Materials Science in Semiconductor Processing 123 (2021) 105515

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WO3/TiO2 hierarchical nanostructures for electrochromic applications

T. Dhandayuthapani a, b, R. Sivakumar c, *, D. Zheng b, H. Xu b, R. Ilangovan d, **, C. Sanjeeviraja e,
J. Lin b, ***
a
Department of Nanoscience and Nanotechnology, Alagappa University, Karaikudi, 630003, India
b
Key Laboratory of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, PR
China
c
Department of Physics, Directorate of Distance Education, Alagappa University, Karaikudi, 630003, India
d
National Center for Nanosciences and Nanotechnology, University of Madras, Chennai, 600025, India
e
Department of Electronics and Communication Engineering, Alagappa Chettiar Government College of Engineering and Technology, Karaikudi 630003, India

A B S T R A C T

In the present work, we report the low temperature preparation of WO3/TiO2 films via a two step process by combining chemical bath deposition and nebulized spray
deposition techniques. We investigate the influence of WO3 layer on the structural, compositional, morphological and electrochemical properties of TiO2 films. The
deposition of WO3 nanoplates on the TiO2 layer effectively improves the current density of the TiO2 films. The electrochemical study of the annealed WO3/TiO2 films
showed a colouration efficiency of 128.3 cm2 C− 1, optical modulation (ΔT) of 78%, reversibility of 77.2% and with a fast response of 6 s for colouration and
bleaching, and importantly, exhibited an excellent durability for 1000 cycles. This enhancement is ascribed to the interconnected nanoplate bundles which
accommodate more charges, facilitate faster charge transport and in particular, the complementarity of the WO3–TiO2 layers, result in complement between each
other, thus leading to efficient electrochromic performance.

1. Introduction infrared range and multi-colouration behavior [12,13]. Numerous

techniques were used to deposit electrochromic metal oxide layer on the
Titanium dioxide (TiO2) is recognized as a promising candidate for surface of already prepared metal oxide films, including hydrothermal,
electrochromic smart window application on account of features such as spin coating, layer by layer assembly, electrodeposition and chemical
excellent electrochemical stability, optical modulation, reversibility and bath deposition (CBD) [8–13]. In the present work, CBD is chosen due to
scalable low cost preparation [1–3]. The innate drawbacks of TiO2 thin its ease in deposition process, large area deposition and scalable
films in electrochromic device, however, are their poor colouration ef­ preparation.
ficiency, high voltage requirement for colouration and the slow Tungsten oxide (WO3) has been widely investigated for electro­
switching kinetics [4,5]. In the previous studies, we have reported that chromic device applications. It was reported that the WO3 layer on the
the spray deposited TiO2 thin films exhibited percolating interconnected TiO2 film can improve the current density, reduce the operating po­
network like channel and provided a better contact between the sub­ tential, cyclic stability and exhibit long term memory effects [12,13].
strate and film, which resulted in efficient electrochromic performance Recently, Song et al. reported that the WO3/TiO2 nanotube arrays,
[6,7]. synthesized by combining CBD and spray pyrolysis techniques, showed
Nowadays, composites or hybrid films (TiO2/M, M = WO3, NiO, increased proton storage capacity, higher contrast ratio and promising
V2O5 and MoO3), have attracted much attention of the researchers and electrochromic performance [14]. Reyes-Gil et al. fabricated a
have been successfully prepared by depositing any of these electro­ WO3/TiO2 composite film by covering a WO3 layer on the TiO2 nano­
chromic metal oxide layer on the surface of TiO2 [8–11]. The individual tube via electrodeposition which exhibited a large ion storage capacity
layers in this type of hybrid films can synergize each other by over­ of 65 mC/cm2, electrochromic contrast of 70% and fast switching time
coming the disadvantages of individual oxide and therefore led to new for colouration and bleaching [12]. Yoo et al. said that the WO3 doped
properties, such as memory effect, optical modulation in the near TiO2 nanotubes exhibited efficient proton intercalation and enhanced

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: krsivakumar1979@[Link] (R. Sivakumar), rilangovan@[Link] (R. Ilangovan), Jianjian_Lin@[Link] (J. Lin).

