Transition Metal Chemistry

https://doi.org/10.1007/s11243-023-00533-y

Microwave‑synthesized γ‑WO3 nanorods exhibiting high current

density and diffusion characteristics
Shreya1 · Peeyush Phogat1 · Ranjana Jha1 · Sukhvir Singh1

Received: 25 January 2023 / Accepted: 3 May 2023

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2023

Abstract
The synthesis of monoclinic (γ) tungsten oxide (­ WO3) nanorods via facile Microwave-assisted hydrothermal route is reported
in the present work. The structural characterization of the as-synthesized material by using X-ray diffraction and Fourier-
transform infrared spectroscopy confirms the formation of crystalline ­WO3 phase. The morphology and microstructural
study along with elemental composition of the material as obtained by scanning electron microscopy and transmission
electron microscopy, respectively, reveals the generation of one-dimensional W ­ O3 nanorods. The nanorods show substan-
tial absorbance in the ultraviolet (UV) region with the bandgap and refractive index of 2.7 eV and 2.48, respectively. Here,
the low value of bandgap without adding any catalyst or co-catalyst is attributed to the microwave treatment. The electro-
chemical properties of ­WO3 are studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).
The nanorods show high current density at different potentials and diffusion-controlled behavior as exhibited by Warburg
impedance. The anodic as well as cathodic peak current values are seen to be increased after the deposition of the thin film
of FTO substrate indicating the better diffusion of ions in the electrolyte. The capacitive and diffusive contribution of the
thin film is investigated at various scan rates using Dunn’s model which shows that the diffusive contribution of the thin film
is 120 times more than the capacitive contribution confirming the diffusive behavior of the thin film. The exchange current
density of the deposited film is calculated which is found to have higher value than that of bare FTO. I–V characteristics of
­WO3 are compared with that of bare FTO which reveals the smaller resistance offered by W ­ O3 film. The equivalent circuit
as obtained from Nyquist plot is used to estimate the resistance of electrolyte, film and charge transfer resistance along with
the double-layer capacitance and Warburg impedance. Further, bode plot is analyzed to study the phase shift and thus the
diffusive behavior of the material.

Introduction spectrum of solar radiations [7–10]. Nanomaterials have

The continuous efforts have been done to increase the effi-
ciency of solar cells since their advent [1–3]. As a result of
these efforts, four generations of solar cells are under the
light [4, 5]. Every newer generation comes with the hopes
and efforts in order to have high efficiency, low cost and
more environment friendly. The latest generations with the
introduction of nanotechnology in the field have given it a
new horizon [6]. It has provided us an unparalleled sea of
opportunities for synthesizing novel materials which are sta-
ble, economical, non-toxic and suitable for absorbing large
* Ranjana Jha
drranjanajha@gmail.com
1
Research Lab for Energy Systems, Department of Physics,
Netaji Subhas University of Technology, Dwarka,
Delhi 110078, India
gained extensive popularity in every multidisciplinary field,
viz., photovoltaics, medical field, environmental applications,
electronics, etc., due to their unprecedented properties [11,
12]. They behave differently from the bulk as they have high
aspect ratio, high mobility, tailored optical and electronic
properties, size-dependent bandgap, enhanced fluorescence,
quantum efficiency, surface plasmon resonance, etc., due to
quantum confinement and tunneling effect [13, 14]. Solar
cells based on nanomaterials show promising properties for
high conversion efficiency and good stability [14].
Transition metal oxides (TMOs) are largely explored
functional materials with fully or partially filled d-shell
and thus existing in numerous structural forms with ionic,
covalent and metallic bonding [15–18]. They have excep-
tional properties like high dielectric constant, wide bandgap,
essential electrical properties, etc., due to their outer d-elec-
trons [18–20] and potential applications in magnetic, optical,

