Materials Science in Semiconductor Processing 118 (2020) 105212

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Materials Science in Semiconductor Processing

journal homepage: http://www.elsevier.com/locate/mssp

Improvement ITO/WO3 photo anode electrode fabrication using

electrodeposition technique for highly efficient photoelectrocatalytic
insecticide degradation
Farut Supanantin a, Chatchai Ponchio a, b, *
a
Department of Chemistry, Faculty of Science and Technology, Rajamangala University of Technology Thanyaburi, Pathum Thani, 12110, Thailand
b
Advanced Materials Design and Development (AMDD) Research Unit, Faculty of Science and Technology, Rajamangala University of Technology Thanyaburi, Klong 6,
Thanyaburi, Pathum Thani, 12110, Thailand

A R T I C L E I N F O A B S T R A C T

Keywords: The improvement of a semiconductor thin film preparation technique is considered to be the primary strategy for
WO3 photoelectrocatalytic technique development. This research study’s focus was to develop an electrodeposition
Thin film fabrication technique for tungsten oxide (WO3) thin film fabrication to improve photoelectrocatalytic activities for water
Electrodeposition method
oxidation and insecticide degradation application. WO3 thin film deposition on conductive glass was developed
Photoelectrocatalytic activity
Insecticide degradation
using the electrochemical amperometric and cyclic voltammetric methods to optimize the essential parameters
that affect the characteristics and photoelectrocatalytic properties of the fabricated WO3 electrode. Character­
istics such as the visible light absorption, morphology, crystalline structure, and photoelectrocatalytic oxidation
activities of the fabricated WO3 electrode were studied and compared with both electrodeposition methods. The
fabricated WO3 electrode was found to improve photoelectrocatalytic water oxidation more with the ampero­
metric method than with the cyclic voltammetric method and the traditional spin coating method, up to 4 times
and 60 times, respectively. Photoelectrocatalytic enhancement is clarified by the effect of visible light absorption,
roughness morphology, crystallinity, and charge transfer rate improvement. We can approve the efficacy of the
developed WO3 electrode for insecticide removal under the photoelectrocatalytic mechanism. This is suitable for
further scaling up the study for a wastewater treatment system application.

1. Introduction
The photoelectrocatalytic technique has received significant atten­
tion for its application to energy and to the environment due to the fact
that it is a technique that provides a highly efficient, economical,
convenient, and low-energy consumption process [1–6]. This technique
can be developed by improving the efficiency of the working electrode
and designing the photoelectrocatalytic cells [7–12]. In particular, the
development of the working electrode involves selecting a suitable
semiconductor and developing a semiconductor thin film preparation
technique on the supporting surface [13–16]. Among semiconductor
materials, a tungsten trioxide (WO3) semiconductor is the most attrac­
tive for use as a anode electrode for an oxidation reaction application
owing to its proper bandgap energy, the high positive potential of its
valent band position, its nontoxicity, and its high stability [17–24].
Furthermore, the WO3 thin film fabrication process on the substrate is
critical in photoelectrocatalytic activity control. The traditional
methods used for WO3 thin film fabrication are the spray pyrolysis
[25–27], spin coating [28–30], and hydrothermal methods [31–33].
However, these methods have many disadvantages; for instance, they
are complicated methods, use high-temperature and high-pressure
conditions, and they are difficult to use for scaling up applications.
The electrodeposition technique is an alternative method that has been
developed to address the previous limitations, as it is a highly efficient
technique for thin film preparation, takes less time, consumes little en­
ergy, and can be used for scaling up applications [23,34–39]. There are
two main modes of electrodeposition thin film preparation techniques:
applied potential and applied current modes [23,40–43]. This research
study focused on the applied potential mode because this mode can
develop a variety of variables that can increase the highest efficiency of

* Corresponding author. Department of Chemistry, Faculty of Science and Technology, Rajamangala University of Technology Thanyaburi, Pathum Thani, 12110,
Thailand.
E-mail address: chatchai@rmutt.ac.th (C. Ponchio).

