crystals

Article
Exploring Relaxation Phenomenon in Cu-Substituted
Ba2NiWO6 Double Perovskites
Shahid M. Ramay 1 , Mohammed H. Aldosary 1 , Ghulam M. Mustafa 2, * , Sadaf Saba 3 , Shahid Atiq 4 ,
Sikandar Aftab 5 and M. A. Ebdah 1

1 Physics and Astronomy Department, College of Science, King Saud University, P.O. Box 2455,
Riyadh 11451, Saudi Arabia
2 Department of Physics, Division of Science and Technology, University of Education, Lahore 54770, Pakistan
3 Department of Physics, Government College University, Faisalabad 38040, Pakistan
4 Centre of Excellence in Solid State Physics, University of the Punjab, Lahore 54590, Pakistan
5 Department of Intelligent Mechatronics Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu,
Seoul 05006, Republic of Korea
* Correspondence: [Link]@[Link]

Abstract: Double perovskites are an emerging class of functional materials with a great deal of
durability perspective owing to their inherent flexibility in cation coordination selection. Here, we
synthesized pristine and Cu2+ -doped Ba2 NiWO6 utilizing the solid-state reaction route to investi-
gate their structural, morphological, and dielectric behavior. Structural examination revealed the
development of a cubic crystal structure for both compositions, and Cu2+ integration in Ba2 NiWO6
decreases the crystallite size. The spherical-shaped grains shrink in size and start agglomeration with
Cu2+ incorporation. The incorporation of Cu2+ reduces the grain size, leads to accumulation of space
charges at the grain boundaries, and thus, facilitates growth in the space charge polarization. This
increases the dielectric constant of the material, thus making these compositions viable for advanced
miniaturized electronic devices.

Keywords: double perovskites; relaxation phenomenon; Maxwell–Wagner model; impedance

Citation: Ramay, S.M.; Aldosary, spectroscopy; dielectric properties
M.H.; Mustafa, G.M.; Saba, S.; Atiq,
S.; Aftab, S.; Ebdah, M.A. Exploring
Relaxation Phenomenon in
Cu-Substituted Ba2 NiWO6 Double
1. Introduction
Perovskites. Crystals 2023, 13, 625.
[Link]
The constantly growing population leads to high demands for energy utilization that
cryst13040625 are expanding enormously with time. The usage of non-renewable energy sources such
as fossil fuels and coal generates CO2 which disrupts the biosphere. Therefore, there is a
Academic Editors: Andrei V.
crucial requirement to develop other cost-effective, non-renewable, and environmentally
Shevelkov and Maxim N. Sokolov
friendly energy sources. Hydro, wind, nuclear and solar power are considered to be the
Received: 16 February 2023 better alternatives of renewable energy sources [1]. Among these sources, solar power
Revised: 30 March 2023 technology has attracted extensive research interest across the globe owing to its eco-
Accepted: 31 March 2023 friendly nature and easy installation. In addition, it does not involve the emission of any
Published: 5 April 2023 hazardous gases. However, there is the fundamental issue with solar power generation that
it cannot work at night time, triggering the need for energy storage devices [2]. At present,
batteries, fuel cells, and electrostatic and electrochemical capacitors are commercially
available energy storage devices with a limited storage capacity. A large part of ongoing
Copyright: © 2023 by the authors.
research work is devoted to enhancing the energy storage capacity of these devices. In
Licensee MDPI, Basel, Switzerland.
this regard, dielectric materials are the most promising class of materials that can enhance
This article is an open access article
energy storage capacity, particularly in devices where energy is stored electrostatically [3].
distributed under the terms and
Transition metal oxides in spinels, perovskites, and double perovskite oxides formulations
conditions of the Creative Commons
have immense potential as a dielectric materials and have been extensively investigated in
Attribution (CC BY) license (https://
[Link]/licenses/by/
the recent past. If these materials possess a higher dielectric constant and lower dielectric
4.0/).
loss, they can be utilized in resonators, capacitors, switches, and in all electrical appliances.