[Link]
Received 13 June 2020; Received in revised form 12 October 2020; Accepted 14 October 2020
Available online 21 October 2020
1369-8001/© 2020 Elsevier Ltd. All rights reserved.
T. Dhandayuthapani et al. Materials Science in Semiconductor Processing 123 (2021) 105515

electrochromic properties compared to pristine TiO2 [15]. In addition, characterized by X-ray photoelectron spectroscopy (XPS) (Krato Axis
Momeni et al. reported that the WO3 nanoparticles anchored on titania Ultra DL with monochromatic Al Kα X-ray (1486.6 eV) at the vacuum
nanotube films exhibited enhanced photoelectrochemical activity than level of 10− 9 Torr. The electrochemical properties of the prepared films
the bare titania nanotubes under Xe illumination [16]. All these earlier were measured by an electrochemical workstation (CH Instruments Inc.,
reports have demonstrated the electrochromic performance of WO3 USA) using working electrode (TiO2 and WO3/TiO2 thin film on FTO
nanoparticles on the TiO2 nanotube surfaces or core-shell type substrate), counter electrode (Pt wire), reference electrode (Ag/AgCl)
WO3/TiO2 films prepared by hydrothermal method. To date, however, and 1 M LiClO4 dissolved in propylene carbonate as electrolyte solution.
there have been no reports on growing WO3 layer by CBD technique on The optical properties of films were recorded in the wavelength range of
the spray deposited TiO2 films. In this work, we propose a single step 300–1000 nm using a UV–visible spectrophotometer (Jasco V-640).
approach to deposit WO3 nanoplate bundles layer on the spray deposited
TiO2 films via CBD technique. The spray deposited TiO2 films act as a 3. Results and discussion
core layer, while the layer of WO3 nanoplate bundles acts as a con­
ducting channel to enhance the charge transport and also as a cover of 3.1. Microstructural characteristics
protection against the degradation during prolonged cycling. The
interface between WO3 and TiO2 provides a synergistic interaction by The X-ray diffraction (XRD) patterns of TiO2 and WO3/TiO2 films are
offering surplus active sites for Li+ intercalation and charge storage. The presented in Fig. 1 (a). The diffraction peaks at 25.4◦ and 38◦ are
results demonstrate that the WO3/TiO2 films showed a current density of indexed with (101) and (004) planes of anatase TiO2 (JCPDS Card No.:
3 mA/cm2, stable optical modulation (ΔT) of 78%, reversibility of 21–1272). The peaks of WO3/TiO2 films at 2θ = 24◦ , 29◦ , 32.2◦ and
77.2%, and durability for over 1000 cycles. In addition, we have 34.5◦ are corresponding to the respective planes of (203), (602), (405),
investigated the effect of WO3 nanoplate bundles on the structural, and (205) of orthorhombic phase β-WO3 (JCPDS data Card No.:
morphological, compositional and electrochemical properties of TiO2. 89–4480). In addition, the signature of substrate (FTO) was seen in the
XRD patterns, which may be due to the crystalline nature of the sub­
2. Experimental strate. Since none of the X-ray diffraction patterns shows any charac­
teristic peaks other than the signatures of WO3, TiO2, and FTO, it
2.1. Materials confirms that the interdiffusion between the layers was not occurred
even at the annealing temperature of 450 ◦ C. This inference is consistent
Titanium tetraisopropoxide (Ti(OC3H7)4, TTIP), glycerol (C3H8O3), with the report of Momeni et al. [16], where they have obtained the
isopropanol (C3H8O), sodium tungstate dihydrate (Na2WO4.2H2O), separate XRD peaks corresponding to anatase TiO2, monoclinic WO3,
oxalic acid (C2H2O4), hydrochloric acid (HCl), lithium perchlorate and metal substrate (Ti) for WO3 nanoparticles anchored on titania
(LiClO4) and propylene carbonate (C4H6O3, PC) are the reagents used in nanotube films. The Raman spectra of TiO2 and WO3/TiO2 films are
the present work. The TiO2, and WO3/TiO2 films were deposited on given in Fig. 1 (b). The prominent vibrational bands at A1g (515 cm− 1), 2
fluorine doped tin oxide (FTO; Rsh = 15Ω/sq) coated glass substrates. B1g (396 and 515 cm− 1) and 3 Eg (145, 199 and 636 cm− 1) are belong to