13
Vol.:(0123456789)

and electronic fields [21–25]. Most of the TMOs exist in
mixed valence states and are found in different magnetic
states, viz., ferromagnetic, ferrimagnetic, and semiconduc-
tive[26, 27]. TMOs based nanocomposites have been largely
explored to achieve the enhanced properties like high sur-
face area, increased surface activity, mesoporosity, reduced
electron–hole recombination and increased charge transfer
process [28–33].
Being a TMO, ­WO3 is a promising candidate for vari-
ous applications such as solar cells, photocatalysis, super-
capacitors, gas-sensing, waste water treatment, and solid-
state batteries. [34–38]. It exists in different structural
forms which are tetragonal, orthorhombic, monoclinic
and triclinic [39–41]. The most commonly found structure
among all is monoclinic which is found in the temperature
range 17–330 °C and below − 50 °C. It is a strong oxidizing
agent and shows magnetic properties. Its bandgap is gener-
ally found to be more than 2.8 eV which can be tuned using
suitable catalyst or co-catalyst like platinum as reported by
Widiyandari et al. [42]. The minority charge carriers, i.e.,
holes in ­WO3, have diffusion length of 150 nm which is
more than ZnO (125 nm). Thus, suitable bandgap and high
diffusion length of minority charge carriers make ­WO3 a
potential candidate for solar cell applications [43]. ­WO3
nanomaterials can be synthesized by a number of differ-
ent methods. Wang et al. reported sol–gel-mediated solvo-
thermal growth of ­WO3 nanoflakes on a fluorine-doped tin
oxide (FTO) glass substrate [44]. Mahan et al. and Dillon
et al. deposited high density crystalline ­WO3 nanorods and
nanotubes, respectively, of monoclinic phase by hot wire
chemical vapor deposition (HWCVD) [45, 46]. The present
work reports the synthesis of W­ O3 nanorods via microwave-
assisted hydrothermal route without introducing any cata-
lyst. Hydrothermal is a low cost and environment-friendly
method as it takes place inside a sealed reactor and produces
high-quality nanomaterials. The introduction of microwave
along with hydrothermal method increases the yield of the
product, reduces the size and bandgap of the nanoparticles
and allows the reactions to take place at a lower temperature
[47, 48]. Further, the as-synthesized material is analyzed
by structural, optical and electrochemical characterizations.
Experimental section
Chemicals and materials
Tungsten Hexachloride (­WCl 6) is purchased from M/s
Sigma-Aldrich. Absolute Ethanol (≥ 99.9% purity) is pur-
chased from M/s Changshu Hongsheng Fine Chemicals Co.
Ltd. DI water (> 5 MΩ cm) is used as the solvent during syn-
thesis. All the chemicals and reagents used are of analytical
grade and used without any further purification.
13
Transition Metal Chemistry
Preparation of ­WO3 nanorods
WO3 nanostructures are synthesized by Microwave and Ultra-
sonication (US)-assisted Hydrothermal route in which the pre-
cursor solution is given simultaneous microwave and ultrasoni-
cation treatment at a defined frequency in Microwave/UV/US
extraction system before keeping it in the Teflon. The sche-
matic diagram of the synthesis process is shown in Fig. 1. The
solution of ­WCl6 (0.025 M) in 50 ml DI is kept in the extrac-
tion system and stirred for 30 min. After some time, the solu-
tion is given microwave and ultrasonic treatments simultane-
ously at 80 °C and 24 kHz, respectively, for few minutes. Later,
the solution is kept in the Teflon-lined autoclave at 200 °C for
20 h. The Teflon is left undisturbed for natural cooling of the
product to maintain the crystallinity of the sample. Further, it
is washed with DI and ethanol multiple times to get rid of the
impurities. The product is finally dried at 70 °C for 12 h. The
obtained powder (as shown in Fig. 2) is of canary yellow color.
The following reaction mechanism is suggested for the syn-
thesis of ­WO3 nanoparticles.
WCl6 + 3H2 O = WO3 + 6HCl.
This reaction occurs only in the boiling solution. The heat
can be provided by conventional heating as well as by intro-
ducing microwaves into the solution. However, the conven-
tional way does not provide uniform heating and thus a wide
range of particles are obtained. However, this is not the case
with microwaves and the heating by microwaves is uniform
leading to uniform particle size. Also, in conventional heating,
a larger amount of heat is required than the microwave heating
to boil the liquid.
Deposition of thin film
The spin coating technique is employed for the deposition of
­WO3 film on a 2 cm × 2 cm FTO coated glass substrate. The
as-synthesized powder (1 mg ­ml−1) is ultrasonicated in abso-
lute ethanol to get well-dispersed solution. Afterward, few
drops of the solution are dispensed on the substrate spinning
at 2500 rpm followed by drying at 60˚C. The cycle is repeated
several times to get the uniform film and the film is eventually
dried for several hours. Finally, the film is analyzed by Stylus
Profilometer and Hall effect measurement system to investi-
gate the thickness and conductivity type of the deposited film.
Characterizations
As-synthesized material is analyzed by X-ray diffraction
technique to identify the phase and structure using pow-
der XRD equipment (make: PAN Anaytical, model:X'pert
PRO). XRD Spectra are recorded using Cu K ­ α radiation
Transition Metal Chemistry
Fig. 1  Schematic diagram representing the synthesis process
Fig. 2  Shows the as-synthesized ­WO3 material
of wavelength 1.5407 Å. Fourier-transform infrared
spectroscopy (FTIR) technique is used to obtain infrared
spectrum of absorption of the as-synthesized material.
Surface morphological features and the elemental com-
positional analysis is done by using high resolution field
emission scanning electron microscope (FE-SEM), make:
Jeol, model 7610F plus attached with energy-dispersive
spectrometer (EDS). Microstructural features and selected
area electron diffraction pattern (SAEDP) are recorded at
different areas and at suitable magnifications using FEI
make TEM, model: TECNAI operated at 200 kV. UV–Vis
diffuse reflection spectroscopy (DRS) is done by using
Shimadzu 2600i UV–visible Spectrophotometer.
X‑ray diffraction
Figure 3 represents the XRD pattern of the as-synthesized
material revealing the monoclinic structure of ­WO3 indexed
to JCPDS reference data 01-072-1465. The pattern shows
the major diffraction peaks at 23.192°, 23.677°, 24.373°,
26.672°, 28.719°, 28.720°, 33.362°, 34.212°, 41.5° and
41.901°. The high intensity sharp peaks denote the crystal-
line nature of the material. (0 0 2) peak indicates the perio-
dicity along c-direction and its high intensity reveals the
small size of the sample. Similarly, (0 2 0) peak is indicative
of periodicity along b-direction and it also gives an idea of
the small size. The lattice parameters are calculated using
the following formula,
1 h2 k2 2hk cos 𝛾 l2
2
= 2
+ 2
− 2
+ 2
dhkl a2 sin 𝛾 b2 sin 𝛾 ab sin 𝛾 c
where d is inter-planar spacing and h, k, l are the miller indi-
ces. A comparison of standard JCPDS data and calculated
values is reported in Table 1. Crystallite size is calculated by
using the Debye–Scherrer equation as follows
D = k𝜆∕𝛽 cos 𝜃
where k = 0.9 is Scherrer constant, λ = 0.154 nm is the wave-
length used to irradiate the material, β is FWHM value and θ
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 Transition Metal Chemistry

