J Mater Sci: Mater Electron
DOI 10.1007/s10854-016-5057-5
Synthesis and characterization of CoWO4 nanoparticles
via chemical precipitation technique
Suresh Sagadevan1 • Jiban Podder2 • Isha Das3
Received: 4 March 2016 / Accepted: 22 May 2016
Ó Springer Science+Business Media New York 2016
Abstract This paper has for its content the synthesis and
the findings of structural, surface morphological, optical
and electrical studies of CoWO4 nanoparticles. Precipita-
tion method was employed for the synthesis of CoWO4
nanoparticles. To determine the average grain size of
CoWO4 nanoparticles the X-ray diffraction pattern was
used. The presence of CoWO4 nanoparticles was confirmed
by the FT-IR spectrum. The scanning electron microscopy
analysis revealed the facts about the surface morphology of
CoWO4 nanoparticles. The transmission electron micro-
scopic analysis helped to measure the size of the particle
formed. The absorption spectrum and photoluminescence
spectrum made it possible to analyze the optical properties
of CoWO4 nanoparticles. The contribution of this work is
that the dielectric properties such as the dielectric constant,
the dielectric loss, and the AC conductivity of the CoWO4
nanoparticles were studied at different frequencies and
temperatures.
1 Introduction
Many metal tungstates exhibit such properties as will make
them suitable for potential applications in different areas of
technology. Nanosize transition metal tungstates have
& Suresh Sagadevan
drsureshnano@gmail.com
1
Department of Physics, AMET University, Chennai, India
2 nanoparticles of desired size and morphology. However,
Department of Chemical and Biological Engineering,
University of Saskatchewan, Saskatoon, SK S7N 5A9,
Canada
3
Department of ECE, Holy Mary Institute of Technology and
Science, Hyderabad, India
received much consideration due to their leading lumi-
nescent behavior and their potential applications in dif-
ferent technologies. Several of the metal tungstates are
more peculiar because of their electrical and magnetic
behavior [1]. The CoWO4 is a material which has been
considered for extensive studies of photoluminescence
(PL), optoelectronic devices, scintillating material, micro-
wave dielectrics and catalysis [2] where the properties of
these materials can be achieved by well-intended synthetic
technique [3, 4]. The tungstates are found highly attractive
and suitable for different methodological applications such
as solid state lasers [5], scintillator [6], optoelectronic
devices besides being promising candidates for super hard
materials [7], which are useful and promising candidates.
In the present research work the focus is on CoWO4
nanostructural morphology like nanorods, nanobelt, nano-
wires and nanoplates etc. [8]. CoWO4 can be synthesized
in the powder form by means of the following methods:
The conventional solid-state reaction method at high tem-
perature, wet chemical methods such as co-precipitation,
polymeric precursor method and hydrothermal/solvother-
mal method, and spray pyrolysis method [8–10] of which
chemical precipitation technique is the most profitable and
appropriate for the synthesis of the metal tungstate. The
metal tungstate could be synthesized by employing the
simplest method called chemical-precipitation method. The
conventional ceramic method has the disadvantage of
consuming long time, much energy besides facilitating
uncontrolled particle growth. Hydrothermal and
solvothermal methods make it possible to synthesize
their wide applications are limited by the specific
requirement of solvents and reaction vessel. The wet
chemical synthesis method was found to be much useful
for the synthesis of nanoparticle in which the particle
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 J Mater Sci: Mater Electron