the crystalline anatase TiO2 [4]. In the case of WO3/TiO2, a shoulder
2.2. Preparation of TiO2 film peak at 145 cm− 1 is observed while the intensity of other peaks of TiO2 is
reduced. In the as-deposited WO3/TiO2 film, the vibrational band is
In detail, 1.5 mL of C3H8O3 was added to 16 mL of C3H8O and then 1 observed at 100 cm− 1, which corresponds to O–W–O bending mode and
mL of TTIP was added to the same solution. Afterwards, the prepared the far intense band observed at 803 cm− 1 is attributed to the W–O
precursor solution was ultrasonicated for 10 min. The obtained pre­ stretching modes [18]. In the case of annealed WO3/TiO2 film, the
cursor solution was deposited on FTO substrate at the temperature of intense band at 803 cm− 1 is disappeared and a W–O stretching mode at
200 ◦ C by nebulized spray pyrolysis technique. The detailed instru­ 1070 cm− 1 is observed, which is caused by the rearrangement of W–O
mentation and deposition procedures were reported elsewhere [7,17]. bond, leading to the variation in crystal structure owing to the annealing
After deposition, the TiO2 film was annealed at 450 ◦ C for 1 h in air to effect.
obtain crystalline TiO2. The thickness of TiO2 film is 600 nm, as The X-ray photoelectron spectroscopy (XPS) analysis was carried out
measured by surface profilometer (Mitytoyo, SJ-301). to identify the surface chemical compositions and oxidation states of the
elements present in the films. The XPS core level spectra of Ti, W and O
2.3. Preparation of WO3/TiO2 films of the as-deposited and annealed WO3/TiO2 films are given in Fig. 2. In
the WO3/TiO2 films, Ti 2p3/2 and Ti 2p1/2 peaks are localized at the
The WO3 precursor solution was prepared by dissolving 0.5 g of binding energy values of 458.9 and 464.6 eV, respectively (Fig. 2 (a1)
C2H2O4 and 1 g K2SO4 in 50 mL of deionized water. Further, 8 mL of HCl and (a2)). The W 4f7/2, W 4f5/2 doublet peaks are located at 35.8 and
was added to the same solution. Later, 0.3 M of Na2WO4.2H2O was 37.5 eV, respectively, which are ascribed to the W6+ oxidation state
added to the growth solution and kept under stirring for 30 min. Now, (Fig. 2 (b1) and (b2)). In addition to that, the peaks observed at lower
the resultant WO3 growth solution was kept in an oil bath and the binding energies of 34.4 and 36.1 eV are related to W5+ oxidation state,
temperature of growth solution was maintained at 95 ◦ C. The spray which is coexistent with the oxygen vacancies (Fig. 2 (b1) and (b2)) [19,
deposited crystalline TiO2 film was immersed in the WO3 growth solu­ 20]. It can be seen that the presence of W5+ state is significantly
tion for 2 h, resulting the formation of WO3 layer (~ 550 nm) on TiO2 decreased in the annealed WO3/TiO2 film (Fig. 2 (b2)) compared to the
film. For comparison, the as-deposited WO3/TiO2 film was subsequently as-deposited one due to the annealing treatment in the air. The O 1s
annealed at 450 ◦ C for 1 h. spectrum was Gaussian fitted. The peaks at 530 eV, and 532.2 eV are
correspond to the lattice oxygen in TiO2 and oxygen vacancies, which
2.4. Characterization are ascribed to the W5+/6+ states (Fig. 2 (c1) and (c2)). In addition, the
peak observed at 534.6 eV in Fig. 2 (c1) is ascribed to the adsorbed
X-ray diffraction (XRD) (X’pert Pro, PANalytical, with a Cu-Kα ra­ hydroxyl groups on the surface of WO3/TiO2 film, while it is compara­
diation of λ = 1.54 Å), Raman spectrometer (Horiba-Jobin, LabRAM HR, tively reduced in the annealed sample (Fig. 2 (c2)) [17,21].
with the laser excitation of 514 nm) and field emission scanning electron The field emission scanning electron microscopic (FESEM) images of
microscopy (FESEM) (Carl ZEISS-ULTRA 55 FESEM) were used to pure TiO2 and WO3/TiO2 films are shown in Fig. 3. Fig. 3 (a) reveals that
characterize the crystallinity and morphology of the samples. The the pure TiO2 film shows a homogeneous distribution of nanoparticles
chemical composition and valence states of the samples were with an average size of ~15 nm. After the deposition of WO3 film by