Crystals 2023, 13, 625. [Link] [Link]

Crystals 2023, 13, 625 2 of 11

The high values of dielectric constant and low values of loss are significant conditions for
manufacturing elegant and miniaturized devices, provided that the fabricated parts show
constant reliability under a wide range of operating temperatures [4].
Among the available potential candidates, double perovskite oxides are a very exciting
class because of their wide compositional range and structural flexibility, which make
them suitable for a wide spectrum of applications. Double perovskites, which have the
general formula A2 MM0 O6 , can accommodate a variety of cations at the A, M and M0
sites such that the overall composition is electrically neutral. They have been a strong
focus of research because of their exciting structural and physical characteristics such
as magnetic, electrical, photocatalytic, and optical properties. Therefore, materials with
the structure of double perovskites possess properties consistent with applications in
luminescent, photocatalytic, and dielectric materials [5]. Tungsten-based double perovskites
have been the subject of scientific inquiry since 1950. The structural properties of double
perovskites have been investigated experimentally using Raman spectroscopy and diffuse
reflectance, and theoretically by density functional theory (DFT), and found to be stable.
Moreover, the dielectric characteristics of the tungsten-based compositions have been
calculated to regulate their capability for microwave and ceramic material applications [6].
In the recent past, researchers devoted their attention to examining the structural, mag-
netic electric, and multifunctional features of double perovskites in both experimental and
theoretical areas. For instance, Hanif et al. studied the cubic double perovskites Sr2 XNbO6
(X = La, Lu) using density functional theory (DFT) and investigated their structural, op-
tical, elastic, thermoelectric, and electronic properties by the FP-LAPW approach. It was
observed that these compounds are direct bandgap semiconductors with bandgap values
of 4.02 eV for Sr2 LaNbO6 and 3.7 eV for Sr2 LuNbO6 [7]. Similarly, Diao et al. calculated
the optical phonons of Ba2 MgWO6 (BMWO) utilizing DFT with a local density approach as
ab initio mode and presented the vibrational and eigenvector configuration of every mode.
The Raman spectra were also analyzed and various modes were identified with the help of
first-principle measurements: F2g (1) , F2g (2) at 126 cm−1 and 441 cm−1 , Eg (O) at 538 cm−1 ,
and A1g (O) at 812 cm−1 . FTIR spectra were calculated and fit utilizing three classical
parameters and four model features. IR active modes were allocated as F1u (1) at 144 cm−1 ,
F1u (2) at 284 cm−1 , F1u (3) at 330 to 468 cm−1 and F1u (4) at 593 to 678 cm−1 . The FTIR
investigation specified that the F1u (2) mode directed by vibrations of Mg–O6 has a greater
impact on the dielectric characteristics of double perovskites [8]. In addition to theoretical
investigations, Dehury et al. experimentally studied the structural, morphological, and
dielectric characteristics of BiHoCoTiO6 composition. The dielectric behavior exhibited
first (Tc1 ) and second (Tc2 ) transition temperatures at 175 ◦ C and 325 ◦ C, respectively.
The Nyquist plot was modeled with capacitance resistance (CR) equivalent circuit, and
various parameters such as bulk or grain, grain boundary, capacitance, and resistance were
investigated. The bulk resistance (Rb ) reduces considerably when the temperature rises
from RT to 300 ◦ C [9]. Likewise, Das et al. examined the structural, dielectric, and magnetic
properties of Pr2 CoTiO6 material. According to this report, the magnetic calculations below
4 K exposed the antiferromagnetic response in the material, whereas at a Neel temperature
(TN ) of about 17 K, the value of magnetic moment (µeff ) was 6.92 µB . The reported value
of the dielectric constant was 45.5 and the loss tangent value was 1.2 [10]. In addition,
Vilesh and Subodh synthesized BaBiLiTeO6 and SrBiLiTeO6 double perovskites through
a solid-state reaction route and studied the structural, morphological, and dielectric char-
acteristics. They observed that the grain size of the microstructure was >3 µm. At a
frequency of 1 MHz, both compounds had porosity-modified dielectric constant. The value
for BaBiLiTeO6 was 49.5 and that for SrBiLiTeO6 was 34.4, whereas the value of loss tangent
for BaBiLiTeO6 was 0.029 and that for SrBiLiTeO6 was 0.028 [11]. In the report of Coskun
et al., iridium (Ir)-substituted LaCrO3 (LCO) was fabricated utilizing a solid-state reaction
approach to examine the influence of Ir substitution on ac-conductivity (σac ) and dielectric
characteristics. It was observed that the value of dielectric constant and conductivity was
Crystals 2023, 13, 625 3 of 11

reduced with the substitution of Ir but with increasing temperature and frequency, the
value was increased [12].
In the current study, we elaborate on the dielectric properties of Ba2 NiWO6 and
Ba2 Ni0.5 Cu0.5 WO6 synthesized by the solid-state reaction method and investigate their
structural, morphological and dielectric characteristics as a function of frequency to explore
their suitability for energy storage and high-frequency miniaturized electronic devices.