https://doi.org/10.1016/j.mssp.2020.105212
Received 27 February 2020; Received in revised form 16 April 2020; Accepted 17 May 2020
Available online 29 June 2020
1369-8001/© 2020 Elsevier Ltd. All rights reserved.
F. Supanantin and C. Ponchio
Fig. 1. Experimental set up for ITO/WO3 electrode fabrication using an elec­
trodeposition technique.
thin film preparation over other modes [23,35,44–46]. The applied
potential mode can also be divided into the applied constant potential
(Amperometric method), as well as the applied cycle potential (Cyclic
voltammetric method). In previous research, no report compared the
two techniques for WO3 thin film preparation. Therefore, this research
focused on developing and comparing the efficiency of WO3 thin film
prepared by the amperometric and cyclic voltammetric methods.
The objective of this research study was to improve and compare
electrodeposition techniques for WO3 thin film preparation, applying
photoelectrocatalytic water oxidation reactions and insecticide degra­
dation. The effect of the precursor concentration and the parameters
that control the properties of WO3 film were optimized for the highest
Fig. 2. Cyclic voltammograms of (a) ITO electrode in a supporting solution of
0.015 M H2O2 and 0.5 M HNO3, and (b) ITO electrode in a precursor solution of
0.0125 M H4Na2O6W, 0.015 M H2O2, and 0.5 M HNO3.
2
Materials Science in Semiconductor Processing 118 (2020) 105212
photoelectrocatalytic activities. We can develop and optimize WO3 thin
film preparation using electrodeposition techniques to achieve the
highest efficiency for insecticide removal, which can further be applied
to treat harmful organic contamination in wastewater as well.
2. Experimental
2.1. Materials
Sodium tungstate dehydrate (H4Na2O6W (Emsure, Merck)),
hydrogen peroxide (H2O2 (30%, Chem-supply)) and nitric acid (HNO3
(70.0%, Sigma-Aldrich)) were used for WO3 precursor solution prepa­
ration. Conducting glass indium doped tin oxide (ITO) (15 Ω/sq, Xin Yan
Technology Co., Ltd) was applied as an electrode substrate and was
cleaned using sodium hydroxide (NaOH (Univar)) and ethanol
(CH2CH3OH (ACL Lab scan)) solutions. The aqueous solution of sodium
sulfate (Na2SO4 (Univar)) and carbosulfan (2, 3-dihydro-2, 2-dime­
thylbenzofuran-7-yl (Pause)) was used to study the photo­
electrocatalytic performance of water oxidation and insecticide
degradation.
2.2. WO3 thin films preparation
The conducting glass ITO substrate was cleaned by sonicating in the
priority solution of detergent for 15 min, 3 M NaOH for 30 min, ethanol
for 15 min, and finally with distilled water for 15 min. The electro­
chemical method was developed for WO3 thin film deposited on the ITO
substrate with a different mode of amperometric and cyclic voltam­
metric methods in a mixing the precursor solution of 0.0125 M
H4Na2O6W, 0.015 M H2O2, and varying HNO3 concentrations. Fig. 1
shows a three electrode system setting by using ITO as a working elec­
trode, Ag/AgCl electrode and Pt as a reference electrode and a counter
electrode, respectively. The amperometric method was optimized by
keep a constant potential at 0.5 V using VersaSTAT 3 (Princeton
Applied Research, Inc.) and varies the HNO3 concentration and depo­
sition time. The cyclic voltammetric method was used to compare with
the amperometric method by control the potential in range of 0.0 to
0.6 V and optimization by varies the HNO3 concentration and number
of cycle scans. The ITO/WO3 thin film prepared by spin coating method
was introduced to compare the photoelectrocatalytic activity of the ITO/
WO3 electrode by using the precursor solution of 0.1 M H2WO3 in 30%
NH4OH and set the spin speed of 1000 rpm for 1 min [15,22]. The
fabricated WO3 thin films were calcined at 500 � C for 30 min, after
which optimization with photoelectrocatalytic water oxidation activity
was considered.
2.3. Characterization and photoelectrocatalytic activity study
The optical properties of the fabricated ITO/WO3 thin film was
studied using the UV/Vis spectrophotometer (Shimadzu, UV-1601). The
crystalline structure was analyzed using X-ray diffraction (XRD, JEOL,
JDX-3530) in the 2θ range from 20� to 70� . Meanwhile, the surface
morphology of thin films was investigated using scanning electron mi­
croscopy (SEM, JEOL, JSM-5410LV). The elemental composition and
chemical state were studied via energy dispersive X-ray spectroscopy
(EDX, Oxford, LINK ISIS300) and X-ray photoelectron spectroscopy
(XPS, JEOL, JPS-9010TR). The photoelectrocatalytic activity for water
oxidation was carried out by using a voltammetry analyzer (Princeton
Applied Research, Inc., VersaSTAT 3) in the electrolyte solution of 0.1 M
Na2SO4 at an applied potential of 1.0 V vs. Ag/AgCl under visible light
illuminated. Moreover, an electrochemical impedance spectroscopy
(EIS) was used to study the charge transfer resistant at frequencies
ranging from 100 kHz to 0.1 Hz under visible light irradiation. The
photoelectrocatalytic insecticide degradation efficiency depending on
an applied potential and on the catalytic mechanism was studied in a
solution of 10 mg/L carbosulfan and 0.1 M Na2SO4 under an applied
F. Supanantin and C. Ponchio Materials Science in Semiconductor Processing 118 (2020) 105212

