Arabian Journal for Science and Engineering

https://doi.org/10.1007/s13369-023-08615-w

RESEARCH ARTICLE-PHYSICS

Investigation of Frequency-Stable Colossal Permittivity in ZnO

Ceramics using Impedance Spectroscopy
Muhammad Rafi1,2 · Uzma Ghazanfar1 · Anas Ramzan1 · Khaqan Shati2 · Muhammad Atif3 ·
Muhammad Nadeem2

Received: 13 August 2023 / Accepted: 14 December 2023

© King Fahd University of Petroleum & Minerals 2024

Abstract
The most recent research and developments are driven by colossal permittivity (CP) materials due to their potential use in
modern microelectronics and high-energy density storage applications. Even though, to date, many CP materials have been
discovered, the task of developing them with the required high performance remains highly challenging. We present a tangible
example, polycrystalline ZnO ceramic, that presents a highly frequency-stable CP (> 104 ) as well as a low dielectric loss (~ 0.3)
over a broad temperature range from 278 to 433 K. Multifunctional polycrystalline ZnO nanoceramics are prepared through
one-pot hydrothermal route and sintered at 300 °C and 600 °C. The highly magnified scanning electron microscopic images
reveal excellent grain growth at high temperature. Temperature-dependent impedance spectroscopy is employed for pellet
sintered at (600 °C) to explore different conduction mechanisms at various temperature ranges. The distribution of relaxation
times (DRT) method is used to design the best equivalent circuit model for fitting impedance data. The non-Debye behavior
of real permittivity (2 ) is well explained by fitting with Cole–Cole formalism. The change in the conduction mechanism is
estimated around 343 K, and an adiabatic polaronic model is used to estimate activation energies of cations through different
electroactive regions. The correlate barrier hopping (CBH) model is applied to measure electrical trapping parameters (like
binding energy, hopping distance, barrier height, etc.) at various temperatures. Our finding presents a systematic approach
toward frequency-independent ZnO ceramics with a stable colossal permittivity which can potentially be applied to develop
energy storage devices.

Keywords ZnO ceramic · Structural analysis · Surface study · Optical study · Dielectric permittivity