2. Synthesis Method and Characterization Techniques

The solid-state reaction approach is versatile in chemical synthesis processes, par-
ticularly when the reaction involves oxides as precursors. It is usually assisted by an
intermediate and repeated ball milling process. This approach gives high yield, a uniform
particle size distribution, fewer impurities and high selectivity of the product. It has been
extensively employed for the synthesis of variety of nanomaterials, including spinels, per-
ovskites, and double perovskites. In the present study, this technique was used for the
synthesis of Cu-substituted Ba2 NiWO6 . In this process, BaO (Reagentplus, 99.99%, Saint
Louis, MO, USA), NiO (Nanochemazone, 99.99%, Saint Louis, MO, USA), CuO (Sigma
Aldrich, 99.99%, Saint Louis, MO, USA), and WO (Sigma Aldrich, 99.99%, Saint Louis, MO,
USA) were used as precursors. These precursors were measured according to stoichiomet-
ric ratios and mixed by the planetary ball-milling technique at a speed of 500 rev/min to
form a homogenous mixture [13]. After that, these materials were ground followed by
calcination at 1000 ◦ C for 2 h to obtain the single phase BaNiWO6 and BaNi0.5 Cu0.5 WO6 .
Alsabah et al. synthesized A2 YVO6 (A = Mg, Sr) double perovskites using solid-state route
and investigated their optical behavior through UV-Vis spectroscopy [14]. Similarly, Bharti
et al. fabricated Sr2 CeSbO6 double perovskites using the same approach and explored
the dielectric behavior. Based on the observed value of activation energy, they suggested
that this type of behavior is associated with the hopping mechanism of electrons [15].
In addition, Chen et al. in their study, covered most of the chemical approaches which
could be employed to synthesize oxides-based double perovskites and highlighted various
aspects regarding their applications [16]. These calcined samples were again ground to
obtain a fine powder and ultimately transformed to pellet form with a 10 mm diameter and
1.1 mm thickness for different characterizations [17]. Before characterizations, the samples
were sintered at 400 ◦ C for 2 h. The schematic of the solid-state reaction method is shown
in Figure 1.

Figure 1. Schematic of solid-state reaction method.

Crystals 2023, 13, 625 4 of 11

The structural examination was performed utilizing Rigaku XRD, and the morpho-
logical study was carried out using Field Emission Scanning Electron Microscope (FESEM
JEOL FESEM (Tokyo, Japan) with Oxford EDX) operated at 5 kV. The dielectric behavior
was evaluated using a Precision Impedance Analyzer (PIA).

3. Result and Discussion

3.1. Structural Analysis
The X-ray diffractograms of the prepared samples of Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6
were used to confirm the development of their cubic double perovskite phases. Figure 2
illustrates the XRD patterns of Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 . It was found that peaks
in the XRD pattern of Ba2 NiWO6 emerged at 18.93◦ , 31.16◦ , 36.71◦ , 38.40◦ , 44.64◦ , 48.90◦ ,
55.44◦ , 59.13◦ , 64.98◦ , 68.35◦ and 73.82◦ 2θ values, and these peaks were in good agreement
with ICSD card no. 01-073-0135, indicating the formation of a cubic double perovskite
phase with space group Fm3m [18]. The value of lattice constant (a) calculated from the
position of the peaks was determined to be 8.0850 Å. A small shift in the (220) peak towards
a smaller 2θ with the incorporation of Cu2+ in the place of Ni2+ is attributed to the larger
ionic radius of Cu2+ (0.73Å) as compared with Ni2+ (0.69Å) [19]. This shifting of peaks
towards smaller 2θ values reflects the expansion of the unit cell and the value of the lattice
parameter for Ba2 Ni0.5 Cu0.5 WO6 to 8.1137 Å [20,21]. The crystallite size (D) was computed
using Scherrer’s expression:
kλ
D = (1)
βcosθ B
where k is 0.9, which is the shape factor, λ represents the wavelength of CuKα , β signifies
the full width at half maximum (FWHM), and θ B is the Bragg diffraction angle [22]. The
reliability of the crystal structure data was further reinforced by performing the Rietveld
refinement using HighScore Plus software. This technique provides a platform to compare
the experimental data of the series under investigation with reference data available in the
database. This comparison generates a difference plot between experimental and standard
Crystals 2023, 13, x FOR PEER REVIEW
data based on the difference in peak position, peak shape, and peak height. This difference 5 of 12
is quantified in terms of various residual factors, including the profile factor (Rp ), weighted
profile factor (Rwp ), and expected profile factor (Rexp ), to determine the most important
factor, 2 (<10) indicates the goodness
factor,the
theso-called
so-calledgoodness of of
goodness fit fit
(GoF). TheThe
(GoF). small value
small of χof
value χ2 (<10) indicates the good-
ofness
fit to structural data. The Rietveld refined graphs of both compositions
of fit to structural data. The Rietveld refined graphs of both compositions along along
with their
with
residual factors are presented in Figure 3a,b.
their residual factors are presented in Figure 3a,b.