Fig. 3. Photocurrent response from water oxidation of ITO/WO3 electrode

prepared with (A) cyclic voltammetric method with various HNO3 concentra­
tions of (a) 0.16, (b) 0.22, (c) 0.27, and (d) 0.32 mol/L, as well as (B) amper­
ometric method with various HNO3 concentrations of (a) 0.16, (b) 0.22, (c)
0.27, (d) 0.32, (e) 0.39, (f) 0.44, (g) 0.50, and (h) 0.55 mol/L.
Fig. 4. Photocurrent response from water oxidation of ITO/WO3 electrode
potential of 1.0 V and visible light irradiation. The concentration of prepared with (A) cyclic voltammetric method with various numbers of scans of
insecticide was observed using a UV-VIS spectrophotometer (SHI­ (a) 10, (b) 20, (c) 30, and (d) 40 cycles, as well as (B) amperometric method
MADZU, UV-2401PC). The insecticide organic degradation efficiency with various deposition times of (a) 15, (b) 30, and (c) 45 min.
was calculated by the following equation.
� � the forward reaction to the WO3 thin film preparation efficiency.
A0 At Therefore, this research study explored the appropriate concentration of
Insecticide degradation ð%Þ ¼ � 100 (1)
A0 nitric acid to the optimum WO3 thin film preparation, which has the
highest photoelectrocatalytic activities. Fig. 3 shows the significant ef­
where A0 is the initial absorbance of insecticide, and At is the absorbance
fect of the nitric acid concentration on the fabricated WO3 electrode in
of insecticide at given time t.
the photoelectrocatalytic water oxidation reaction using both the cyclic
voltammetric and the amperometric method. Fig. 3B shows that the
3. Results and discussion optimum conditions of the amperometric technique at the optimum
nitric acid concentration of 0.5 M allowed for the preparation of WO3
3.1. ITO/WO3 thin films fabrication and characterization thin films with higher photoelectrolytic activities over the optimum
condition of the cyclic voltammetric method (Fig. 3A). The result
To study the suitable applied potential for the electrodeposition of
WO3 on the ITO substrate, we have studied the cyclic voltammograms
characteristics of ITO electrodes during immobilized WO3 in the pre­
cursor solution, compared with only supporting electrolytes without a
tungsten precursor solution. Fig. 2 shows a distinct difference in the
reduction peak between W2O211 reduction to form a WO3 film (Fig. 2 b)
and the water reduction to hydrogen (Fig. 2 a) at the ITO electrode. We
found that the reduction reaction of WO3 formation starts at a potential
of 0.2 V and that more sharpness is observed at 0.5 V, which confirms
the appropriately applied potential of 0.5 V to deposit the WO3 film for
the amperometry method. The chemical reaction for tungsten oxide
(WO3) thin film preparation can be explained in equation (2), in which a
tungstate ion (WO24 ) is oxidized by excess hydrogen peroxide (H2O2)
and converse to a peroxytungstate (W2O211 ) ion in a bulk solution. The
W2O211 ion in the acidic solution was reduced to a WO3 thin film and was
deposited onto the ITO substrate under a negative apply potential as
shown in equation (3).

