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Abstract
Tungsten Oxide (WO3) is a well-known transition metal oxide which exhibits non-toxicity and
stability in its nanoparticle form. It is a potential candidate for a variety of applications due to its low
cost and facile synthesis process. In the present work, WO3 nanoparticles were synthesized via facile
acid-coprecipitation method to explore the effect of surfactants on the morphology of WO3
nanoparticles and thus, on its structural, optical and electrochemical properties. The morphology
analysis revealed the formation of spherical nanoparticles in the absence of any surfactant while
nanoflakes and nanosheets were observed in the presence of cetyltrimethylammonium bromide
(CTAB) and polyethylene glycol (PEG), respectively. Moreover, the presence of surfactants was found
to influence the crystallinity state of the samples. The different morphologies exhibited optical band
gap of 2.2–2.7 eV as analyzed by UV–vis spectroscopy along with other optical properties like
absorbance range and refractive index. The electrochemical properties of the samples were studied by
employing potentio electrochemical impedance spectroscopy (PEIS) and cyclic voltammetry (CV)
techniques. CV analysis revealed the diffusion-controlled behavior of the samples which may be
suitable for photovoltaic applications. Furthermore, impedance study showed the presence of
Warburg impedance which indicates that there is an infinite layer of excitons on the surface of thin
film, further suggesting WO3 as a prominent material for solar cell applications. The incorporation of
surfactants resulted in the reduction of charge transfer resistance indicating more efficient charge
transfer process.
1. Introduction
The persistent and progressively escalating global energy demand necessitates the exploration of the new ways to
exploit and enhance the efficiency of the renewable sources of energy. One of those is the solar energy with
boundless potential to fulfill the energy needs of the world [1–3]. To harness this potential, researchers continue
their pursuit to find the efficient and cost-effective photovoltaic cell materials to replace the traditional and
expensive silicon solar cells, which have achieved maximum efficiency of > 25% [4–6]. The Sun produces
1.38 × 106 exajoules of energy yearly i.e., 2500 times the energy demand of humans on Earth [7]. Solar cells work
on the principle of photovoltaic effect to convert light energy into electrical energy. Despite the efforts going on
in the entire world to achieve maximum efficiency, it is not possible to increase the efficiency of solar cells over a
limit known as Shockley Quisser limit [7]. It is the theoretical limit up to which the efficiency of a solar cell is
achievable for a material made up from a single p-n junction as a function of band gap energy. It is determined by
the amount of maximum energy being produced by a single photon.
Many of the transition metal oxides are the potential candidates for optoelectronic applications due to their
suitable optical and electronic properties [8–20]. One of them is tungsten oxide (WO3), which has a bandgap of
∼2.6–3.0 eV [21]. It is a well-known n-type semiconductor which is often present in the sub-stoichiometric ratio
of (WO3-x) form like WO2.9, WO2.83, etc due to oxygen vacancies, indicating the ability of WO3 lattice structure
Table 1. Shows the list of chemicals and analytical reagents chemicals and analytical reagents list.
to sustain the oxygen vacancies with W+5 state [22]. This variation in the oxygen vacancies enables the tuning of
electron density, which in turn alters the material’s conductivity. WO3 strictly satisfying the stoichiometric ratio
exhibits the property of an insulator, while the non-stoichiometric WO3-x is n-type semiconductor. Hence a
minor change in oxygen’s proportion of WO3-x stimulates large changes in its electrical properties to exhibit
metal or semi-conductor behavior at times [23]. Therefore, WO3 can exhibit required properties without
addition of another material in the form of composites or doping. Moreover, WO3 is a stable and non-toxic
material with an appropriate band gap, thus making it a viable option for the several electrochromic and optical
instruments [24, 25]. Additionally, WO3 exhibits the phase conversion as follows [26]
Monoclinic 330 C Orthorhombic 710
C Tetragonal.