Fig. 3  XRD pattern of as-synthesized W

­ O3 depicting polycrystalline nature

Table 1  Lattice parameters of the synthesized material as matched )2 ( 2

∗ 𝛽hkl ∗ cos 𝜃 + 𝜀2 ∕4.
( )
dhkl ∗ 𝛽hkl ∗ cos 𝜃 = k𝜆∕t ∗ dhkl
with JCPDS data
Lattice parameter JCPDS value Calculated value Plotting graph by taking (dhkl*βhkl*cosθ)2 as y-axis and
(dhkl2*βhkl*cosθ) as x-axis gives us the slope and intercept
a (Å) 7.30 5.32
which can further be used to get the values of crystallite
b (Å) 7.53 7.51
size and strain developed in the sample. Figure 4b shows
c (Å) 7.68 7.66
the linearly fitted size–strain curve. Here, the value of
α (°) 90 90
slope can be seen as 0.00512 which gives us kλ/t equals
β (°) 90 90
to 0.00512. Using this, we get crystallite size as 28.3 nm.
γ (°) 90 90
Further analysis gives us the modulus of intercept as
6.943 × ­1 0 –6. Calculations using this value gives us the
strain of the order of 5.2 × ­1 0 –3. Table 2 shows a com-
is the position [49]. The equation gives the average crystal- parison of the crystallite size and strain calculated using
lite size as 42.9 nm. different methods.
Further, Williamson–Hall plot is plotted to estimate the It is important to mention here that three different meth-
strain in the sample and confirm the crystallite size. The ods are taken into account to calculate the crystallite size.
relation used for the plot is given as An assumption of Debye–Scherrer equation is that the
sample powder is an ideal powder having infinite identi-
𝛽 cos 𝜃 = 4 𝜀 sin 𝜃 + k𝜆∕D
cal particles spread in all directions. It does not take strain
where β is FWHM, θ is position, ε is strain value, k is shape into the account and thus the obtained crystallite size is not
factor and D is crystallite size. The graph taking βcosθ as very accurate and it gives only a rough idea and thus other
y-axis and 4sinθ as x-axis is called W–H plot. The linearly methods are used to calculate the crystallite size. Wil-
fitted W–H plot is shown in Fig. 4a. The strain in the mate- liam–Hall plot takes the strain into account while calculat-
rial is given as the slope of this plot and the intercept of this ing the crystallite size and thus gives more precise results
plot can be used to calculate the crystallite size. Here, we than Debye–Scherrer equation. Also, Debye–Scherrer
can see that the slope is 1.15339 × ­10–4. Thus, we get the equation follows a 1/cosθ dependency but not tanθ as W–H
strain in the sample of the order of 1.15 × ­10–4. method. This basic difference is that both microstructural
Moreover, the intercept of W–H plot is equal to 0.00418 causes small crystallite size and microstrain occur together
which gives us crystallite size equal to approximately 34 nm. from the reflection broadening. However, this method
Another method of calculating crystallite size and strain of assumes that the stain is uniform in all crystallographic
the material is by using size–strain plot. The relation used directions and the line broadening is isotropic, which is not
in the method is as follows. the case in our sample. Another method used to calculate