2WO4 2-
þ 4H2O2(aq) → W2O211 (aq) þ 2OH þ 3H2O(l) (2)
Fig. 5. Absorption spectra, inset of electrode color, and the correlation between
(aq) (aq)

W2O211 (aq) þ 6Hþ(aq) þ 4e → 2WO3(s) þ O2(g) þ 3H2O(l) (3) the absorbance coefficient and bandgap energy of (a) ITO and ITO/WO3 elec­
trodes prepared by the different methods of (b) spin coating method, (c) cyclic
In equation (3), it can be explained that the acid (Hþ) content affects voltammetric method, and (d) amperometric method.

3
F. Supanantin and C. Ponchio
Fig. 6. X-ray diffraction patterns of (a) bare ITO and the ITO/WO3 prepared
with the different methods of (b) spin coating method, (c) cyclic voltammetric
method, and (d) amperometric method.
confirms the photoelectrocatalytic properties of a WO3 thin film fabri­
cated using the electrodeposition method depending on the concentra­
tion of the nitric acid in the solution, according to equation (3). The
cyclic voltammetric method can improve the efficiency of WO3 film
fabrication by controlling the number of scan cycles, which is shown in
Fig. 4A. The photocurrent of the fabricated WO3 electrode is related to
the number of scans and is optimized for 30 scan cycles. Meanwhile, the
efficiency of WO3 electrodes fabricated using the amperometric method
can be improved by varying the deposition time. Fig. 4B shows the
photocurrent of the WO3 electrode increasing with the deposition time,
which goes from 10 min to 30 min. The photocurrent was decreased
when the deposition time increased to 45 min as a result of the WO3 film
deposition as well as the effect with the electron transfer rate at the
electrode surface. The result shows that the fabricated WO3 electrode
presents higher photoelectrocatalytic oxidation activities with the
amperometric method compared with the cyclic voltammetric method.
Fig. 5 shows the absorbance properties of the WO3 thin film fabricated
with the amperometric method in the visible light region. The WO3 thin
film thickness is higher with this method than with the cyclic voltam­
metric method. The inset of Fig. 5 shows the correlation between the
absorbance coefficient and the bandgap energy of the ITO/WO3 elec­
trodes prepared using different methods. The bandgap energy values of
the WO3 prepared with the amperometric and cyclic voltammetric
methods were 2.74 and 2.88, respectively [21,47]. Meanwhile, the WO3
thin film prepared with the spin coating method presents a very low in
visible light as a result of the effect of the lowest efficiency of WO3 film
deposition on the ITO substrate. Moreover, in the inset of Fig. 5, one can
observe a very light yellow color of the WO3 film fabricated using the
spin coating method compared with the amperometric and cyclic vol­
tammetric methods, where the films are clearly a yellow color. These
results indicated that the WO3 thin film prepared with the amperometric
method has a narrower band gap energy and is more effective in
deposition efficiency on the ITO substrate compared with other
methods, thus causing an improvement in the visible light absorption
properties, and resulting in the highest photoelectrocatalytic properties.
Fig. 6 shows the crystalline structure of bare ITO containing tetragonal
tin oxide and presenting a monoclinic WO3 structure with different
characteristics depending on the deposition method. The XRD patterns
of the WO3 film fabricated with the amperometric method present the
highest intensity of XRD peaks at 2θ of 23.6� , 24.4� , 47.3� , and 50.6� ,
which indicate the diffractions of the monoclinic WO3 crystalline
structure on the ITO substrate [20,48,49]. However, the WO3 thin film