A variety of methods can be employed to synthesize the WO3 nanoparticles like chemical vapour deposition
(CVD), sol-gel, hydrothermal, sonochemical, solvothermal, etc [27, 28]. Acid co-precipitation method is one of
the numerous methods that can be used to synthesize WO3. In this method, the metal hydroxide part from the
salt precursor is precipitated in the base solvent. The controlled release of the ions into the solvent helps to
regulate the process of nucleation and the particles’ growth kinematics, finally forming the nanoparticles [29].
However, the controlled nature of the reactions is difficult to achieve in mixed oxide precipitation and hence, the
surfactants can be used which assists in regulating the morphology of the synthesized material. Further the
parameters like temperature, concentration of ions and the solution’s pH are important in determining the
precipitation process. Chelating agent like oxalic acid had been used in this work to direct the structure for the
formation of the crystalline phase by binding the metal ions in the reaction [21]. Surfactants were also used in the
synthesis of WO3 nanoparticles in the present work. Surfactants are the surface modifying compounds led to
controlling of the characteristic properties of nanomaterials like catalytic activity, charge transfer or any other
surface related activity [30]. The co-precipitation process involves mainly the nucleation, growth and the
agglomeration of the particles, consecutively. It majorly involves four stages [29]:
2. Experimental section
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Phys. Scr. 98 (2023) 085936 T Kumar et al
dissolved in 50 ml DI water and stirred continuously. After few minutes, 5 M HNO3 and 0.185 M oxalic acid,
15 ml each were mixed with the former solution and stirred at 90 °C for 1.5 h. The pH of the samples was also
tested simultaneously and it was observed to be ∼5. Soon, the formation of the neon greenish colored
precipitates of WO3 was clearly visible. After the formation of the precipitates, the sample was left undisturbed
for few minutes to get the sedimentation of precipitates. Afterwards, the sample was centrifuged and rinsed
several times with absolute ethanol and distilled water for the removal of the impurities. Thereafter, the sample
was dried over in the vacuum oven for 12 h and then grinded to get the uniform WO3 particles resulting in the
formation of T01 sample. The schematic diagram of the synthesis is represented in figure 1. The same procedure
was repeated to prepare other samples of the series with an additional step of adding up 0.1 g and 0.2 g of CTAB,
after mixing of oxalic acid resulting in next two consecutive synthesis of C01, C02 samples, respectively.
Furthermore, PEG assisted synthesis includes the addition of 0.1 g, 0.2 g, 0.3 g of PEG after dissolution of oxalic
acid to finally get P01, P02, P03 samples, respectively. For easy understanding, the color codes are assigned to
each of the sample as: grey for T01, red for C01, blue for C02, green for P01, purple for P02, golden for P03.
The reaction involved for the synthesis of WO3 nanoparticles is shown in equation (1).
Various characterization techniques were carried out to analyze the as-synthesized samples. x-ray diffraction
(XRD) pattern was obtained using Panalytical X’Pert - Pro Diffractometer. Shimadzu 2006i UV–Visible
spectrometer was utilized to get the UV–visible spectrum which was used to analyze the samples’ optical
properties. Cyclic voltammetry (CV) and potentio electrochemical impedance infra-red spectroscopy (PEIS)
were performed using the EC-lab Biologic SP-240 instrument. Fourier transform infrared spectroscopy (FTIR)
was performed using Perkin Elmer IR spectra to reveal the presence of adsorbed functional groups and the
bonds present in the as-synthesized materials and thus confirming the formation of WO3. Field emission
scanning electron microscopy (FESEM) was employed using the instrument of make JEOL and model 7610F
plus to get the surface morphology, structure and elemental composition of the samples. High resolution
transmission electron microscopy (HRTEM) using TECNAI 200 kV TEM was performed to determine the
samples’ particle size along with EDX for the elemental composition and Selected Area Electron Diffraction
Pattern (SAEDP) for the identification of planes.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 2. XRD spectra of the samples (a) T01, (b) C01, (c) C02, (d) P01, (e) P02 and (f) P03.