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Fig. 1. (a) XRD patterns and (b) Raman spectra of TiO2 and WO3/TiO2 films.

Fig. 2. (a1) Ti 2p, (b1) W 4f, and (c1) O 1s XPS core level spectra of as-deposited WO3/TiO2 film. (a2) Ti 2p, (b2) W 4f, and (c2) O 1s XPS core level spectra of
annealed WO3/TiO2 film.

CBD, the pure TiO2 film was covered with WO3 nanoplates all over the 3.2. Electrochemical and electrochromic performance
entire substrate (Fig. 3 (b)). The surface of WO3 is made up of nanoplates
with an edge of 50 nm as calculated from Fig. 3 (b). The WO3 nanoplates The electrochromic performance of the films was analyzed at
are elongated to bigger plates with a rough edge of 110 nm size and different scan rates and the related cyclic voltammograms (CV) are
modified to porous interconnected nanowalls after annealing at 450 ◦ C, shown in Fig. 4. The simultaneous intercalation/deintercalation of Li+
(Fig. 3 (c)), due to the rearrangement of W–O bonding as observed from ions into WO3/TiO2 films under an applied voltage results in a colored
the Raman spectra Fig. 1 (b). (blue) or bleached (white) states. The surplus active sites redox reaction

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Fig. 3. FESEM images: (a) TiO2, (b) as-deposited WO3/TiO2 and (c) annealed WO3/TiO2 films.

Fig. 4. Cyclic voltammograms of (a) TiO2, (b) as-deposited WO3/TiO2, and (c) annealed WO3/TiO2 films.