fabricated with the spin coating method shows only one small-intensity
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Materials Science in Semiconductor Processing 118 (2020) 105212
Fig. 7. XPS spectra of W4f, O1s, and C1s elements on ITO/WO3 electrode.
Table 1
EDX data of elements and compounds containing the ITO/WO3 electrode.
Elements % (w/w) Compounds % (w/w)
Si 18.69 SiO2 39.98
In 17.26 In2O3 20.87
W 21.15 WO3 26.68
O 34.43
XRD peak at 2θ of 24.4� due to the small amount and low crystallinity of
WO3. This result is consistent with previous research showing that the
WO3 thin film prepared with the spin coating method provides a
low-intensity XRD signal [16,22]. The XRD result can be used to confirm
the crystallinity improvement of the WO3 thin film prepared with the
amperometric method, which enhances the photoelectrocatalytic ac­
tivity. Fig. 7 shows the XPS spectra of all elements on WO3 film that
corrected the binding energy with C1s (284.6 eV). The binding energy at
36.8 and 34.6 eV of W4f5/2 and W4f7/2 have confirmed the oxidation
state of W6þ on WO3 film [50,51]. The XPS peak at 529.6 eV of O1s is
related to the oxidation state of oxygen in a lattice, which confirms the
formation of the WO3 compound on the ITO/WO3 electrode [52]. EDX
was used to confirm the elemental composition of W and O on the
ITO/WO3 electrode, which confirms the existing composition of W, O
elements, and the WO3 compound containing the ITO/WO3 electrode
[52] (Table 1). Table 1 also presents the percentage ratio by weight of Si,
In elements, SiO2, and In2O3 compounds that originated from a ITO
substrate. The XPS and EDX results provide critical information that can
be used to confirm the chemical composition and chemical state of WO3
existing on the ITO substrate. Fig. 8 shows the morphology of the WO3
thin film on the ITO substrate prepared with the amperometric method.
There are significant differences in particle size and distribution when
compared with fabrication using the spin coating method. The WO3 film
prepared with the spin coating method shows a flat surface due to the
fusing together of the WO3. Meanwhile, the WO3 film prepared with the
amperometric method presents high porosity and high surface rough­
ness, which can confirm the enhancement of the surface area via the
developed method. This result supports the idea that the improved
photoelectrocatalytic properties of the WO3 electrode stemming from
the surface roughness improvement caused a high surface area that was
sufficient for the reactant contact and the transfer electron at the elec­
trode surface.
3.2. Photoelectrocatalytic activities
Fig. 9A shows the photocurrent from water oxidation at the optimum
condition of the ITO/WO3 prepared with the amperometric method as
being significantly higher than that of the ITO/WO3 electrode prepared
with the cyclic voltammetric method and the spin coating method, up to
F. Supanantin and C. Ponchio Materials Science in Semiconductor Processing 118 (2020) 105212

Fig. 8. SEM images of (a) bare ITO substrate and ITO/WO3 electrode prepared with the different methods of (b) amperometric method and (c) spin coating method.

Fig. 10. Cyclic voltammograms of ITO/WO3 in 10 mg/L carbosulfan and a 0.1

M Na2SO4 solution under (a) visible light irradiation and (b) a dark condition.

Fig. 9. (A) Photocurrent and (B) Nyquist plot of WO3 electrode for water
oxidation under visible light irradiation prepared with the different methods of
(a) spin coating method, (b) cyclic voltammetric method, and (c) ampero­
metric method.