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Phys. Scr. 98 (2023) 085936
Table 2. Parameters including crystallite size micro strain, stacking fault and dislocation density for the samples C01, C02, P01, P02 and P03.
Crystallite size (in nm) from debye- Crystal-lite size (in nm) from Crystal-lite size (in nm) from Micro strain, ε from Micro strain, ε from size
5
Sample code scherrer equation W-H plot size-strain plot W-H plot strain plot Stacking fault Dislocation density
T Kumar et al
Phys. Scr. 98 (2023) 085936 T Kumar et al
Table 3. As-calculated lattice parameters as compared with JCPDS data are as follows.
Lattice parameters JCPDS File no. 00-018-1420 JCPDS File no. 01-084-0886 C01 C02 P01 P02 P03
The crystallite size of the samples was determined by using Debye–Scherrer equation as follows
(equation (2)) [31]
Kl
D= (2)
b cos q
where D is the crystallite size (in nm); λ is the x-ray wavelength, equal to 0.154 nm; K is the shape factor, equal to
0.9, β is the broadening at full width-half maximum, Ɵ is the Bragg’s angle (in radian) [31]. Putting the respective
values in the above formula, the calculated values of crystallite size were found to be 14.8 nm, 22.9 nm, 15.4 nm,
18.7 nm, 15.6 nm for sample C01, C02, P01, P02 and P03, respectively.
The precise values of crystallite size and micro strain values of the samples were calculated by another
method i.e., Williamson Hall (W-H) plot (figure S1) plotting βcosθ versus 4sinθ in accordance with the
following relation as equation (3).
Kl
b cos q = 4e sin q + (3)
D
where ε represents micro strain, β is the broadening at full width-half maximum, θ. Equating the above equation
with the general line equation, if the plot is between βcosθ and 4sinθ figure (S1), the intercept and slope gives the
value of crystallite size and strain respectively. Here, 16.6 nm, 22.5 nm, 82 nm, 9.49 nm and 9.97 nm were the
obtained values of crystallite size for C01, C02, P01, P02 and P03 samples respectively as depicted in table 3.
Moreover, the values of the strain present in the samples as estimated were 0.0031,0.0084, 0.0044, 0.0044 and
0.003 for C01, C02, P01, P02 and P03 sample series as shown in table 2. The increase in crystallite size as
compared with the crystallite size (D) from Debye–Scherrer equation in P01 is attributed to the tensile strain
while the decrease in crystallite size in P02 and P03 samples are due to compressive strain.
Additionally, one more method i.e., the size-strain plot ((d βcosθ)2 versus d2 βcosθ) method (figure S2) was
used to determine the strain using the relation in equation (4).
Kl 2 e2
(db cos q )2 = (d b cos q ) + (4)
D 4
where d is the d-spacing (in nm). The values of strain as calculated by using the intercept and slope of size strain
plots (figure S2) were 0.0029, 0.0018, 0.0044, 0.0043, 0.0040 of C01, C02, P01, P02 and P03 respectively as shown
in table 2. Some other important parameters viz. stacking fault and dislocation density were also investigated by
using the equation (5) and (6).
Stacking faults are the 2-dimensional planar defects which may be present inside the crystal structure. The
stacking fault equation is given by equation (5).
2p 2b
s= (5)
45( 3tanq )
where β is FWHM broadening value. Stacking fault was calculated for C01, C02, P01, P02, P03 comes out to be
0.00609, 0.00506, 0.00552, 0.00477, 0.00476 respectively as per table 2.
The dislocation density is the measurement of the number of dislocations lines present in the crystalline
material’s unit volume. It was calculated as given in equation (6).
1
d= (6)
D2
where δ is Dislocation Density, D is crystallite size which is determined using Debye–Scherrer equation.