and faster ion intercalation between the WO3–TiO2 layers render the CV confirmed its significant electrochemical stability. The reduction of
curves of WO3/TiO2 films more distinct than the pure TiO2 film. The as- active sites in WO3 layer caused the slight shift in the cathodic spike and
deposited and annealed WO3/TiO2 films exhibit a maximum cathodic minor degradation in cathodic current density, which impeded the Li+
current density of 3.8 and 3.2 mA/cm2, respectively. These values are ion diffusion.
two times higher than the pure TiO2 film and much higher than the Electrochemical impedance spectroscopy (EIS) was carried out to
reported data [10,12,14]. The anodic current densities are lower than understand the charge transport behavior of TiO2 and WO3/TiO2 films.
that of the cathodic for WO3/TiO2 films (Fig. 4(b–c)). In the annealed The Nyquist plots (Fig. 5 (a)) reveal a small semicircle in the high and
WO3/TiO2 film, the onset potential was decreased from − 1.2 to 0.2 V medium frequency range, which signify the high ionic conductivity and
due to the annealing effect, which varied the crystal phase of WO3 fast charge transfer reaction of the TiO2 and WO3/TiO2 films [22,23].
nanoplates and facilitated a faster charge transport. The increase in the The slope lines in the low frequency range are assigned to the Warburg
current density is due to the interconnected nanoplate structure of WO3 Li+ ion diffusion process. The as-deposited and annealed WO3/TiO2
surface, which provided more active sites for redox reactions and films have an enhanced charge transfer and faster ion diffusion
additional channel for Li+ ion intercalation/deintercalation, resulting compared to the pure TiO2 film. Interestingly, the charge transfer
the great improvement in Li+ ion storage capacity. The slight shift in the resistance of the as-deposited WO3/TiO2 films was increased after 1000
redox peaks and the increase in area with increasing scan rate for both cycles, however, no major decrement was seen in the annealed
as-deposited and annealed WO3/TiO2 films can be due to the faster WO3/TiO2 film (Fig. S2 in the supplementary information). The
redox reaction rates. These results substantiate that the WO3 nanoplate annealing effect effectively improves the adhesion between the surface
bundles on TiO2 surface significantly improves the current density of the and the W–O core layers and offers a better contact, which helps to
TiO2 films. The CV curves of WO3/TiO2 films subjected to 1000 cycles overcome the degradation of the surface layers after prolonged cycling.
are shown as supplementary information (Fig. S1). The negligible The chronoamperometry (CA) measurements were performed to
reduction in current density of WO3/TiO2 films after 1000 cycles investigate the switching kinetics of the films and the results are shown

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Fig. 5. (a) Nyquist plots (b) chronoamperometry curves and (c) chronocoulometry curves of TiO2 and WO3/TiO2 films.