[Link]
Figure IndexedXRD
XRDpatterns
patternsofofBa
Ba22NiWO
NiWO66 and
and Ba
Ba22Ni0.5
0.5Cu
Cu0.5
0.5WO
WO6. 6 .
Crystals 2023, 13, 625 5 of 11

Figure 2. Indexed XRD patterns of Ba2NiWO6 and Ba2Ni0.5Cu0.5WO6.

Figure 3. Rietveld refinement plot of (a) Ba2NiWO6 and (b) Ba2Ni0.5Cu0.5WO6.

Figure 3. Rietveld refinement plot of (a) Ba2 NiWO6 and (b) Ba2 Ni0.5 Cu0.5 WO6 .

3.2.
[Link]
Morphologicaland andElemental
ElementalAnalysis
Analysis
Figure 4a,c illustrate the FESEM
Figure 4a,c illustrate the FESEM images
images of of
thethe NiWO
Ba2Ba 6 and
2 NiWO Ba2Ni
6 and Ba0.52Cu 0.5WO
Ni0.5 6 com-
Cu0.5 WO6
pounds,
compounds,respectively
respectively[23].[23].
TheThe
FESEM
FESEM imageimage of of
undoped
undopedBaBa 2NiWO
2 NiWO 6 reveals
6 revealsthe thewell-
well-
shaped
shapedgrains
grainsofofvarious
varioussizessizesstacked
stackedover
overone oneanother.
another. The
Thesize
sizeof ofthese
theseparticles
particleslies
liesin
in
the
therange
rangeof of200–600
200–600nm. [Link]
smallergrains
grainsare aremostly
mostlyspherical
sphericalininshape;
shape;the themedium-
medium-
sized grains
sized grainsare
are of
of oval-shaped,
oval-shaped,and andthe
thelarger
largergrains
grains(>400
(>400nm)nm)are areofofirregular
irregularshape.
shape.
However,these
However, these particles
particlesare are well-connected,
well-connected,leaving leavingbehind
behindaa very
verysmall
small spacespace between
between
them,which
them, whichleads
leadsto tothe
theformation
formationof ofaaquite
quitedensedensecomposition
compositionthat thatisisfavorable
favorablefor forbetter
better
dielectric materials.
materials. TheThe incorporation
incorporation of of Cu 2+
Cu resulted
resultedin
inaareduction
reductionin inaverage
averagegrain grainsize
size
dielectric 2+

owingto
owing tothe
the difference
differencein in ionic
ionic radius
radius of
of the
the host
host and
and dopant
dopant [24].
[24]. This
This mismatching
mismatchingof of
ionic radius
ionic radius may induce
inducestructural
structuraldeformation,
deformation,prevent preventcrystal
crystalgrowth,
growth, andand thusthus
suppress
sup-
the particle
press size [25].
the particle size [25].

Figure 4. (a) FESEM image of Ba2 NiWO6 , (b) EDX spectrum of Ba2 NiWO6 , (c) FESEM image of
Ba2 Ni0.5 Cu0.5 WO6 , and (d) EDX spectrum of Ba2 Ni0.5 Cu0.5 WO6 .
Crystals 2023, 13, 625 6 of 11

EDX spectroscopy is a powerful approach and when used in conjunction with SEM, is
capable of distinguishing the presence of different elements in any composition by detecting
the X-rays emitted from those elements. In addition to the detection of elements, it also
helps to quantify these elements. The EDX spectra of Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6
are presented in Figure 4b,d. The presence of Ba, W, Ni, and O in the EDX spectrum of
pure Ba2 NiWO6 and the presence of Cu in addition to all other elements in the spectrum of
Ba2 Ni0.5 Cu0.5 WO6 indicate impurity-free compositions within the detection limit of EDX.
The atomic and weight percentage of all involved elements are also incorporated in the
EDX spectra and are in good agreement with their stoichiometric formula, thus confirming
the formation of the exactly targeted compositions [26].