13
Transition Metal Chemistry
Fig. 4  a W–H plot of synthesized ­WO3, b size–strain plot of synthesized ­WO3
Table 2  A comparison of crystallite size and strain calculated using
different methods
Method Crystallite size Strain
(nm)
Debye–Scherrer equation 42.9 –
Williamson–Hall plot 33.16 1.15 × ­10–4
Size–strain plot 28.3 5.2 × ­10–3
crystallite size is the size–strain plot. Size–strain param-
eters can be obtained from the “size–strain plot” (SSP).
This has a benefit that less importance is given to data
from reflections at high angles. In this estimation, it is
assumed that profile is illustrated by “strain profile” by a
Gaussian function and the “crystallite size” by Lorentzian
function. This method gives most precise results among all
the above methods for our sample.
UV–vis spectroscopy
The optical properties of the sample are studied using UV–vis
spectroscopy. The absorbance data obtained are used to esti-
mate the other properties like optical bandgap, conduction
band, valence band and refractive index of the material. For
this analysis, the sample is dispersed in DI water and the
reflectance curve is obtained using spectrophotometer. Fur-
ther, using the Kubelka–Munk function, the reflectance curve
is converted to absorbance curve as depicted in Fig. 5a. The
absorbance curve shows the absorbance peaks at 245, 290 and
331 nm. The absorbance data are used to get the Tauc plot
between (αhυ)2 and hυ for the material and by extrapolating
the linear part of the plot, the bandgap is calculated as 2.7 eV
as shown in Fig. 5b. The bandgap is also calculated from the
reflectance curve (Fig. 5c) using Kubelka–Munk theory by
plotting the graph between (F(R)hυ)2 and hυ and extrapolating
the linear part of this plot as shown in Fig. 5d. Here, F(R) is
known as Kubelka–Munk function dependent on R (reflec-
tance) which is equal to K/S, where K = (1 − R)2 is the molar
absorption coefficient and S = 2R is the scattering factor. The
bandgap values are observed to be same from both, the absorb-
ance and reflectance plot.
Refractive index
It is an essential property of a material which plays an
important role in the efficiency of a solar cell. It is calcu-
lated by using the obtained value of bandgap. The follow-
ing relation is used to calculate the refractive index of the
synthesized material.
√
n2 − 1 Eg
2
=1−
n +2 20
where n and Eg denote the refractive index and bandgap,
respectively. Putting Eg as 2.7 eV, we get refractive index
as 2.48.
Conduction band and valence band
The UV–vis data are further used to calculate the valence
and conduction bands of the material using the following
relations.
13

Fig. 5  a UV–vis absorbance curve, b Tauc plot, c UV–vis reflectance plot and d bandgap calculation of ­WO3
EVB = 𝜒 − Ee + 0.5 Eg and
ECB = EVB + Eg
Here χ is absolute electronegativity, Ee (4.5 eV) is free elec-
tron energy. The value of absolute electronegativity is 6.59 eV
for ­WO3 [50]. Putting these values in the former equation, we
get valence band at energy 3.44 eV. Using this value in later
equation, conduction band is found to be at 6.14 eV.
Fourier‑transform infrared spectroscopy (FT‑IR)
The infrared spectra of W
­ O3 nanoparticles recorded in the
wave number range of 4000–600 ­cm−1 are shown in Fig. 6.
It gives the information about chemical interactions and
13
Transition Metal Chemistry
functional groups present in the sample. The broad peak in
the wave number range 3640–3040 ­cm−1 indicates the O–H
stretching vibrations which represents adsorbed water mol-
ecules on the surface of the sample. There are two sharp peaks
at 2973 and 2890 ­cm−1 which denotes the C–H stretching.
This was the information about the presence of functional
groups. In the fingerprint region, the peak at 1400 ­cm−1
denotes the presence of W-OH vibration while two other
peaks at positions 1085 ­cm−1 and 1045 ­cm−1 denotes W–O
bending modes [51]. The peak at 880 ­cm−1 shows the pres-
ence of W=O [52] while the low intensity peak at 810 ­cm−1
represents the O–W–O bridging mode [53]. The peak at
634 ­cm−1 shows the presence of W–O–W bridging [53].
Table 3 presents the summary of the information about all
the peaks.
Transition Metal Chemistry

Characteristics of thin film

Thickness of film

The deposited thin film is analyzed by Stylus Profilometer

to measure the thickness of the film which is found to be
about 100 nm.

Conductivity type of film

The conductivity type of the thin film is studied by Hall

Effect Measurement System (HMS-5000 series) at 298 K
temperature with 5 mA current. The average Hall Coefficient
as observed in Hall effect data is − 2.3 × ­102 ­m3 A-s−1. The
negative value of Hall coefficient reveals the n-type conduc-
Fig. 6  FT-IR spectra of W
­ O3 nanoparticles tivity of the deposited thin film.