Dislocation density values as-obtained are 0.00865, 0.00467, 0.00789, 0.00524 and 0.00516 respectively for C01,
C02, P01, P02 and P03 sample as depicted in table 2.
To determine the lattice parameters for the monoclinic and orthorhombic crystal systems, equations (7) and
(8) were used:
1 h2 k2 2hl cos l l2
= 2 2 + 2 2 - + 2 for monoclinic (7)
d2 a sin l b sin l ab sin l
2 c
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 3. (a) Absorbance spectra and (b) Tauc plots of all the as-prepared samples showing the corresponding energy band gaps.
1 h2 k2
= 2 2 + 2 2 for orthorhombic (8)
d2 a sin l b sin l
where
h, k and l are the miller indices values; a, b and c are the lattice parameters; β is the lattice angle. The
comparison for the obtained values of lattice parameters with standard values is presented in table 3. It is visible
that there is a slight deviation in the lattice parameters from the standard values which might due to the addition
of oxygen vacancy defects during the synthesis.
where h is Planck’s constant, υ is the frequency of the incident light, β is the constant depending upon transition
probability,α is absorption coefficient and Eg is the band gap energy, n is equal to 2 and ½ for the direct and
indirect semiconductor respectively.
Figure 3(b) shows that the change in band gap energy is prominent in the samples C01 (2.5 eV) and P03
(2.2 eV), which shows significant deviation from the band gap of T01 sample (2.7 eV) due to the alteration of
electronic properties in the vicinity of WO3 nanoparticles by the adsorption of CTAB or PEG molecules and
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 4. FTIR spectra of the as- prepared samples (a) T01, (b) C01, (c) C02, (d) P01, (e) P02 and (f) P03.
Table 4. Optical band gaps and refractive indices of the samples (a) T01,
(b) C01, (c) C02, (d) P01, (e) P02 and (f) P03.
formation of complexes. The optical band gap values thus obtained are suitable enough to allow materials to
evince the photovoltaic effect.
Refractive index of a material is also an important optical property to confirm its suitability for solar cell
applications. No long-range propagation is possible because of the large number of carriers resulting in higher
number of collisions, if the refractive index value is lower than 1 [32]. Lower is the reflectivity of the material,
better the material will perform as a solar cell. The refractive index of the sample materials was determined using
the relation given in equation (10).
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 5. FESEM images of the samples (a) T01, (b) C01, (c) C02, (d) P01, (e) P02 and (f) P03.
n2 - 1 Eg
=1- (10)
n2 + 2 20
where n is refractive index of the material and Eg is optical band gap (in eV). The optical band gap values and
corresponding refractive indices are summarised in table 4.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 6. HRTEM images of samples (a) and b) T01 and (c) and (d) C01, (e) SAED pattern of sample C01, HRTEM images of samples
(f) C02, (g) P01, (h) P02, (i), (j) and (k) P03, (l) SAED pattern of P03 sample
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Phys. Scr. 98 (2023) 085936 T Kumar et al
The CTAB-assisted samples were revealed to be in the form of agglomerated nanoflakes. The flakes were
visible on the surface of agglomerated structure in C01 sample. This agglomeration may be attributed to the high
surface energy of the nanoflakes due to their large surface area to volume ratio. This agglomeration of the nano-
flakes increased abruptly in C02 sample. It can be deduced here that the presence of CTAB obstructed the
formation of spheres due to which particles were seen to be agglomerated which increased by increasing the
amount of CTAB. The observed change in morphology of the CTAB assisted synthesized samples C01 and C02 is
attributed to the decomposition of the tungstate acid during ultrasonication to produce WO3 nuclei having
layers of octahedrons [WO6]6−. CTAB after being added to the solution get ionized as CTA+ and Br− thus
leading the CTA+ getting to attract to the four negatively charged oxygen atoms of [WO6]6− planar surface. This
leads to the formation of [CTA- WO6]6−, leading to change the orientation of the planes of the particles to form
nanoflakes [35].