3.3. Dielectric Properties

The dielectric behaviors of Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 are controlled by various
parameters, including the dispersion of cations, polarization process, and nano-structural
configuration. The determined value of parallel capacitance (Cp ) was used in relation
ε0 = Cp d/Aε0 to compute the real part of the dielectric constant (ε0 ), where A, d and ε0 repre-
sent the area of the pellets, thickness, and permittivity of free space (ε0 = 8.85 × 1012 F/m),
respectively. The equation ε00 = ε0 tan δ was used to estimate the imaginary part of the
dielectric constant (ε00 ), where tan δ represents the loss tangent. Figure 5a,b depict the
frequency-dependent variation of ε0 and ε00 for Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 , respec-
tively. The values of ε0 and ε00 are greater for Ba2 Ni0.5 Cu0.5 WO6 because, as can be seen
in the SEM image of Ba2 Ni0.5 Cu0.5 WO6 , the grain size is very small. According to Koop’s
theory, the reported dielectric distribution is ascribed to Wagner and Maxwell’s type of
Crystals 2023, 13, x FOR PEER REVIEW 7 of 12
interfacial polarization, as the cumulative results of ionic, interfacial, dipolar, and electronic
polarizations determine the characteristics such as the dielectric constant [27]. The polar-
ization of space charges at the heterogeneous dielectric structure and grain boundaries
of space
are charges
associated at the
with theheterogeneous ε0 and ε00 structure
large values ofdielectric and grain is
. This polarization boundaries
caused byaretheasso-
con-
ciated with the large values of ε′ and ε″. This polarization is caused by the contaminants,
taminants, sintering temperature, synthesis methods, grain structure, and pores [28]. The
calculated value of ε0 forsynthesis
sintering temperature, methods, grain
both compositions structure,
at various and
applied pores [28].are
frequencies The calculated
presented in
value 1.
Table of ε′ for both compositions at various applied frequencies are presented in Table 1.

Figure 5. Frequency-dependent variation in (a) real part, (b) imaginary part of dielectric constant,
Figure 5. Frequency-dependent variation in (a) real part, (b) imaginary part of dielectric constant,
and (c) loss tangent.
and (c) loss tangent.
TableFigure 5c shows
1. Calculated how
values thereal
of the losspart
tangent
of the (tan δ) forconstant,
dielectric Ba2 NiWO 6 and Ba
imaginary 2 Ni
part of0.5 Cudielectric
the 0.5 WO6
samples responds to the applied field with
constant and the loss tangent at various [Link] frequency. It was calculated using the
relation tan δ = 1/2πfRp Cp , where 2πf represents the angular frequency (ω), Rp stands
for theFrequency
parallel resistance, and CBa 2NiWO6 Ba2Ni0.5Cu0.5WO6
p denotes the parallel capacitance. The polarization lags
the electric field because of impurities, defects, and grain boundaries,ε″
ε′ ε″ tan δ ε′ which aretan δ
linked
1 kHz
to the loss 16.40 amount
tangent. The highest 9.53 of electrical
0.58 23.38 is transferred
energy 19.75 to ions0.84 when
10 kHz frequency16.32
the vibrational 9.87
of charge carriers 0.60
matches the22.97
frequency of 20.12 0.89 as
the electric field;
100
a result, wekHz 15.98loss peak
can see a power 9.05 in Figure
0.57 5c. The 21.62
relation for18.35
higher loss0.85 in the
sample250 is ωτ
kHz = 1, where τ represents
15.80 relaxation
8.85 time,
0.56 which
21.07 is related to
17.43 τ = 1/2p 0.83p is
as
the jumping
500 kHz probability per unit time,
15.72 8.75so ωτ =0.55
1 can also20.80
express as ω max
19.99= 2p [29].0.82It was
750 kHz 15.69 8.72 0.55 20.69 16.82 0.81
1 MHz 15.68 8.71 0.55 20.62 16.70 0.80

Figure 5c shows how the loss tangent (tan δ) for Ba2NiWO6 and Ba2Ni0.5Cu0.5WO6 sam-
Crystals 2023, 13, 625 7 of 11

observed that Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 exhibited a rapid decrease at frequency
104 Hz, which indicates that at this frequency, the space charge polarization was no longer
actively responding to the applied field [30,31].