Table 3  Summary of FT-IR spectra peaks

Morphological study
Peak position (­ cm−1) Chemical bond The surface morphology of the material is studied by FE-
3640–3040 O–H stretching SEM images. Figure 7a, b shows SEM images recorded at
2973 C–H stretching different areas and at suitable magnifications. The images
2890 C–H stretching show the formation of rods of varying sizes. The sizes of
1400 W–OH all the rods are found to be in nanoscale range. Most of
1085 W–O the rods are found to be in the range of 70–150 nm size
1045 W–O as depicted in Fig. 7b; however, few smaller (40–50 nm)
880 W=O and larger size rods (above 600 nm) are also found to be
810 W–O–W present in the overlapping manner. The agglomeration of
nanorods is also visible at some places. The elemental

Fig. 7  a, b SEM micrographs recorded at different areas depicting of ­WO3 nanorods

13
 Transition Metal Chemistry

Fig. 8  EDS pattern of the corresponding selected area of W

­ O3 shown in (inset)

compositional analysis is studied by recording the EDS Microstructural studies

spectra of the corresponding area of the material (Fig. 8).
Area of which the EDS is recorded is shown as an inset
of Fig. 8. The intensity peaks of W and O elements can
be seen in the EDS spectra confirming the presence of
these elements. The presence of carbon element in EDX
spectra is because of the carbon tape used to record the
FESEM images.
Microstructural features and crystal structure associated
with ­WO3 is carried out by using TEM. TEM images are
observed by dispersing a very small amount of sample
in DI Water, sonicated and loaded on a carbon-coated
copper grid. TEM micrographs are recorded at different
magnifications and at suitable areas which reveals the

Fig. 9  TEM image of as-synthesized W

­ O3 material recorded at different magnifications

13
Transition Metal Chemistry

formation of different shapes and size of nanostructures SAED pattern

as shown in Fig. 9a, b. Some of the formed structures
are nanosheets while some are in the form of nanorods.
Size of the nanosheets is found to be in the range of from
50 to 200 nm. However the rods vary in size from 100 to
200 nm. The structure of the as-synthesized material is
found to be monoclinic as matched with ICDD file number
01-072-1465. Figure 10 shows the EDX pattern of W ­ O3
where peaks correspond to energies of W, O, Cu and C
confirming the presence of tungsten and oxygen.
Figure 11a represents the TEM image at further higher
magnification revealing actual shape of rod like struc-
tures. Selected area electron diffraction pattern (SAEDP)
is recorded at suitable camera length. Figure 11b shows the
SAEDP image of the corresponding area of the material
depicting polycrystalline nature with fine crystallites. Here,
different spots of varying intensities can be observed in the
image which are analyzed in order to identify the planes and

Fig. 10  EDS pattern of ­WO3 powder material taken on carbon-coated TEM grids

Fig. 11  a Shows the bright field TEM micrograph and b SAEDP of corresponding area depicting polycrystalline nature