1 Introduction
Temperature and frequency-stable colossal permittivity (CP)
materials (ε’ ~ 1000) with low tangent loss have got much
attention, because of their enormous demand in swiftly pro-
gressing electronic industries [1]. The colossal permittivity
(2 ) materials have great importance due to their basic aca-
demic physics and their practical applications in various
electronic devices. In the last decade, many researches have
B Muhammad Rafi
rajarafi786@gmail.com
B Muhammad Nadeem
mnadeemsb@gmail.com
1 Department of Physics, University of Wah, Wah Cantt, P.O.
Wah Cantt, Pakistan
2 Polymer Composite Group (PCG), Directorate of Science,
P.O. Nilore, PINSTECH, Islamabad, Pakistan
3 Functional Materials Lab, Department of Physics, Air
University, PAF Complex E-9, Islamabad, Pakistan
been carried out on high dielectric materials (ε’ > 103 ) mostly
PbTiO3 , CaCu3 Ti4 O12 (CCTO), etc., but applications of
these materials are restricted to a specific temperature range
[2, 3]. In comparison with multilayer ceramic material, zinc
oxide (ZnO) is considered the most functional ceramic mate-
rial for the manufacturing of electronic, photonic, and solar
cell devices due to its attractive attributes. This comprises
high real permittivity, low tangent loss, wide energy gap (E g
~ 3.37 eV), and outstanding mechanical stability [4]. Zinc
oxide belongs to the n-type semiconductor family (II-VI)
having some unique properties, such as piezoelectric, dielec-
tric, and optical, due to tetrahedrally bonded ions (Zn2+ –O2− )
with hexagonal wurtzite structure [5].
ZnO has some substantial advantages over other oxides
like natural abundance, inexpensive, easy to synthesis, and
environment-friendly with excellent physical and chemical
stability. Many chemical approaches are used to prepare
ZnO nanoceramics such as sol–gel [6], solvothermal [7],
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microwave [8], co-precipitation [9], and hydrothermal [10].
These chemical approaches have various synthesis param-
eters (like sintering temperature, pressure, reaction time,
surfactant, etc.) which are mandatory to control the growth
and shape of nanostructures [11]. The hydrothermal method
is considered the most preferred, suitable, and direct method
that can produce the desired shape of nanostructures with
good morphological control [12]. It is a widely used tech-
nique for the mass-scale production of nanomaterials involv-
ing growth of nanoparticles by employing high-pressure and
temperature conditions in an aqueous solution. Li et al. [13]
prepared undoped high-pressure-treated ZnO ceramics by
conventional sintering. Similarly, S. Ibadat et al. [14] reported
high dielectric constant at low frequency (~ 102 Hz) for ZnO-
sintered microstructures at high temperature. In these studies,
the realistic high permittivity 2 of ZnO is associated with
porosity, Maxwell–Wagner (MW) polarization, and hetero-
geneities present in the system [15].
Achieving high dielectric constant with low tangent loss
in a single crystal is an extremely challenging task. This
increases the demand of high dielectric materials which are
easy to prepare. In contrast with complex high permittivity
materials, ZnO is easy to fabricate. ZnO has got consider-
able attraction due to its versatile nature in supercapacitors,
resistive switches, and piezotronics [16]. Various kinds of
ZnO structures, ceramics, and films are reported relatively
having low permittivity (< 1500 at 102 Hz) through vari-
ous temperature ranges [17]. The dielectric characteristics
of ceramic materials are greatly influenced by geometrical
morphology, amount of porosity, and the grain bound-
aries. Porous ceramics with controlled porosity can have
a low-frequency dielectric constant of about ~ 106 . In a
recent article, Ndayishimiye et al. [18] reported polydimethyl
siloxane composites prepared using cold sintering. In cold
sintering, ZnO structures at high-frequency value of dielec-