Table 1. Calculated values of the real part of the dielectric constant, imaginary part of the dielectric
constant and the loss tangent at various frequencies.

Frequency Ba2 NiWO6 Ba2 Ni0.5 Cu0.5 WO6

ε0 ε00 tan δ ε0 ε00 tan δ
1 kHz 16.40 9.53 0.58 23.38 19.75 0.84
10 kHz 16.32 9.87 0.60 22.97 20.12 0.89
100 kHz 15.98 9.05 0.57 21.62 18.35 0.85
250 kHz 15.80 8.85 0.56 21.07 17.43 0.83
500 kHz 15.72 8.75 0.55 20.80 19.99 0.82
750 kHz 15.69 8.72 0.55 20.69 16.82 0.81
1 MHz 15.68 8.71 0.55 20.62 16.70 0.80

The complex modulus graph provides significant information on the relaxation prop-
erty of the material [32]. The following equations were used to calculate the electric
modulus’s real part (M0 ) and imaginary part (M00 ):

M0 = ε0 /(ε0 2 + ε00 2 ) (2)

Crystals 2023, 13, x FOR PEER REVIEW M00 = ε00 /(ε0 2 + ε00 2 ) 8 of (3)
12

Here, ε0 and ε00 represent the real and imaginary parts of the dielectrics, respectively.
The frequency-dependent values of M0 and M00 are displayed in Figure 6a,b. In Figure 6a,
the lower
values werevalues M0 started
smallofand and M00increasing
are shown in the
with the low-frequency range. Initially,
increase in frequency, these
became maxi-
values
mum atwere small and
a particular started increasing
frequency with thedeclining.
and then started increase in frequency,
Different became
values of M′maximum
in differ-
at a frequency
ent particular ranges
frequency and
reveal then
the started declining.
asymmetric behavior of Different of M0 in different
valuesperovskites.
these double In ad-
frequency
dition, theranges reveal
position thepeak
of the asymmetric
in the M″behavior
graph of thesetodouble
helps identifyperovskites.
the regimesIn for
addition,
long-
the position of the peak in the M 00 graph helps to identify the regimes for long-range
range hopping and short-range hopping, which is a fundamental feature of polycrystal-
hopping
line andmaterial.
ceramic short-range
In thehopping, whichrange,
low-frequency is a fundamental featuremove
the charge carriers of polycrystalline
over the long-
ceramic material. In the low-frequency range, the charge carriers
range whereas, in the high-frequency range, charge carriers can only jump move over the
tolong-range
the short-
whereas,
range [33].in the high-frequency range, charge carriers can only jump to the short-range [33].

Figure
Figure 6.
6. Variation
Variation in
in (a)
(a) real
real part,
part, and (b) imaginary
and (b) part of
imaginary part of modulus
modulus with
with frequency
frequency for
forBa
Ba2NiWO
NiWO6
2 6
and Ba2Ni0.5Cu0.5WO6.
and Ba2 Ni0.5 Cu0.5 WO6 .

Complex impedance analysis is an interesting and exciting approach to investigating

a material’s electrical response to the applied a.c. field in the given frequency range. The
measurement of impedance is similar to sensing the material’s accumulative resistive and
capacitive response originating from the different intergrain and intragrain nature. The
reorientation of dipoles, charge transport, and generation of space charges all are influ-
ls 2023, 13, x FOR PEER REVIEW 9 of 12

