACVD-SnO2 and (b) SC-SnO2 electron transport layer. (c) and (d) represent their
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respective grain size distribution.

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Surface morphology of perovskite layer on different SnO2 layer was also investigated
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using FESEM image (Fig. 7). Even though both perovskite layers were fabricated in ambient
air with relative humidity 40% under similar processing condition and using identical type of
perovskite (i.e. MAPbI3), the layer showed different morphology when grown on different
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underlying SnO2. Perovskite layer prepared on SC-SnO2 had much rougher morphology and
smaller average grain size of ~103 nm which is a common phenomenon for perovskite
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fabricated in ambient air using one-step deposition technique and chlorobenzene drop
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treatment.[71] Surprisingly, AACVD-SnO2 film led to the formation of smoother and larger
perovskite grains (average size ~138 nm). Several research groups claimed that the growth of
perovskite layer is affected by the structure of the pre-formed underlying layer.[60,72] Such
difference in morphological properties of perovskite layer could be attributed to the difference
in wettability of the underneath ETL.[24] As described earlier, AACVD-SnO2 demonstrated
higher water contact angle and lower wettability compared to SC-SnO2. Upama et. al.[24]
described that the surface tension dragging force of less wettable ETL (in our case AACVD-
SnO2) is lower which improves the grain boundary mobility. As a consequence, less
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perovskite nuclei are formed on AACVD-SnO2 layer. This nuclei will grow further to form
perovskite grains and eventually touch the surrounding crystals at grain boundaries. This
means that larger and well-defined perovskite grains are formed as the number of nuclei
decreases. Bigger grain size also reflects lower amount of grain boundaries which could
prevent non-radiative charge recombination at grain boundaries and consequently enhance the
performance of AACVD-SnO2-based solar cells.[73–75]

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Fig. 8. (a) Normalized PCE of PSC based on AACVD-SnO2 and SC-SnO2 as ETL that have
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been exposed to ambient air with RH level 75%. Perovskite layer on (b,c) AACVD-SnO2 and
(d,e) SC-SnO2 before and after 1 day exposure to air.
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One of the major concern in fabricating PSC is to ensure the long-term stability of the
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device as inorganic-organic metal halide perovskite is easily degraded when exposed to

humid air.[76] Fig. 8 (a) shows the normalized PCE of the fabricated devices after exposure to
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ambient air with relative humidity (RH) of 75%. Fig. 8 (b)-(d) display the perovskite layer on
different SnO2 films right after deposition and after 1 day of exposure. It was observed that
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the dark brown colour of perovskite films on both SnO2 coated substrates gradually turns to
yellow when expose to air but sample based on SC-SnO2 showed much faster colour changes
than that of AACVD-SnO2. The colour change indicate the formation of PbI2 due to the
degradation of organic component by humidity in perovskite layer. Since the perovskite film
on both samples were fabricated and exposed in similar condition, the difference in
degradation rate is governed by the difference of SnO2-based ETL. The faster degradation rate
of the device employing SC-SnO2 is related to the higher hydrophilic properties of the SC-

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SnO2 layer as discussed earlier. As a consequence, this layer tends to absorb more humid from
air and accelerate perovskite degradation process.
It is noted that the efficiency of PSC obtained in this study is relatively low compared
to most reports regarding PSC. This is due to the fact that our devices were assembled in
ambient air with RH level of 40% and were measured in ambient environment without
encapsulation. Such environment is actually harsh for PSC device as perovskite material is

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easily degraded in the presence of humidity and oxygen. Yet, the highest PCE acquired in this
study which exceeds 10% threshold can be considered as impressive and the trend of device

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performance attained from using different ETL provided a valuable information in
understanding the significance of fabrication process for future commercial viability of the

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device.

Conclusion

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In this study, SnO2 thin films were fabricated at low temperature via two distinctive
deposition techniques namely solution-based and vapour-based techniques. Solution-based
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route which is represented by spin coating method yielded SnO2 layer that consists of a great
amount of oxygen vacancy while this defect was eliminated through the employment of
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AACVD technique which represents vapour-based route. The oxygen vacancy in spin coated
SnO2 led to lower water contact angle and reduction of band gap energy. When applied as
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photoanode for PEC water splitting process, oxygen vacancy in SnO2 is beneficial as it
reduced band gap energy and increase the light absorption of SnO2. As a consequence, more
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electrons are photogenerated which foster the PEC performance. On the other hand, PSC
devices based on spin coated SnO2 had lower efficiency, more severe hysteresis and poorer
ambient air stability compared to AACVD-based SnO2 counterpart. The reasons lay in the
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fact that oxygen vacancy hinders charge transfer from perovskite light harvesting layer and
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tend to absorb more humid in air which accelerate the degradation of perovskite material.
Thus, we recommend that future work should focus on controlling the formation of oxygen
vacancy in oxide layer through manipulation of processing protocols. After all, this work
proved that appropriate selection of thin film fabrication technology is very important to
achieve an optimized condition for large-scale manufacturing of a particular solar-based
device.

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Conflicts of Interest
There are no conflicts of interest to declare.

Acknowledgements
This work was financially supported by Dana Impak Perdana (DIP-2016-003) of Universiti

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Kebangsaan Malaysia (UKM).

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Highlights:
• Spin coating technique increases oxygen vacancy formation
• AACVD technique reduces oxygen vacancy formation
• Oxygen vacancy improves photoelectrochemical performance
• Oxygen vacancy deteriorates efficiency, stability and hysteresis of perovskite solar
cell.

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