tric constant (2 ~ 140 at 105 Hz) belong to dense isotropic
grains and charges are accumulated at grain boundaries.
Consequently, the origin of the high dielectric permittivity
is credited to an extrinsic mechanism, e.g., the barrier layer
capacitances (BLC), likely at twin boundaries [19]. Some
discussions are present about grain boundaries where non-
linear current–voltage behavior of CCTO and barrier layer
capacitance, where TEM measurements shows that grain
boundaries play key role on electrical properties. We have
already published the temperature- and frequency-dependent
impedance spectroscopy about ZnO nanoparticles prepared
via novel composite hydroxide-mediated approach. Here
large dielectric permittivity arises from Maxwell– Wagner
relaxation occurring at the interfaces of grains (Gs) and grain
boundaries (GBs) [20].
Generally the realistic high dielectric constant of ZnO
corresponds to Maxwell–Wagner polarization effects but the
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Arabian Journal for Science and Engineering
proper explanation about the origin of observed real permit-
tivity at both sides (low and high frequency) [21].
Latest data published by Maru et al. [19] show low
dielectric permittivity due to incorporation of TiO2 in ZnO
structure. Due to the formation of the conductive networks
at the interface of ZnO and TiO2 (having similar ZnO and
TiO2 contents) across the composite. Similar trends at room
temperature are also reported by Tkachenkov et al. [22],
showing Co-, Cu-, Ni-doped ZnO nano-objects. Reduced
real permittivity ranging from (2 ~ 20–70) with significantly
low tangent loss is reported for different nanosheets whose
thickness varies between 18 and 34 nm. Various contribu-
tions to the resistive and capacitive characteristics of ceramic
materials can be convoluted using impedance spectroscopy.
Charge transport mechanism in polycrystalline materials is
typically influenced by physical parameters like grain bound-
ary, grain resistance/capacitance, and electrode interface.
Detailed understanding of functionality of electroceramic
materials is essential to deconvolute these contributions.
In the present research, we report temperature- and
frequency-stable giant dielectric constant for ZnO material
with low tangent loss. The dielectric characteristics of a
material originate from the shape of microstructures and the
nature of dipoles. The two major constituents that account
for a high dielectric constant are grains and grain bound-
aries. Various dielectric relaxation processes are present in
various frequency ranges. Interfacial polarization plays a
key role in colossal permittivity at the low-frequency side.
For central frequency range (102 –105 ), interfacial polariza-
tion is relaxed and reached toward the plateau region (ε’
becomes fixed with frequency) for each temperature range.
Comprehensive structural, electrical, and optical studies are
carried out using X-Ray diffraction (XRD), scanning electron
microscopy (SEM), impedance spectroscopy (IS), and dif-
fuse reflectance spectroscopy (DRS). Temperature-sensitive
dielectric parameters like dielectric constant, tangent loss,
complex impedance spectra, dielectric relaxation, modulus,
and the ac conductivity in the applied frequency range are
analyzed. To the best of our knowledge, very few studies are
available about colossal dielectric studies of frequency-stable
ZnO ceramic materials in a temperature range of 278–433 K
with the change of conduction mechanism around 343 K.
2 Experimental Section
One-pot hydrothermal process is employed here for the syn-
thesis of ZnO nanoparticles. Analytical-grade 99% pure (Zn
(NO3 )2 .6H2 O & NaOH) (Sigma-Aldrich) are thoroughly
mixed and transferred to autoclave and heat-treated in an
oven for 180 °C for 24 h. Resultant white precipitates are
filtered and washed repeatedly. After drying precipitates at
60 °C in the oven, it is ground using mortar and pestle to make
Arabian Journal for Science and Engineering