Crystals 2023, 13, 625 8 of 11

of the material [37]. The value of resistance offered by these parts can be computed from
the x-intercepts ofComplex
these semicircles.
impedanceThe following
analysis is an relation couples
interesting the values
and exciting of grain
approach to investigating
boundary resistance (Rgb) resistance and grain boundary capacitance (Cgb):
a material’s electrical response to the applied a.c. field in the given frequency range. The
measurement of impedance is R
ωmax similar to sensing the material’s accumulative
gbCgb = 1 (4) resistive and
capacitive response originating from the different intergrain and intragrain nature. The
where ωmax signifies the maximum
reorientation of dipoles, value of frequency.
charge transport, and generation of space charges all are influenced
The peaks byofthe
semicircles
frequency areofconnected
the applied to relaxation
field [34]. frequency.
The variation At room
of realtemperature,
(Z0 ) and imaginary (Z00 )
the relaxationparts
timesof(τ) for this composition
impedance are presented canin beFigure
determined by these
7a,b. The peaks of
high value andZ0 can be frequency is
at low
calculated using the equation:
associated with the accumulation of space charges at the grain boundaries giving rise to
the large value of space charge τ=R polarization.
gbCgb
The value of Z0 decreased with (5) the increase
in frequency, which is due to the enhanced conductivity of the materials. The value of
However, Z0inisthe present
larger for Baanalysis, we
2 Ni0.5 Cu found
0.5 WO only one semicircle
6 compared with Ba2 NiWOwhich6 , matched with
and this difference is more
the grain boundary,
pronouncedwhichinwas
the significantly
lower frequency affecting theThis
region. electrical value of Zof0 for
larger response fabricated
Ba2 Ni0.5 Cu0.5 WO6 is
compounds. The maximum
consistent with diameter of the semicircle
its morphology. of Ba2Nigrains
The smaller-sized 0.5Cu0.5 WO6 demonstrates
provide more intergrain area and
its highly insulating
thus provide more resistance to the charge flow. The imaginary partresistance
performance in contrast to other compositions because the of the impedance is the
parameter forcapacitive
this semicircle is its of
reactance diameter. However,
the material, which with
hasCu substitution,
an2+inverse a consistent
relationship with the frequency
increase in sample
of thediameter was observed.
applied field; therefore,Additionally,
the value of Z 00 decreases
this increase in diameter
with demon-
an increase in frequency, as
shown
strates a rise in in Figureof
the resistance [Link] sample and a decrease in the conductivity [38].

Figure 7. Variation in (a) real part, (b) imaginary part of impedance with frequency, (c) Nyquist plot,
Figure 7. Variation in (a) real part, (b) imaginary part of impedance with frequency, (c) Nyquist plot,
and (d) variation in ac conductivity with frequency for Ba2NiWO6 and Ba2Ni0.5Cu0.5WO6.
and (d) variation in ac conductivity with frequency for Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 .

The a.c. conductivity

Figure 7c (σ ac) of Ba2a
illustrates NiWO 6 and
Nyquist Baa2Ni
plot, 0.5Cu0.5
graph WO6 was
which studied
compares theusing
Z0 and Z00 parts of
Josher’s power law. This law is stated as σ(ω) = σ + σ , where the total
impedance over a wide frequency range between 1 kHz and 1 MHz. This graph
ac o conductivity of the is typically
system is denoted by σ(ω), σ denotes the electrical conductivity which is frequency
used to explore the electrical characteristics of grain borders and grains. Ba2 NiWO6 and
ac de-
pendent, andBa σₒ 2indicates
Ni0.5 Cu0.5the
WO frequency-independent
6 exhibit non-Debye type part relaxation
of the conductivity.
and haveTherefore,
a semicircular, curved
σac is formulated as σacTwo
pattern. = ε′εdifferent
0ωtan δ, where
types ε′
ofissemicircles
the dielectric
canconstant,
be seen in ε0 the
signifies the plot
Nyquist per- based on the
mittivity of free space, ω
electrical denotes the
properties angular
of the frequency,
composition. and
The tanform
first δ represents the loss which
of a semicircle, tan- appears at
gent. Figure higher
7d displays the frequency-dependent
frequencies σac responses
and illustrates the existence of Ba
of resistance of2NiWO
grains,6 isand
also known as a
Ba2Ni0.5Cu0.5WO . The graphs can be understood on the basis of the polaron mechanism.
bulk feature. The second semicircle, which appears in the low-frequency range, illustrates
6

the grain boundaries effect [35,36]. The maximum value of Z00 from the topmost region
Crystals 2023, 13, 625 9 of 11

of the semicircle can be used to calculate the capacitance of the respective electroactive
regions of the material [37]. The value of resistance offered by these parts can be computed
from the x-intercepts of these semicircles. The following relation couples the values of grain
boundary resistance (Rgb ) resistance and grain boundary capacitance (Cgb ):

ω max Rgb Cgb = 1 (4)

where ωmax signifies the maximum value of frequency.