in Fig. 5 (b). The bleaching (tb) and colouration (tc) response time are the nanoplate porous layer provides the surplus active sites, which in turn
key parameters for an electrochromic device. The as-deposited and efficiently improved the optical modulation of hybrid WO3/TiO2 films.
annealed WO3/TiO2 films exhibit a tb of 5 and 6 s, tc of 5 and 6 s which is The photographs of WO3/TiO2 films in colouration state are shown in
consistent with many of the reported composite films [19,24,25]. This Fig. S3 (supplementary information).
decrement in tb of WO3/TiO2 films is owing to the accommodation of Colouration efficiency (CE) and optical density change (ΔOD) are
more charges to reach full optical modulation; it, therefore, takes a few significant factors for an electrochromic material. CE is defined as the
seconds longer than the pure TiO2 film. variation in optical density at a particular wavelength per unit charge of
We further performed the chronocoulometric (CC) measurements on intercalated into or deintercalated from the electrochromic film [27].
TiO2 and WO3/TiO2 films with a step potential of − 1.4 V to + 1.2 V and The optical density change (ΔOD = log (Tb/Tc)), colouration efficiency
the plots are shown in Fig. 5 (c). The as-deposited and annealed WO3/ (CE = (ΔOD/Qi)) and the change in transmittance (ΔT = Tb–Tc; Tb and Tc
TiO2 films exhibited an intercalated charge density (Qi) of 11.4 mC/cm2 are the transmittance in the bleached and colored states, respectively) of
and 6.6 mC/cm2, and a deintercalated charge density (Qdi) of 6.3 mC/ TiO2 and WO3/TiO2 films at 600 nm were calculated and the values are
cm2, 5.1 mC/cm2, respectively, (Fig. 5 (c)). The reversibility (Qdi/Qi) of listed in Table 1. The CE value of pure TiO2 film is 47.6 cm2 C− 1 and an
the as-deposited and annealed WO3/TiO2 films was estimated to be 55.2 optical density of 0.62. The as-deposited and annealed WO3/TiO2 films
and 77.2%, which is higher than the pure TiO2 film (47.1%), as sum­ exhibit an optical density (ΔOD) of 0.64 and 0.77, respectively. The
marized in Table (S1) in the supplementary information. The observed obtained CE values of as-deposited and annealed WO3/TiO2 films are
reversibility of WO3/TiO2 film in the present work is higher than the one 58.1 and 128.3 cm2 C− 1, respectively. It is worth to mention here that
(54.1%) reported for pure WO3 film prepared by radio frequency the obtained colouration efficiency of WO3/TiO2 films is higher than the
magnetron sputtering technique [26]. The increase in reversibility of one reported for pure WO3 and other electrochromic oxide thin films.
WO3/TiO2 film is due to the porous percolating channels of WO3 For instance, Meenakshi et al. reported the CE value of 40.75 cm2 C− 1 for
nanoplates greatly enhanced the Li+ ion insertion/de-insertion kinetics. radio frequency magnetron sputter deposited undoped WO3 thin film
Interestingly, the higher reversibility of annealed WO3/TiO2 films might [26]. In addition, the CE value of electron beam evaporated WO3 films
be induced by the enhanced crystallinity of the samples and the effective was varied between 6 and 22 cm2 C− 1 for Li+ ion [28]. Further,
adhesion between the surface and core layers after the annealing pro­
cedure. In addition, in order to identify the stability of the film, the
Table 1
chronoamperometry and chronocoulometry measurements of
Response time, transmittance modulation, ΔOD, and CE of pure TiO2, and WO3/
WO3/TiO2 films were checked for 10 steps. The negligible variation in
TiO2 films.
the anodic/cathodic current density and the charge inter­
calated/deintercalated process further substantiates the stability of Sample Response Transmittance (%) ΔOD = log CE = ΔOD/
time (s) (at 600 nm) (Tb/Tc) Qi (cm2 C− 1)
WO3/TiO2 films. (at 600
The transmittance modulation of TiO2 and WO3/TiO2 films in tb tc Tb Tc ΔT
nm)
colored and bleached states are shown in Fig. 6. The transmittance
TiO2 2.5 4 77.6 18.6 59 0.62 47.6
response was recorded in the range of 350–800 nm by applying a step WO3/TiO2 as- 5 5 90.6 20.6 70 0.64 58.1
potential between ±1.4 V for TiO2 and WO3/TiO2 films. The annealed deposited
and as-deposited WO3/TiO2 films show the respective optical modula­ WO3/TiO2 6 6 93.6 15.6 78 0.77 128.3
annealed
tion of 78 and 70% which is higher than the pure TiO2 film. The WO3

Fig. 6. Colored and bleached transmittance spectra of (a) TiO2, (b) as-deposited WO3/TiO2, and (c) annealed WO3/TiO2 films.