Table 1 Comparison of
presented method against other Methodology Sintering Crystallite size 2 tan δ E g (eV) References
established methods temperature (nm)

Gel combustion 600 °C/3 h 16 10 0.8 3.50 [23]

Co-precipitate 550 °C/2 h 46 200 1.6 3.3 [24]
Solid state 900 °C/2 h 50 500 – – [25]
CHM 400 °C/4 h 15 1800 0.9 – [26]
Sol–gel 350 °C/6 h 42 160 – – [27]
Hydrothermal 600 °C/4 h 22–32 5200 0.3 3.21 This study

a fine powder. The resultant powder is sintered in the furnace

at 300 °C and 600 °C for 4 h. The obtained powders are pel-
letized under a hydraulic press into pellets having thickness
~ 1.5 mm and diameter ~ 10 mm. We further sintered pellets
at 300 °C and 600 °C in the carbolite furnace for 6 h. Table
1 represents comparison of hydrothermal method with other
established techniques.
The PANalytical Xpert Pro DY 3805 Powder (λ  1.54 Å)
is used for X-ray diffraction. The prepared samples are
scanned with a step size of 0.02° within the range of
20° – 80°. The surface studies of ZnO nanoparticles are
carried out using FESEM Hitachi-S4800 and MIA3 TES-
CAN. Pellet sintered at 600 °C (labeled as ZnO-600) is
selected for optical and dielectric studies. Diffuse reflectance
spectroscopy (DRS), Shimadzu UV2450PC, is employed
to perform optical studies for band gap analysis. Compre-
hensive impedance spectroscopic analysis is followed using
Alpha-N analyzer (Novocontrol, Germany). Temperature-
dependent electrical studies of ZnO-600 are carried out in
a temperature range (278–433 K) over the wide frequency
range. Temperature control is maintained using a DC power
supply and immersing the improvised sample holder in a flow
of liquid nitrogen Dewar. Before impedance measurement,
pellets are silver painted on both sides to make contacts and Fig. 1 Refined XRD of ZnO samples sintered at (a) 300 °C and (b)
600 °C
dried in an oven at 100 °C for 2 h; an AC voltage amplitude
of 0.2 V is set for the whole temperature range in the applied
frequency range. parameters, scale factors, asymmetry coefficients, lattice
parameters, and (FWHM) full width at half maximum are
all refined at the same time [2]. Debye Scherrer’s formula is
3 Results and Discussion used to determine the crystallite size D [30].