While PEG being an organic stabilizer and easily soluble in water, it passivated the surface of the
nanoparticles, thus reducing the surface energy. In P01, P02 and P03 samples, PEG promoted the growth of the
WO3.H2O crystallites due to the hydrogen bond formation between PEG’s hydroxyl group and a highly unstable
intermediate product [WO3-OH-H-[OCH2CH2]n] and H2O. This unstable intermediate then got reduced to
WO3.H2O due to the prevailing of the acidic environment. Thus, the presence of the –OH bond in PEG
promotes the growth of WO3 nanoparticles [36]. The PEG-assisted samples showed the clear formation of
nanosheets without any agglomeration. These samples have large surface area to volume ratio with altered
surface energy as to inhibit the agglomeration or spherical shape. The EDX of all the samples revealed the
elemental composition of the samples. All the spectra showed same results thus, only one of the EDX spectra is
shown in figure S3. It is ascertained that W and O elements are present in all the materials.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 7. Cyclic voltammograms of samples (a) T01, (b) C01, (c) C02, (d) P01, (e) P02 and (f) P03.
the as-synthesized samples at multiple scan rates varying from 20 to 120 mV s−1 in the potential window of −1 V
to 1 V in 1 M KOH solution.
The conduction mechanism of charge diffusion in the WO3 sample as follows [38]:
During the forward scan:
Oxidation reaction: WO3 (s) WO3+ (aq) + e- (11)
Reduction reaction (at the counter electrode) : 2H2 O(l) + 2e - H2 (g) + 2OH-(aq) (12)
Overall reaction: WO3 (s) + 2H2 O(l) WO3+ (aq) + H2 (g) + 2OH-(aq) (13)
This oxidation process generates WO+ 3 ions and releases electrons into the electrolyte. The positive charge
carriers (holes) are created within the WO3 lattice.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 8. A comparison of voltammograms of all the as-prepared samples at scan rate 60 mV s−1, (inset) showing peaks at high
voltage.
Figure 9. (a) Variation of peak current w.r.t Scan rate and (b) variation of log (current) versus log (scan rate) for as-synthesized
samples.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 10. Specific capacitance versus scan rate plot for all the synthesized samples.
electrochemical process, where the oxidation and reduction reactions exhibit similar kinetics and occur with
comparable efficiency. This suggests a symmetric behavior of the system, indicating that the reactants are easily
converted to products during both the forward and reverse scans. On the other hand, a switch ratio significantly
different from 1 implies an irreversible or asymmetrical electrochemical process. A higher switch ratio (>1)
suggests a greater efficiency of the oxidation process compared to the reduction process, indicating an imbalance
in the electrochemical reactions. Conversely, a lower switch ratio (<1) suggests a more efficient reduction
process relative to the oxidation process [38]. For an example, the switch ratio of P02 sample at 60 mV s−1 scan
rate was calculated which was found to be ∼4. A comparison of the voltammograms of all the samples at a single
scan rate is shown in figure 8. A regular increase is seen in peak current with increasing scan rates following
Randle Sevick equation given in equation (17), which was confirmed by the plot shown in figure 9(a). It is
representing the variation of peak current with Scan rate (mV /s) . The linearity of this plot for all the samples
indicates diffusion-controlled behavior of the materials [32, 38].
nFvD ⎞
i p = 0.446nFAC⎛ (17)
⎝ RT ⎠
where ip is peak current, n is the number of participating electrons in the redox reaction, F is the Faraday’s
constant, A is the electrode surface area (cm2), D° is the diffusion coefficient analyte undergone oxidation
(cm2 s−1), C° is the bulk concentration of the analyte ( mol cm−3). This equation helps in predicting whether the
analyte if freely diffusing in the solution or it may get adsorbed over the electrode surface [37].