13

their orientations. Inter-planar spacing ‘d’ corresponding to
three different spots is analyzed and found to be 0.276 nm,
0.388 nm and 0.325 nm corresponding to (0 2 2), (0 0 2) and
(2 1 0) planes, respectively, as matched with JCPDS file no.
01-072-1465 of ­WO3. All these planes are also found to be
present in XRD data. Thus, the data obtained from SAEDP
is in accordance with XRD data as both show the presence
of same planes and phase.
Electrochemical studies
The electrochemical studies are performed using Biologic
SP-240 electrochemical workstation. The three-electrode
setup is employed in which the saturated calomel electrode
(SCE) ­(HgCl2|Hg) and platinum work as the reference and
counter electrode, respectively, while 0.5 M KOH solution
Fig. 12  a Cyclic voltammetry plot of ­WO3 nanoparticles at 0.5 M KOH. b Cyclic voltammetry plot of FTO substrate. c Cyclic voltammetry plot
of ­WO3 nanoparticles at 1 M KOH. d Degradation study at 60 mV ­s−1 for 20 cycles
13
Transition Metal Chemistry
is used as the electrolyte due to its high ionic conductivity.
The working electrode is the deposited film of the W ­ O3 as
discussed above. Cyclic voltammetry and electrochemical
impedance spectroscopy are used to study the electrochemi-
cal properties of ­WO3.
Cyclic voltammetry
Cyclic Voltammetry is an electrochemical technique which is
used to study about the oxidation and reduction processes of
the sample by the measure of electron transfer initiated reac-
tions when positive and negative voltage is applied. It repre-
sents the redox reactions being taking place on the electrode
surface [54–56]. Figure 12a, b shows the CV curve of ­WO3
film and FTO substrate, respectively, in a potential window of
− 1.0 to 1.0 V at the scan rate ranging from 20 to 140 mV ­s−1.
Transition Metal Chemistry
Here, the variation in current is studied at applied potential
during oxidation and reduction processes. The anodic peak
current for the bare FTO is observed in the range 3.8–2.5 mA
which is decreasing with the scan rate due to irreversibility of
the process while the cathodic peak current is varying from
− 0.4 to − 1.2 mA. Whereas the anodic peak current of the
deposited film is found to be in the range between 6.12 and
4.03 mA which is again decreasing with the increase in scan
rate because of the irreversible nature of the reaction while the
cathodic peak current is in the range from − 0.5 to − 1.5 mA.
It is clearly evident that the anodic as well as cathodic peak
current values have increased after the deposition of the thin
film of FTO substrate indicating the better diffusion of ions in
the electrolyte and thus the diffusive behavior of the material.
Here, we can clearly see that the ratio of cathodic and anodic
peak current is far from unity, confirming that the process is
irreversible [57]. Another cyclic voltammetry analysis of the
deposited film has been done by changing the concentration
of the electrolyte from 0.5 to 1 M as shown in Fig. 12c. From
the figure, it is observed that the peak current value seems to
be lower than the peak currents in 0.5 M KOH. The former
molarity of the electrolyte is showing better electrochemi-
cal results and thus, this concentration is used in the further
analysis.
Oxidation and reduction reactions taking place in the
applied potential window are:
WO3 + 2KOH → W6+ + 2K+ + 4O2−
+ H+ + OH− → K2 WO4 + H2 O
WO3 + KOH → KWO3 + OH−
Fig. 13  a Variation in peak current with (scan rate)1/2. b Variation in log (current) with log (scan rate)
Figure. 12d shows the degradation study of the working
electrode at 60 mV ­s−1 scan rate for 20 cycles. It shows
that there is a little decrease in the value of peak current
for 20 cycles. The value of peak current has reduced from
4 to 3.5 mA. It indicates the stability of the film and W
­ O3
nanoparticles
The capacitive and diffusive contribution of the thin
film is investigated at various scan rates using Dunn’s
model. This model states that at a fixed potential, the rela-
tion of the current with scan rate decides the behavior
of the material that whether it is capacitive or diffusive.
According to this model, if the current varies linear the
scan rate, it√exhibits capacitive nature and if it varies lin-
early with scan rate , it is diffusive in nature. The varia-
tion in peak current has been studied with the square root
of scan rate and the linear relationship between the two
is shown in Fig. 13a. The value of peak current increases
with the scan rate, thus indicating the linear relationship
between the two and hence confirming the diffusion-con-
trolled reaction [58].
Capacitive current: i(ν) α ν implies i(ν) = k1 ν; where
ν is scan rate and k1 is a proportionality constant known
as capacitive coefficient.
Diffusive current: i(ν) α ν 1/2 implies i(ν) = k 2 ν 1/2;
where k2 is a proportionality constant known as diffusion
coefficient.
Considering the above two relations, the current meas-
ured by CV is as following:
13

i(𝜈)
i(𝜈) = k1 𝜈 + k2 𝜈 1∕2 or = k1 𝜈 1∕2 + k2
1∕
𝜈 2
Following this equation, the intercept and slope of the
plot between 𝜈i(𝜈)
1∕2
and 𝜈 1∕2 gives the value of diffusive and
capacitive contribution, respectively. The plot is shown in
Fig. 15a, and the estimated intercept and slope is 0.12 and
0.001, respectively. This shows that the diffusive contribu-
tion of the thin film is 120 times more than the capacitive
contribution of the device. These results confirm that the
material shows diffusion behavior and thus suitable can-
didate for optoelectronic devices.
The diffusion-controlled behavior is also confirmed by
another plot between log (peak current) and log (scan rate)
(as shown in Fig. 13b). If the slope of this plot comes
out near unity, it denotes the capacitive behavior of the
material while if the value of slope is near 0.5, it shows
diffusion-controlled behavior [59]. The slope of this plot
is found to be 0.46 and thus, it confirms the diffusion-
controlled process.
Specific capacitance is also calculated using the voltam-
mograms. It is given as
Q interfacial properties of the semiconductors. It is performed
C=
mV
where C is specific capacitance, Q is charge, m is the mass
of active ions in the electrolyte and V is the applied voltage.
Putting the value of current, I = Q/t, we get,
It I
C= or C = V
mV mt
Fig. 14   a Dunn’s model plot to estimate the diffusive and capacitive contribution. b Variation in specific capacitance with scan rate
13
Transition Metal Chemistry
Here, V/t is the scan rate and is represented by ν. Thus, we
get,
I
C=
m𝜈
In CV plot, the current is varying with variation in poten-
tial. Thus, after integrating both sides of the above equation
w.r.t potential, the equation will be
∫ i(V)d𝜈
C=
mΔV𝜈
This formula has been used to calculate the value of specific
capacitance for different scan rates which are found to be
0.066, 0.021, 0.013, 0.010, 0.008, 0.006 and 0.005 F ­g−1
for 20, 40, 60, 80, 100, 120 and 140 mV ­s−1, respectively.
Figure 14b shows the variation in specific capacitance w.r.t
scan rate.
Electrochemical impedance spectroscopy
The electrochemical impedance spectroscopy analyses the
by applying a small AC voltage and measuring the current
across the semiconductor and thus, the impedance is meas-
ured as a function of frequency. To identify the equivalent
circuit and the value of its components like resistance, capac-
itance, etc., EIS study has been performed from 10 mHz to
100 kHz frequency. The Nyquist plot (as shown in Fig. 15a)
has been plotted to analyze EIS data and Z-fitted using EC-
lab software. As the film is deposited on the FTO substrate,
the Nyquist plot of bare FTO has also been plotted (Fig. 15b)
Transition Metal Chemistry