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Sivakumar et al. evaluated the colouration efficiency of MoO3 thin films L acknowledge the National Natural Science Foundation of China
at different wavelength ranges and their magnitudes were in the range (NSFC) (61604070, 21701096), the Natural Science Foundation of
from 15 to 66 cm2 C− 1 [29]. Usha et al. have reported the highest CE Shandong Province (No. ZR2016BQ03), and the State Key Laboratory of
values of 15.79 cm2 C− 1 (for Li+ ion) and 69.80 cm2 C− 1 (for H+ ion) for Fine Chemicals (KF 1601) for the support.
mixed Nb2O5:MoO3 thin film [30]. The hydrothermally grown anatase
TiO2 nanowires exhibited the CE value of 13 cm2 C− 1 [31]. These results Appendix A. Supplementary data
suggest that the WO3/TiO2 films prepared in the present work exhibit
high CE values, fast switching kinetics, high reversibility and excellent Supplementary data to this article can be found online at [Link]
optical modulation compared to pure TiO2, WO3 and other electro­ org/10.1016/[Link].2020.105515.
chromic oxide thin films. These improvements in electrochromic per­
formance originate from its porous structure offering more sites, which References
in turn control the diffusion path length and faster access for ion diffu­
sion. Therefore, the WO3/TiO2 nanoplate films can be desirable for high [1] S. Cao, S. Zhang, T. Zhang, J.Y. Lee, Chem. Mater. 30 (2018) 4838–4846.
[2] A.K. Haridas, B. Gangaja, P. Srikrishnarka, G.E. Unni, A.S. Nair, S.V. Nair,
performance electrochromic devices. D. Santhanagopalan, J. Power Sources 345 (2017) 50–58, 345.
[3] R.A. Patil, R.S. Devan, Y. Liou, Y.R. Ma, Sol. Energy Mater. Sol. Cells 147 (2016)
4. Conclusions 240–245.
[4] J.Z. Chen, W.Y. Ko, Y.C. Yen, P.H. Chen, K.J. Lin, ACS Nano 6 (2012) 6633–6639.
[5] S. Liu, X. Zhang, P. Sun, C. Wang, Y. Wei, Y. Liu, J. Mater. Chem. C 2 (2014)
We successfully fabricated WO3/TiO2 films on FTO substrates by a 7891–7896.
two step process combining nebulized spray deposition and chemical [6] T. Dhandayuthapani, R. Sivakumar, R. Ilangovan, C. Gopalakrishnan,
C. Sanjeeviraja, A. Sivanantharaja, J. Solid State Electrochem. 22 (2018)
bath deposition techniques. These hierarchical WO3/TiO2 nanoplate 1825–1838.
architectures having closely interconnected channels possess improved [7] T. Dhandayuthapani, R. Sivakumar, R. Ilangovan, C. Gopalakrishnan,
current density, ion storage capacity, excellent durability, and a satis­ C. Sanjeeviraja, A. Sivanantharaja, Electrochim. Acta 255 (2017) 358–368.
[8] D.D. Yao, M.R. Field, A.P.D. Mullane, K.K. Zadeh, J.J. Ou, Nanoscale 5 (2013)
factory optical modulation and fast switching kinetics. This enhanced
10353–10359.
charge transport and charge storage behavior of WO3/TiO2 film is due to [9] J.H. Yu, H. Yang, R.H. Jung, J.W. Lee, J.H. Boo, Thin Solid Films 664 (2018) 1–5.
its porous nanoflake structure which offer faster ion transport and [10] Y.Y. Song, Z.D. Gao, J.H. Wang, X.H. Xia, R. Lynch, Adv. Funct. Mater. 21 (2011)
accommodate large volume changes. This work proves that a viable low 1941–1946.
[11] S. Kim, M. Taya, C. Xu, J. Electrochem. Soc. 156 (2009) 140–145.
temperature approach of depositing WO3 nanoplate architectures on [12] K.R.R. Gil, Z.D. Stephens, V. Stavila, D.B. Robinson, ACS Appl. Mater. Interfaces 7
TiO2 surface can effectively improve its electrochromic performance. (2015) 2202–2213.