The electrochemical reactions are generally dominated by any of the two mechanism [32] namely capacitive
behaviour or diffusion controlled charge storage of the thin film material. The exact nature can be visualized
using relation 18.
I = (n)m (18)
where I represents current, ν denotes scan rate and n & m are the positive constant values. Now, on taking log on
both sides of the above equation and comparing it with standard line equation y = mx+c, it results in
equation (19).
where m here behaves as the slope of the equation, as shown in (figure 9(b)) If the value of slope is nearly 0.5,
indicates the diffusion controlled behaviour, and if equal to 1, indicates the capacitive behaviour [32]. The slopes
that obtained were 0.347, 0.215, 0.062, 0.219, 0.335 and 0.194 for T01, C01, C02, P01, P02 and P03 respectively,
all indicating towards the diffusion controlled nature of the thin films of the deposited samples which was in
accordance with the linearity of the current versus Scan rate (figure 9(a)).
Degradation study of the working electrode (as-deposited thin film) was undertaken for 10 consecutive
cycles at 60 mV s−1 scan rate as shown in figure S5. The electrochemical reversibility here means the kinetics
between analyte and electrode. There was negligible degradation being observed in the deposited thin film
materials. It indicated the stability of the films and WO3 nanoparticles.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 11. Representation of Nyquist plots for: (a) T01; (b) C01; (c) C02; (d) P01; (e) P02; (f) P03 with inset showing the Randle circuit
for each as inset.
The specific capacitance was also determined using the following relation (equation (20)).
C=
ò Idv (20)
Av (DV)
where C is Areal capacitance (F/cm2) (ref.), V is scan rate (mV/s) and ΔV is the potential window which is 2
V here.
The specific capacitance values calculated for different scan rates for the samples are reported in table S3. The
continuously decreasing nature of Specific capacitance was clearly visible from Specific Capacitance versus Scan
rate plots in figure 10, indicating that the material is not showing significant capacitive behaviour and thus
mainly exhibiting diffusion controlled behaviour.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Table 5. Values of components forming Randel circuits of samples (a) T01, (b) C01, (c) C02, (d) P01, (e) P02 and (f) P03.
Parameter Value for T01 Value for C01 Value for C02 Value for P01 Value for P02 Value for P03
E (W)
Z (W) = (21)
I (W)
where, Z(w) is impedance of the film, E(w) is applied potential and I(w) is the current on the surface of the film.
The benefit of the EIS technique is that it can be used to study both the bulk and surface features of the material.
The imaginary versus the real impedance component (Re Z) was analyzed for each of the thin films in
Nyquist plots (figure 11), where Z is the impedance of electric double layer capacitor (EDLC). The Randle
equivalent circuits mainly composed of R-C components were used for the interpretation of the Nyquist plot
[39]. These circuits were determined using the EC-Lab software and Z-Fit. L1 is the inductance, R1, R2, R3 and
R4 are the resistances of the electrolyte (Rs), thin film (Rf) and charge transfer (Rct) explicitly; C is the capacitance
due to electrochemical double layer, Q2 is the constant phase element, W4 is the Warburg impedance. The
presence of the resistance and capacitance in parallel combinations led to the formation of the semi-circular
figures in Nyquist plots of the deposited thin film samples.
PEIS also revealed the presence of Warburg impedance at 45° mainly in T01 and C01 samples indicating
their credible solar cell applications. Warburg impedance was small at higher frequency since the diffusing
reactants didn’t have to move much farther while at lower frequency values because the diffusing reactants have
to move farther leading to increase in Warburg impedance [40, 41]. The decrease in Rct value as compared to T01
indicates better charge transfer on addition of surfactants [42]. The various impedance parameters were
determined using EC- lab software and Z-fit as tabulated in table 5.
The exchange current density, which represents the rate at which redox reactions occurring on the electrodes
at equilibrium, was determined using equation (22).