growth and the morphology could be controlled. Therefore, nanoparticles were analyzed using a HIOKI 3532-50 LCR
we opted for the co-precipitation method for the synthesis HITESTER over the frequency range 50 Hz–5 MHz.
of CoWO4 nanoparticles because this method offered
advantages like simple and rapid preparative procedure,
easy control of particle size and composition besides 3 Results and discussion
offering various possibilities to modify the particle surface
state and overall homogeneity. This paper discusses the 3.1 XRD analysis
preparation of CoWO4 nanoparticles using the precipitation
method. The prepared nanoparticles were characterized by The crystal structure and phase purity of the samples were
powder X-ray diffraction analysis, FTIR, scanning electron characterized by XRD. X-ray powder diffraction patterns
microscopy (SEM), EDX, transmission electron micro- of CoWO4 nanoparticles are shown in Fig. 1. All the peak
scope (TEM) UV-analysis, PL and dielectric properties of positions and their relative intensity were indexed with ore
the CoWO4 nanoparticles that could be determined. of tungsten CoWO4 monoclinic phase with space group:
P2/c. Later the XRD pattern indicated that due to Wo4 and
Co3O4, there was no ternary oxide phase. This result was in
2 Experimental procedure harmony with the earlier reports [10]. The average grain
size (D) was calculated using the Scherrer formula
CoWO4 nanoparticles were synthesized via chemical pre- 0:9k
cipitation technique. Typical synthetic procedures required D¼ ð1Þ
b cos h
analytical grade cobalt II acetate [Co(C2H3O2)2] and dis-
odium tungstate (Na2WO4) to be dissolved in double dis- where k is the X-ray wavelength, h is the Bragg diffraction
tilled water separately under constant stirring. On adding angle, and b is the FWHM of the XRD peak appearing at
the prepared Cobalt metal-ion solution to tungstate solution the diffraction angle h. The average grain size of the
drop by drop for minimum 15 min, the violet colored CoWO4 nanoparticles could be determined by employing
precipitates were got. Then without losing time 0.1 M of the Scherrer’s formula and it was found to be about 54 nm.
polyethylene glycol (C2nH4n?2On?1) was added to the
above mixture as a surfactant. Stirring was to be done 3.2 FTIR analysis
continuously until the completion of precipitation followed
by 15 h aging. Then the end product was separated by FTIR spectroscopy finds extensive use in the study of the
means of centrifugation and washed thoroughly with nature of surface adsorbents in nanoparticles. Because of
deionized water, ethanol and acetone, one after the other. their large surface area, the modification of the surface of
Lastly after drying at ambient temperature for 24 h, the the nanoparticles by a suitable adsorbate can generate
powder was calcined at 500 °C for 6 h. The XRD pattern different properties. The high surface to volume ratio
of the CoWO4 nanoparticles was recorded by using a influences the activity at the surface of the nanoparticles,
powder X-ray diffractometer (Schimadzu model: XRD which differentiates it from that of the bulk. The study of
6000 using CuKa (k = 0.154 nm) radiation, with a the oxidation levels of nanoparticles prepared at different
diffraction angle between 20° and 70°. The grain size was
determined from the broadenings of corresponding X-ray
spectral peaks by using Scherer’s formula. The FTIR
spectrum of the CoWO4 nanoparticles was taken using an
FTIR model Bruker IFS 66W Spectrometer. SEM studies
were carried out on JEOL, JSM-67001. The samples nee-
ded a coating of gold for SEM analysis for the avoidance of
charging effect. TEM image was taken using an H-800
TEM (Hitachi, Japan) with an accelerating voltage of
100 kV. The colloidal nanoparticles solution had to be
dried on the copper grid before analysis. UV–Vis absorp-
tion spectrum for the CoWO4 nanoparticles was recorded
using a Varian Cary 5E spectrophotometer in the range of
400–750 nm. The PL spectrum of the CoWO4 nanoparti-
cles was recorded using the Perkin–Elmer lambda 900
spectrophotometer with a Xe lamp as the excitation light
source. The dielectric properties of the CoWO4 Fig. 1 XRD pattern of CoWO4 nanoparticles

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J Mater Sci: Mater Electron

partial oxygen pressures could be made from the FTIR

data. In order to determine the chemical structure of the
CoWO4 nanoparticles, the FTIR spectrum was observed
over the frequency range of 4000–500 cm-1 as shown in
Fig. 2. The intense band that appeared in the low frequency
region of 400–1000 cm-1 belonged to the characteristic
deformation modes of Co–O, W–O and W–O–W bridges.
The IR spectrum below 500 cm-1 could be ascribed to the
deformation modes of W–O bonds in Wo6 octahedra or the
deformation of W–O–W bridges [11]. The bands appearing
at 820 and 621 cm-1 could be associated with the O–W–O
vibration mode and the W–O bond stretching, respectively
[12]. The OH stretching vibration of surface absorbed or
internally bonded water molecules accounted for the strong Fig. 3 SEM image of CoWO4 nanoparticles
intense band in the region of 3000–3800 cm-1 [13]. The
bending mode of H–O–H was located at about 1640 cm-1.