3.1 XRD Study 0.9λ

Figure 1 demonstrates XRD intensity patterns for ZnO
samples sintered at 300 °C and 600 °C, which reveals
a single-phase polycrystalline hexagonal wurtzite structure
having space group P63mc with a characteristic peak (101)
(JCPDS#36–1451) [28]. To estimate structural parameters,
Rietveld refinement is performed using FullProf software
[29]. Crystallinity is identified by employing pseudo-Voigt
function to model peak profile. The background polynomial
D (1)
βcosθ
where λ value is (~ 1.54 Å), β is the FWHM of the strongest
peak’s intensity (101), diffraction angle is given in radi-
ans. The estimated values of lattice constant, cell volume,
microstrain, dislocation density, crystallite size, and relia-
bility factors are compared in Table 2; these results are in
well accordance with previously reported values [31, 32].
Moreover, at 300 °C, the average crystallite of ZnO-300

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Table 2 Structural parameters: a comparison of ZnO-sintered samples on the alignment of dipoles under applied electric field. In
at different temperatures nature, electroceramics are electrically inhomogeneous due
Parameters ZnO-300 ZnO-600 to the presence of different electroactive regions. Interfacial
polarization plays an important role in tuning the dielectric
Lattice parameters ab 3.26 3.24 characteristics of materials, while at low frequencies (f < 102
(Å) Hz) grain boundaries effect is more dominant than grains
c (Å) 5.22 5.20 [26]. Figure 3a, b demonstrates the frequency dependence
c/a 1.60 1.60 of dielectric permittivity (2 ) and tan loss for the ZnO-600
V (Å3 ) 48.26 47.61 sample, where temperature varies from 278 K to 433 K. It
Average micro-strain (%) (ε) 0.33 0.21 is clearly seen that in all temperature ranges dielectric per-
Average dislocation density (δ) 0.29 0.13 mittivity becomes frequency independent within frequency
(%) range (1–105 Hz); this plateau region shifts with the rise of
D Average (nm) D(nm) 22 32 temperature (> 278 K) up to 105 Hz. In the upcoming section,
Rietveld reliability Rp 11.2 9.2 Cole–Cole formalism is tried to understand multi-dispersive
parameters Rwp 13.9 9.0 relaxation present in this plateau region. The subject mate-
Re 12.2 10.0
rial shows giant dielectric behavior in all temperature ranges,
which improves significantly with the rise of temperature and
χ2 3.60 1.87
exhibits a colossal response [4].
The sample ZnO-600 generally shows different relaxation
behaviors at different frequency ranges. Moreover, the dielec-
nanoparticles is close to 22 ± 0.2 nm. The crystallite size
tric properties of ZnO-600 show frequency-independent
increased significantly as sintering temperatures increased
behaviors over a very broad temperature-frequency range,
(600 °C), and is estimated as 32 ± 0.4 nm [28].
which makes this material the most suitable candidate for
energy storage devices [35]. At frequency (~ 102 Hz), ε’ is
3.2 SEM Study maximum and then slightly decreases with increasing fre-
quency to 105 Hz. High dielectric behavior is mainly due
Surface morphology and grain growth of different sintered to interfacial polarization occurring at low-frequency region
samples are investigated using FESEM. Figure 2a and b [28]. For the intermediate frequency range (102 –105 Hz),
shows extremely dense semi spherical [33] nanostructures extrinsic effect is more dominant which is caused by grain
with a wide, inhomogeneous distribution of crystallite sizes boundaries, interfacial polarization, and voids, respectively
[14]. All of these micrographs are taken from the sin- [36]. Real permittivity estimated at low frequency is around
tered powder of ZnO samples. In comparison with the (ε’ ~ 3.4 × 105 ) and decreases to (ε’ ~ 8.82 × 103 ) at 102
ZnO-300 sample, high-temperature-sintered ZnO-600 dra- Hz. The grain boundary effect is more effective below 102
matically introduces voids and grain development due to Hz, so interfacial polarization is accountable for tuning the
the diffusion of smaller crystallites into relatively larger dielectric value in this frequency range. For the intermedi-
ZnO crystallites. Morphological analysis supports structural ate frequency range, interfacial polarization is relaxed and
studies, which reveals that ZnO-600 sample shows good reaches toward the plateau region (ε’ becomes fixed with
crystallinity with improved structural parameters as shown frequency) for each temperature range [1]. Drop in dielec-
in Table 2, so this sample is chosen for further electrical tric (ε’) at high frequency is caused due to slow response of
studies [34]. Inset of Fig. 2a, b shows the distribution of dipoles, as these dipoles are unable to follow rapidly varying
crystallite size using Image J software which estimates crys- AC field [10].
tallite size (D) between 35 and 60 nm. Moreover, Fig. 2c, Figure 3a (inset) shows activation energy (E a ~ 0.32 eV)
d shows electron-dispersive spectroscopy (EDS), a compo- calculated from peak frequency (τ  1/2πfmax ) for each tem-
sitional comparison of sintered samples. Elemental spectra perature range using Arrhenius relation [24, 37]
confirm purity of the sample, having zinc and oxygen atoms
belonging to ZnO matrix; no foreign element is detected  
Ea
within the detection limit. The lower inset of Fig. 2c, d shows τ  τo exp − (2)
KT
the atomic and weight percentage of each element.
Figure 3b shows frequency dependence of tanδ at vari-
3.3 Dielectric Analysis ous temperatures. At low-frequency region, tan delta shows
relaxation peak that corresponds to variation in ε’; with the
The dielectric constant (2 ) measures the energy storage rise of frequency this peak gradually decreases to lowest
capacity of dielectric materials while polarization is based value (tanδ ~ 0.3) as shown in Table 3. The tangent loss