RT
R ct = (22)
nFi
where R is gas constant, Rct is charge transfer resistance, T is temperature (in Kelvin), n is the number of electrons
involved i.e. n = 1 (here), F is Faraday’s constant, io is exchange current density [41]. The exchange current
density values calculated were 4.213 × 107 A cm−2, 0.002585221 A cm−2, 0.002585221 A cm−2,
0.001384841 A cm−2 and 0.002585221 A cm−2 respectively for T01, C01, P01, P02 and P03.
Another method to analyze the PEIS data is Bode plots as shown in figure 12, which are sketched between
(log (Z) versus log(frequency) versus Phase (Z)), where Z is impedance. The advantage of using Bode plots is that
they allow to know the frequency value alongside unlike Nyquist plots where frequency is not a part of the plot.
The presence of only one maximum in each Bode plot represents the stability of the sample material which can
be observed for T01, C01, P02 and P03 sample.
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Phys. Scr. 98 (2023) 085936 T Kumar et al
Figure 12. Bode plot for (a) T01; (b) C01; (c) C02; (d) P01; (e) P02; (f) P03.
4. Conclusion
WO3 nanostructures were synthesized using a feasible, cost-effective and environment friendly method of acid
co-precipitation with and without the surfactants, CTAB and PEG. FESEM analysis confirmed the formation of
the agglomerated nanoflakes (∼50 nm) in CTAB assisted synthesized samples due to the surfactant being
adsorbed over the surface of nanostructures to lower down their active surface energy resulting in nucleation of
nanomaterial. In PEG assisted synthesized sample series, formation of nanosheets was confirmed. The optical
analysis has revealed P03 to be the best among all as-synthesized WO3 nanomaterials for photovoltaic
application due to its comparatively lower optical band gap value i.e., 2.2 eV.
XRD results confirmed the formation of the monoclinic phase of prepared samples. It was also visible from
XRD that the surfactant free sample was amorphous in nature while the samples prepared with surfactants were
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Phys. Scr. 98 (2023) 085936 T Kumar et al
crystalline as the surfactants act as nucleating agents for promoting ordered crystalline structures. The crystallite
size of the as synthesized samples was calculated out to be 14.817 nm, 22.925 nm, 15.401 nm, 18.790 nm and
15.643 nm for C01, C02, P01, P02 and P03 respectively.
Cyclic Voltammetry analysis of the deposited thin films of the samples showed the diffusion-controlled
behavior of the sample series. The peak current versus square root of scan rate and log (peak current) versus log
(scan rate) graphs were plotted and analyzed to confirm the diffusive behavior of the samples. Linearity of Peak
current versus Scan rate (mV /s) plot also predicted the stability of the samples. PEIS study revealed that the
addition of surfactants (CTAB and PEG) has led to lowering down of the charge transfer resistance value thus
indicating improved and more efficient charge transfer. Also, there was lowering down of Rs value in P02
indicating good contact and better charge transfer. Therefore, it is observed that there is an improvement in the
electrochemical properties of P02 and P03 samples especially which is attributed to the addition of PEG
surfactant.
Acknowledgments
The authors would like to acknowledge Prof J P Saini, Vice-Chancellor, Netaji Subhas University of Technology
for providing essential resources for the research work. The authors are also thankful to Prof. Sukhvir Singh for
his additional support and efforts. One of the authors, Tarun appreciates the emotionalsupport by his
colleagues, Ms Deepa and Ms Dipti. In addition to the aforementioned, the authors would like to formally
acknowledge the unwavering support and encouragement provided by their respective families throughout the
entire research endeavour.
All research data is included in the manuscrip. The data that support the findings of this study are available upon
reasonable request from the authors.
Conflicts of interest
ORCID iDs
Shreya https://orcid.org/0000-0002-4339-1756
Peeyush Phogat https://orcid.org/0000-0002-3858-6233
Ranjana Jha https://orcid.org/0000-0003-4495-3519
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