[13] H. Ling, L.P. Yeo, Z. Wang, X. Li, D. Mandler, S. Magdassi, A.L.Y. Tok, J. Mater.
Chem. C 6 (2018) 8488–8494.
CRediT authorship contribution statement [14] Y.Y. Song, Z.D. Gao, J.H. Wang, X.H. Xia, R. Lynch, Adv. Funct. Mater. 21 (2011)
1941–1946.
T. Dhandayuthapani: Conceptualization, Investigation, Writing - [15] H. Yoo, K. Oh, Y.C. Nah, J. Choi, K. Lee, ChemElectroChem 5 (2018) 3379–3382.
[16] M.M. Momeni, Y. Ghayeb, M. Davarzadeh, Surf. Eng. 31 (2015) 259–264.
original draft. R. Sivakumar: Conceptualization, Writing - review & [17] T. Dhandayuthapani, R. Sivakumar, R. Ilangovan, C. Gopalakrishnan,
editing, Supervision. D. Zheng: Data curation, Formal analysis. H. Xu: C. Sanjeeviraja, K. Jeyadheepan, Mater. Res. Express 6 (2019), 065053.
Data curation, Formal analysis. R. Ilangovan: Supervision, Resources. [18] S. Poongodi, P. Suresh Kumar, Y. Masuda, D. Mangalaraj, N. Ponpandian
C. Viswanathan, S. Ramakrishna, RSC Adv. 5 (2015) 96416–96427.
C. Sanjeeviraja: Visualization, Resources. J. Lin: Supervision, Funding [19] D. Zhou, D. Xie, F. Shi, D.H. Wang, X. Ge, X.H. Xia, X.L. Wang, C.D. Gu, J.P. Tu,
acquisition. J. Colloid Interface Sci. 460 (2015) 200–208.
[20] K. Tang, Y. Zhang, Y. Shi, J. Cui, X. Shu, Y. Wang, J. Liu, J. Wang, H.H. Tan, Y. Wu,
J. Mater. Chem. C 6 (2018) 12206–12216.
Declaration of competing interest
[21] S. Zhang, H. Yang, H. Huang, H. Gao, X. Wang, R. Cao, J. Li, X. Xu, X. Wang,
J. Mater. Chem. A 5 (2017) 15913–15922.
The authors declare that they have no known competing financial [22] G.F. Cai, J.P. Tu, D. Zhou, X.L. Wang, C.D. Gu, Sol. Energy Mater. Sol. Cells 124
interests or personal relationships that could have appeared to influence (2014) 103–110.
[23] L. Zhu, C.K.N. Peh, T. Zhu, Y.F. Lim, G.W. Ho, J. Mater. Chem. A 5 (2017)
the work reported in this paper. 8343–8351.
[24] K. Tang, Y. Zhang, Y. Shi, J. Cui, X. Shu, Y. Wang, J. Liu, J. Wang, H.H. Tan, Y. Wu,
Acknowledgements J. Mater. Chem. C 6 (2018) 12206–12216.
[25] J. Zhang, J.P. Tu, D. Zhou, H. Tang, L. Li, X. Wang, C.D. Gu, J. Mater. Chem. C 2
(2014) 10409–10417.
R.S gratefully acknowledges the Department of Education, Govern­ [26] M. Meenakshi, V. Gowthami, P. Perumal, R. Sivakumar, C. Sanjeeviraja,
ment of India for the financial support under RUSA – Phase 2.0 Scheme Electrochem. Acta 174 (2015) 302–314.
[27] S.H. Yang, G.Y. Tseng, C.F. Kao, J. Electrochem. Soc. 166 (2019) 70–76.
(Ref. No.: F. 24–51/2014-U, Policy (TN Multi-Gen), dt. October 09, [28] R. Sivakumar, K. Shanthakumari, A. Thayumanavan, M. Jayachandran,
2018). In addition, R.S sincerely acknowledges the Department of Sci­ C. Sanjeeviraja, Surg. Eng. 23 (2007) 373–379.
ence and Technology, New Delhi, India for the financial support in [29] R. Sivakumar, K. Shanthakumari, A. Thayumanavan, M. Jayachandran,
C. Sanjeeviraja, Surg. Eng. 25 (2009) 548–554.
general and infrastructure facilities sponsored under PURSE 2nd Phase [30] N. Usha, R. Sivakumar, C. Sanjeeviraja, Mater. Sci. Semicond. Process. 30 (2015)
(Ref. No.: SR/PURSE Phase 2/38 (G) dt. February 21, 2017) and FIST 31–40.
(SR/FST/PSI-202/2015) programmes. Further, R.S acknowledges the [31] S. Liu, X. Zhang, P. Sun, C. Wang, Y. Wei, Y. Liu, J. Mater. Chem. C 2 (2014)
7891–7896.
University Grants Commission, New Delhi, India for the financial sup­
port under SAP (F.530/18/DRS-III/2015) scheme. T. D, D. Z, H. X, and J.