Fig. 15  a Nyquist plot of ­WO3 (inset-zoomed portion of Nyquist plot at high frequencies, Randle circuit). b Nyquist plot of bare FTO (inset-
Randle circuit). c A comparison of Nyquist plots of ­WO3 and FTO. d Bode plot of ­WO3

and Z-fitted. The comparison between the Nyquist plots of that the Warburg diffusion is present in case of the deposited
bare FTO and the deposited film is shown in Fig. 15c. The film which is absent in FTO, thus confirming the better dif-
plot of W­ O3 is showing a merged semicircle with a slant fusion for the film. As the parameters are compared for both,
line indicating the diffusion-controlled reaction which has the substrate and thin film, it is observed that the resistances
already been shown in cyclic voltammetry. The plot of FTO of bare substrate are much higher than the deposited film.
also seems to be semicircle of larger radius followed by a The drastic change in the charge transfer resistance is due
slant line. As the two plots are compared, it is visible that the to the increased intrinsic conductivity in case of W ­ O3 film
radius of the semicircle formed by the deposited film at low
frequencies is smaller than that of FTO, indicating reduced
resistance of the ­WO3 film. The equivalent Randle circuit of Table 4  The values of components in Randle circuit
both the plots is also shown as respective insets in Fig. 15a, Parameter WO3 Bare FTO
b. Here, R1, R2 and R3 are the resistances of electrolyte, film
R1 (resistance of electrolyte) 20 Ω 734 Ω
and charge transfer, respectively. Q is the constant phase ele-
R2 (resistance of film) 205 Ω 705 Ω
ment due to the double layer formed at electrode–electrolyte
R3 (charge transfer resistance) 250 Ω 17 kΩ
interface by the ions’ adsorption on the electrode surface, C
Q (constant phase element) 35.73 μF ­sa−1 3 μF ­sa−1
is double-layer capacitance and W is Warburg coefficient.
C (double-layer capacitance) 198 μF 30 μF
The values of all these parameters obtained for FTO and
W (Warburg impedance) 880.6 Ω ­s−1/2 –
­WO3 film are compared and reported in Table 4. It is found