3.3 SEM and EDX analysis

The samples were made to remain suspended in methanol

and the specimen stub was taken out after being dipped into
the liquid. The sample powder could be seen deposited
onto the surface of the stub evenly after methanol had
evaporated. This specimen was then given a coating of
gold for 2 min. Proper study of materials can be made only
when they are electrically conducting or else they give rise
to charging phenomena resulting in blurred images. The
SEM images of the CoWO4 nanoparticles were taken and
are shown in Fig. 3. The nanostructure morphology of Fig. 4 EDX spectrum of CoWO4 nanoparticles
orderly allocation of the particles was ensured from the
SEM images. The images of the particles indicated that
they were closely spherical in feature with an average appropriate amount without any impurities. This describes
crystalline size of &30–50 nm. The composition and the the atomic scale stochiometry of the compound.
element present in the compounds were studied using EDX
analysis which is illustrated in Fig. 4. There was sufficient 3.4 TEM analysis
indication that all the elements were present in the
To confirm it further, TEM observation was taken for
CoWO4 nanoparticles and the same is shown in Fig. 5.
This image bears clear evidence to the formation of
CoWO4 nanoparticles. The particles were crystalline and
equally distributed. The compounds had the particles uni-
formly distributed and were polycrystalline in nature. The
CoWO4 nanoparticles were found to have an average size
of &70 nm.

3.5 Optical properties

3.5.1 UV analysis

UV–Vis absorption spectrum of as-prepared CoWO4

nanoparticles is shown in Fig. 6. On account of the charge
transfer between ligand and metal within the ðWo2 4 Þ; the
Fig. 2 FTIR spectrum of CoWO4 nanoparticles absorption band had risen; this had been hinted by strong

123

Fig. 5 TEM image of CoWO4 nanoparticles
Fig. 6 UV–Vis absorbance spectrum and plot of (ahm)2 versus (hm)
as inset
red-shift in the absorption spectrum of CoWO4. Later it
suggested that this absorption for the formation of [Wo6]6-
complex within the wolframite structure could be directly
related. Due to the strong interaction between hole (on
oxygen) and electron (on tungsten) excitation occurred in
the excited (Wo2- 2
4 ) state. The plot of (ahm) versus (hm) for
the CoWO4 nanoparticles is shown in the inset of Fig. 6. It
reveals that the band gap of CoWO4 nanoparticles is about
2.80 eV.
3.5.2 PL studies
The PL spectrum of as-prepared CoWO4 nanoparticles
with the excitation wavelength of 350 nm is shown in
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J Mater Sci: Mater Electron
Fig. 7 PL spectrum of CoWO4 nanoparticles
Fig. 7. The spectrum clearly shows that the prepared
sample exhibits the broad blue-green emission band
centred at 453 nm with shoulders which are directly
related to the radiative transition within the [Wo4]2-
tetrahedral group. The luminescent efficiency seems to be
closely related to the process of synthesis for obtaining
particles that are not agglomerate but well formed crystals
[14].
3.6 Dielectric properties
The CoWO4 nanoparticles pellets in disk form were
studied at different temperatures. For measurements, the
samples were obtained with the diameter of *10 mm and
thickness *1 mm and a sample was placed between the
electrodes with a conventional four terminal sample
holder for investigations involving temperature variations
along with a conventional two terminal sample holder for
only ambient conditions. The sample was mounted
between copper platforms and electrodes. To ensure good
electrical contact, the faces were coated with the silver
paint. The capacitance and the dissipation factor of the
parallel plate capacitor formed by the copper plate and the
electrode having the sample as a dielectric medium were
measured. The dielectric constant was evaluated using the
relation,
Cd
er ¼ ð2Þ
e0 A
where d is the thickness of the sample, A is the area of
the sample, C is the capacitance and e0 is permittivity of
free space. Analysis of the dielectric nature of CoWO4
nanoparticles gives facts about the electric field alloca-
tion within the CoWO4 nanoparticles. The experiment
was carried out for the frequencies from 50 Hz to 5 MHz
with the different temperatures 30, 50, and 70 °C
J Mater Sci: Mater Electron