4 times and 60 times, respectively. The result can be used to confirm the
photoelectrocatalytic improvement of the advanced amperometric
method for WO3 film fabrication over other electrochemical and tradi­
tional methods. The EIS measurement was used to confirm the charge
transfer resistant properties at the interfacial electrode/electrolyte of the
prepared ITO/WO3 photoanode electrode. Fig. 9B shows that the nar­
rowest semi-circle of the Nyquist plot of the WO3 electrode prepared
with the amperometric method represents the lowest charge transfer
resistant properties or the highest electron transfer rate at the electrode
surface. This result supports the highest photocurrent of the developed
ITO/WO3 electrode due to the improvement of the charge transfer rate
at the electrode surface during water oxidation at the electrode surface.
Fig. 11. % Carbofuran insecticide degradation using ITO/WO3 electrode pre­
pared by the developed amperometric method with the different applied po­
tentials of 0.5, 1.0, 1.5, and 2.0 V.
The photoelectrocatalytic property enhancement with the ampero­
metric method can be explained by the improvement of the visible light
absorption, crystalline structure, and high-porosity properties. This re­
sults in highly efficient electron-hole generation, high charge separa­
tion, and a high reaction surface area resulting in the highest

5
F. Supanantin and C. Ponchio
Fig. 12. % Carbofuran insecticide degradation using ITO/WO3 electrode pre­
pared with the developed amperometric method using the different PEC, EC,
and PC catalytic mechanisms.
photoelectrocatalytic properties. Therefore, the improved ITO/WO3
electrode fabricated with amperometric method was selected for further
study regarding a photoelectrocatalytic insecticide degradation
application.
3.3. The insecticide organic degradation efficiency
Fig. 10 shows the oxidation reaction of carbosulfan insecticides in an
aqueous solution under visible light irradiation compared with a dark
condition at the ITO/WO3 photoanode. We observed the oxidation peak
of carbosulfan starting from 0.3 V, and a constant from 0.6 to 1.5 V.
Therefore, we studied the optimized applied potential to the highest
carbosulfan degradation efficiency in the range of 0.5–2.0 V. Fig. 11
shows photoelectrocatalytic carbosulfan degradation using the devel­
oped WO3 electrode with the optimized applied potential condition of
1.0 V, which can remove insecticide up to 55% for 1h. The degradation
percentage was decreased when the applied potential went up to
1.5–2.0 V due to the competition effect between water oxidation to
oxygen and organic degradation in a high applied potential condition.
Moreover, the catalytic mechanism for insecticide degradation was
studied with the different catalytic mechanisms of photoelectrocatalytic
(PEC), electrocatalytic (EC), and photocatalytic (PC) mechanisms. It can
be observed that the PEC mechanism presents the highest removal ef­
ficiency over EC and PC with degradation percentages of 55%, 51%, and
42%, respectively (Fig. 12). The results confirm that the developed ITO/
WO3 electrode presents photoelectrocatalytic oxidation efficiency for
insecticide degradation in an aqueous solution.
4. Conclusions
We have succeeded in developing WO3 thin film fabrication on the
ITO substrate using the electrodeposition method, and we have pre­
sented high photoelectrocatalytic activities for water oxidation and
organic degradation. The amperometric method shows the best elec­
trodeposition method for WO3 thin film fabrication with the optimum
condition at a nitric acid concentration of 0.50 M, keeping the potential
of 0.5 V for 30 min. We can confirm and compare the characteristics
related to the photoelectrocatalytic properties of the fabricated WO3
electrode with the electrodeposition and traditional methods. The
amperometric method presents the improvement of the visible light
absorption, roughness morphology, crystalline structure, and charge
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Materials Science in Semiconductor Processing 118 (2020) 105212
transfer rate properties of the fabricated ITO/WO3 electrode over other
methods, thus resulting in the highest efficiency for water oxidation and
insecticide degradation via the PEC process. The WO3 thin film fabri­
cation improvement using the electrodeposition technique is essential
knowledge for semiconductor thin film fabrication development, and it
is suitable to apply to wastewater treatment on a large scale as well.
CRediT authorship contribution statement
Farut Supanantin: Data curation, Writing - original draft. Chatchai
Ponchio: Formal analysis, Writing - original draft, Data curation.
Acknowledgments
This work was supported by the project of the Research and Re­
searchers for Industries (RRI), Thailand Research Fund (TRF), and Siam
Aqua Tech Development System Co., Ltd. (MSD61I0073).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.mssp.2020.105212.
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