13

which is very low for FTO. The double-layer capacitance
also has high value in case of the film as the ions are more
diffusive in this case and hence accumulation is more, form-
ing the double layer.
The exchange current density can be calculated using the
value of charge transfer resistance according to the follow-
ing formula.
RT
Rct =
nFi
where Rct is charge transfer resistance, R is gas constant, T is
temperature, n is no. of electrons involved (n = 1), F is Fara-
day’s constant and ‘i’ is exchange current density [57]. Thus,
putting all the values, the exchange current density of the
bare FTO and the deposited film is calculated as 1.5 × ­10–6
and 1.01 × ­10–4 ­Am−2, respectively. The reason of the low
exchange current density for bare FTO is because of its high
charge resistance.
To get an idea of impedance and phase simultaneously
w.r.t the frequency for the diffusive behavior of the mate-
rial, another presentation method has been employed which
is Bode plot (as shown in Fig. 15d). This is a plot between
log (frequency) on the x-axis and log (Z) and phase shift
on the y-axis. Here, it is shown that at low frequencies, the
phase is around 40° which gradually changes to − 80° in the
mid frequency region after which it shifts to − 40° in high
frequency region. The maxima is observed to be at − 80°
in the mid frequency region indicating the stability of the
material. Also, it shows the variation in impedance with the
frequency. In the lower frequency region, highest value of
impedance is seen, showing the diffusion process. At higher
frequency, value of impedance falls abruptly because of
the pure resistive behavior and corresponds to the solution
resistance.
Current–voltage characteristics
It is an important technique to get insights about the elec-
tronic properties of a material. The current variation w.r.t the
applied voltage for the deposited ­WO3 thin film is studied
by the current–voltage characteristics (I–V characteristics)
and compared with the I–V characteristics of FTO as shown
in Fig. 16. Here, we can see that the variation in current
with voltage is linear for both, the substrate and film and
thus, they are following ohm’s law. The current at a specific
voltage is more for the deposited film than the bare sub-
strate, hence supporting the usage of W­ O3 for optoelectronic
applications. The larger slope of ­WO3 I–V shows the smaller
resistance than the FTO substrate.
13
Transition Metal Chemistry
Fig. 16  I–V characteristics of ­WO3 thin film and FTO substrate
Conclusions
WO 3 nanostructures are successfully synthesized via
microwave-assisted hydrothermal route which gives a
canary yellow-colored powder. The introduction of micro-
wave treatment lowers the bandgap of ­WO3 without adding
any catalyst or co-catalyst. The XRD data obtained for the
synthesized material is matched with the JCPDS file no.
01-072-1465 which reveals the formation of W ­ O3 having
single phase and monoclinic structure. Average crystallite
size is found to be in the range 28–43 nm as calculated by
Scherrer equation, W–H and size–strain plots. Further, the
strain in the material is found to be 1.15 × ­10–4 and 5.2 × ­10–3
as calculated by W–H and size–strain plot, respectively.
The optical properties of W ­ O3 are studied by utilizing
UV–vis spectroscopy. The absorbance peak is found to be at
331 nm. Tauc plot is obtained by using the absorbance graph
which gives the value of bandgap as 2.7 eV. The bandgap is
used further to calculate the refractive index of the material
and the value obtained is 2.48. Moreover, the valence and
conduction bands at 3.44 eV and 6.13 eV, respectively, are
calculated using the bandgap. FTIR study shows the forma-
tion of W–O, W=O and O–W–O bonds along with O–H,
C–H and C=O stretching.
Morphological study by FE-SEM images shows the for-
mation of nanorods of varied size. Microstructural studies of
the material reveal the formation of nanorods and nanosheets
of different size. SAEDP revealed the polycrystalline nature
of the as-synthesized material. The presence of (0 2 2), (0 0
2) and (2 1 0) planes in SAEDP are in good agreement with
XRD data.
The electrochemical analysis of the material as done by
CV and EIS reveals the diffusion-controlled behavior of
Transition Metal Chemistry
the material along with the presence of Warburg element.
The analytical results of ­WO3 are compared with that of
bare FTO substrate. It is evident that the anodic as well
as cathodic peak current values in cyclic voltammograms
have increased after the deposition of the thin film on FTO
substrate indicating the better diffusion of ions of ­WO3
in the electrolyte. The ratio of cathodic and anodic peak
current is observed to be far from unity revealing the irre-
versible process. The capacitive and diffusive contribution
of the thin film is investigated at various scan rates using
Dunn’s model. The linear relationship between the peak
current and square root of scan rate confirms the diffusion-
controlled reaction. Dunn’s model is also used to observe
that the diffusive contribution of the material is 120 times
more than the capacitive contribution.
The Nyquist plots of W­ O3 and bare FTO are compared
and it is found that the radius of the semicircle formed by
the deposited film at low frequencies is smaller than that of
FTO, indicating reduced resistance after the deposition of
­WO3 film. The drastic change in the charge transfer resist-
ance is due to the increased intrinsic conductivity in case
of ­WO3 film which is very low for FTO. It is also found
that the Warburg diffusion is found to be present in case
of the deposited film which is absent in FTO, thus con-
firming the better diffusion for the W­ O3 film. The double-
layer capacitance also found to have high value in case
of the film as the ions are more diffusive in this case and
hence accumulation is more, forming the double layer. The
exchange current density of the bare FTO and the depos-
ited film is calculated as 1.5 × ­10–6 and 1.01 × ­10–4 ­Am−2,
respectively, and the difference is due to the reduced resist-
ance after film deposition. Finally, IV characteristics of
­WO3 are obtained and compared with that of FTO sub-
strate. The larger slope of W ­ O 3 I–V in observed which
again shows the smaller resistance than the FTO substrate.
Acknowledgements We are extremely grateful to the Vice-Chancellor,
NSUT, Delhi, India, for providing us the opportunity to work in this
encouraging environment where we can have substantial contribution
to the research. One of the authors, Shreya would also like to acknowl-
edge the financial support for research given by university as University
Research Fellowship (URF).
Author contributions S did the conceptualization, investigation, data
collection, writing—original draft preparation, visualization and inves-
tigation of the research work.PP helped in the formal analysis of the
research work.RJ supervised the whole research work and reviewed
the manuscript.SS supervised, reviewed and edited the manuscript.
Declarations
Conflict of interest The authors declare that there is no conflict of in-
terest.
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