Fig. 8 Variation of dielectric constant with log frequency at various Fig. 9 Variation in the dielectric loss factor with frequency at various
temperatures (30, 50 and 70 °C) temperatures

respectively. Figure 8 shows the variation of dielectric 3.7 AC conductivity studies

constant with log frequency at various temperatures (30,
50 and 70 °C). It is observed that both the dielectric The AC conductivity of the CoWO4 nanoparticles, could
constant and the dielectric loss show similar nature. The be calculated by using the following relation:
dielectric constant of materials depends on the contri-
rac ¼ 2pe0 er f tan d ð3Þ
bution of electronic, ionic, bipolar and space charge
polarization of the frequencies [15]. All the four polar- where e0 is permittivity in free space, er is dielectric con-
ization mechanisms are active at low frequencies. Lower stant, f is the frequency and tan d is the loss factor. Electrical
frequencies and high temperatures normally assist the conduction in CoWO4 nanoparticles takes place due to
progress of space charge polarization. The low value of electrons jumping from low valence state to high valence
the dielectric constant with increasing frequency may be state. The frequency reliance behaviour in the temperature
ascribed to the loose or weak bond of ions at the lower interval 30–70 °C for the ac conductivity is shown in
frequency range [16]. Still higher values of the dielectric Fig. 10. With the increase in frequency for all temperatures
constant at low frequencies are possible due to the charge the ac conductivity increased. It was observed that due to the
accumulation at the grain boundaries. Another possibility electron hopping frequency [16] ac conductivity gradually
to gain higher values is that the interfacial/space charge increased with increase in the frequency of the applied ac
polarization due to heterogeneous dielectric structure.
Due to the fact that beyond a certain frequency of the
external field, the polarization decreases with the
increase in frequency and then reaches a constant value,
the hopping between various metal ions cannot follow
the alternating field. It was noticed that the value of the
dielectric constant decreased with the increase in the
frequency [17]. The dielectric loss represents the energy
dissipation in the dielectric system. Figure 9 shows the
variation in the dielectric loss factor with frequency at
various temperatures. It was observed that the dielectric
loss decreased with the increase in frequency and
acquired a low value in the high frequency region. The
study showed that the dielectric loss suddenly fell at
lower frequencies and constant nature was noticed at
higher frequencies. Due to the space charge polarization
it was observed that the dielectric loss decreased with the Fig. 10 Variation in the AC conductivity with frequency at various
increase in frequency for all temperatures [18, 19]. temperatures

123

field. Reduction in space charge polarization with higher
frequencies could cause increase in conductivity.
4 Conclusion
The paper thoroughly discussed the synthesis of CoWO4
nanoparticles by the employment of simple chemical pre-
cipitation technique. The fact that the CoWO4 nanoparti-
cles belonged to the monoclinic structure with the space
group of P2/c was revealed by the XRD pattern. In addition,
the average grain size of the CoWO4 nanoparticles could
be determined by employing the Scherrer’s formula and it
was found to be about 54 nm. FTIR spectrum also sup-
ported the formation of CoWO4 nanoparticles. The fact that
the nanoparticles agglomerated to form spherical-shaped
particles was established by the SEM analysis. The average
particle size of CoWO4 nanoparticles was found to be
70 nm. With the help of UV–visible absorption spectrum
and PL spectrum, the optical properties were studied. The
optical band gap was found to be 2.80 eV. The fact that the
prepared CoWO4 nanoparticles exhibited the broad blue-
green emission band centred at 453 nm was confirmed by
the PL spectrum. Analysis with regard to variations of the
dielectric constant, the dielectric loss, and the AC con-
ductivity with frequency and temperature for CoWO4
nanoparticles was performed. From the dielectric studies it
became clear that with an increase in the frequency both
the dielectric constant and the dielectric loss decreased.
The AC electrical conductivity was found to increase with
an increase in the temperature and the frequency.
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J Mater Sci: Mater Electron
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