The peaks of semicircles are connected to relaxation frequency. At room temperature,
the relaxation times (τ) for this composition can be determined by these peaks and can be
calculated using the equation:
τ = Rgb Cgb (5)
However, in the present analysis, we found only one semicircle which matched with
the grain boundary, which was significantly affecting the electrical response of fabricated
compounds. The maximum diameter of the semicircle of Ba2 Ni0.5 Cu0.5 WO6 demonstrates
its highly insulating performance in contrast to other compositions because the resistance
parameter for this semicircle is its diameter. However, with Cu2+ substitution, a consis-
tent increase in sample diameter was observed. Additionally, this increase in diameter
demonstrates a rise in the resistance of the sample and a decrease in the conductivity [38].
The a.c. conductivity (σac ) of Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 was studied using
Josher’s power law. This law is stated as σ(ω) = σac + σo , where the total conductivity of
the system is denoted by σ(ω), σac denotes the electrical conductivity which is frequency
dependent, and σo indicates the frequency-independent part of the conductivity. Therefore,
σac is formulated as σac = ε0 ε0 ωtan δ, where ε0 is the dielectric constant, ε0 signifies the
permittivity of free space, ω denotes the angular frequency, and tan δ represents the loss
tangent. Figure 7d displays the frequency-dependent σac responses of Ba2 NiWO6 and
Ba2 Ni0.5 Cu0.5 WO6 . The graphs can be understood on the basis of the polaron mechanism.
Because of moving charge carriers, the nearby lattice becomes polarized when an electric
field is employed, allowing polarons to originate [39]. Small polarons form when the
lattice’s 3-D expansion of distortion or malformation is equal to the order of the lattice
constant, and giant polarons appear when the growth of distortion in the 3-D lattice
increases after the lattice constant. When σac decreases with an increase in frequency, large
polaron transport is used to explain the phenomenon, whereas a small polaron mechanism
describes the behavior when it increases with frequency, as in the present study. It is
observed that electrical conductivity increases suddenly in the higher frequency range and
is nearly constant in the lower frequency range. The small value of σac in the low-frequency
range is because of the active nature of grain boundaries here, which results in the large
impedance. As a result, it is found that at lower frequency ranges, a.c. conductivity is
constant, and then there is a rapid increase observed at higher frequencies [40].

4. Conclusions
In the current report, we synthesized Cu2+ -doped Ba2 NiWO6 using the solid-state
reaction technique. The structural parameters were studied utilizing X-ray diffraction,
which confirmed the formation of a double perovskite structure with an expansion of
the unit cell and incorporation of Cu at the Ni sites in Ba2 NiWO6 . The well-shaped
distinct grains of pure Ba2 NiWO6 with an average grain size of 400 nm were observed,
and a considerable decrease in grain size was observed with the incorporation of Cu. The
decrease in grain size was associated with an increase in the dielectric constant from 16.3 to
23.4 and an increase in the value of impedance from 14.1 kΩ to 23.5 kΩ at 1k Hz for
Ba2 NiWO6 and Ba2 Ni0.5 Cu0.5 WO6 , respectively. This increase in conductivity provides
better control of electronic transport and increases the feasibility of these compositions to be
utilized in miniaturized electronic devices. The significant involvement of grain boundaries,
detection of the scale of frequency for short-range and long-range hopping mechanisms,
and the involvement of small polaron provide a comprehensive understanding of the
Crystals 2023, 13, 625 10 of 11

dielectric and electrical behavior of these compositions and demonstrate their suitability
for multiple technological applications.

Author Contributions: S.M.R.; Conceptualization, Methodology, M.H.A.; Software, Data curation,

G.M.M.; Visualization, Investigation, and graph plotting, S.S.; Data analysis, S.A. (Shahid Atiq);
Supervision, Reviewing and Editing, S.A. (Sikandar Aftab); Final proof read, M.A.E.; Helping in
preparing the revision. All authors have read and agreed to the published version of the manuscript.
Funding: The authors would like to acknowledge Researcher’s Supporting Project Number (RSP2023R71),
King Saud University, Riyadh, Saudi Arabia.
Data Availability Statement: All data presented in this manuscript will be available on demand.
Acknowledgments: The authors would like to acknowledge Researcher’s Supporting Project Number
(RSP2023R71), King Saud University, Riyadh, Saudi Arabia.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.

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