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Arabian Journal for Science and Engineering

Fig. 2 FESEM micrographs of (a) ZnO-300 (b) ZnO-600 and (c, d) represent EDS spectra with atomic and weight %age

Fig. 3 Frequency and temperature dependence of real permittivity and Tan δ

Table 3 Comparison of real

permittivity with tangent loss Dielectric constant (ε ) Tan (δ)

Temp(K) 10 Hz 103 Hz 105 Hz 5 MHz 10 Hz 103 Hz 105 Hz 5 MHz

278 770 630 28 12 112 3 1 0.3

318 1045 852 50 18 303 4 1.8 0.5
358 1495 1145 130 38 1072 6 2 0.8
408 10,125 4386 2892 545 1512 18 3 4
433 52,072 6918 5422 2892 2895 76 3.2 4.2

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Fig. 4 a–c Cole–Cole nonlinear curve fitting of real permittivity (278–433 K). d Arrhenius plot for dielectric relaxation
peak at high frequency (> 105 Hz) is originated due to
the relaxation process caused by Zn+2 –Vo dipoles present
at grains [14]. Due to grain growth relaxation peak shifts
toward high-frequency side. Figure 3b (inset) shows acti-
vation energy E a ~ 0.36 eV calculated from peak position
using Arrhenius method as already discussed. S. Cole and H.
Cole proposed an empirical formula, to understand nature of
dielectric relaxation over a wide range of frequencies [38].
Figure 4 shows temperature-dependent nonlinear curve fit-
ting of Cole–Cole equation for non-Debye type relaxation
behavior present in real permittivity; this formulation is
applied over the frequency-independent region 102 –105 Hz.
Mathematical definition of the complex dielectric constant
(ε*) by Cole–Cole equation is as follows [39]:
εs − ε∞
ε∗  ε∞ +
1 + (iωτ )β
where ε∞ is the limiting value of the dielectric constant at
high frequencies, εs is the static dielectric constant, τ is the
relax time, and β is the constant whose values lie 0 to 1.
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Arabian Journal for Science and Engineering
Equation 4 denotes real part of the Cole–Cole expression:
1 + (ωτ )cos βπ
ε  ε∞ +(εs −ε ∞ ) 2
(4)
1 + 2(ωτ )β cos βπ
2 + (ωτ )
2
Table 4 shows Cole–Cole study directed multi-dispersive
relaxation and showed a deviation from Debye relaxation
process. As distribution factor (β) has value less than 1
which implies that distribution of relaxation has broader peak
than Debye peak. The fitted distribution factor (β) values at
various temperatures lie within 0.77 to 0.9 indicating that
ZnO-600 has wider relaxation peak [39]. It is found that fitted
(3) relaxation time (τ ) at different temperatures follows Arrhe-
nius law Eq. 2. Figure 4d shows plot Ln (τ ) vs 1/T, where
solid lines are fitted lines using relation Eq. 2. From slope
of fitted lines, we estimate activation energies (E a ) of dielec-
tric relaxations which vary from 0.29 eV to 0.7 eV, where
conduction mechanism changes around 343 K [10] (Fig. 5).
Arabian Journal for Science and Engineering

Table 4 Dielectric parameters

extracted from fitting of Temp (K) ε∞ εs τ β
Cole–Cole Eq. (4)
278 15 820 1.05 × 10–5 0.77
328 38 1123 2.9 × 10–5 0.9
373 30 1400 1.01 × 10–5 0.79
403 25 3800 2.02 × 10–6 0.77
433 50 6500 3.4 × 10–7 0.8

Fig. 5 a–d Complex impedance plots (Z" vs. Z’) of ZnO-600 are shown for various temperature ranges tested

3.4 Impedance Study
Complex impedance study is used to explain the electroactive
regions and electrical properties of polycrystalline materials
[14, 40]. Figure 6a–d illustrates complex impedance plane
plots for ZnO-600 sample comprising of experimental and
fitted data which are explained on the basis of the best equiv-
alent circuit model as proposed by distribution of relaxation
time (detailed discussion is presented in the next section)
[41]. At each temperature range, there are two semicircular
arcs: high-frequency arc represents grains and low-frequency
arc represents grain boundaries. The total resistance (RT 
RG + RGB ) of the material is given by the intersection of the
curve at the low-frequency side. Figure 5a–c shows high-
frequency arc passing through origin which confirms there
is no contribution of any contact resistance. With the rise of
temperature, high-frequency arc shows small shifts above the
origin due to high relaxation frequencies above measurement
limit which is more easily resolved using DRT formalism will
be explained in the equation 6.
Table 5 indicates the value of capacitance increases with
the decrease in resistance of grain RG and grain boundaries
RGB in operational temperature range. Both depressed semi-
circular arcs having centers lie below the real Z’- axis and

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 Arabian Journal for Science and Engineering

Fig. 6 Temperature-dependent distribution of relaxation time (DRT) on ZnO Ceramic at a 278 K to 373 K and b 398 K to 433 K

Table 5 ZView fitted parameters

for ZnO-600 Temp (K) R1 ( ) RG ( ) RGB ( ) C G (pF) C GB (nF)

278 – 80,000 110,710 2.35 2.58

318 – 25,930 27,392 2.54 2.80
338 – 12,200 13,103 3.62 3.08
413 80 98 300 7.5 8.1
433 32 55 173 7.2 8.8

Fig. 7 Bod plots for a (Z") vs. log (f)) and b (M") vs. log (f)) formalisms

can be seen in the impedance spectrum showing semicon-
ducting behavior with non-Debye type relaxation follows the
Cole–Cole formalism. There are two relaxation mechanisms
associated with two semi-circular arcs having various relax-
ations with different time constants (τ  RC), where C is
the capacitance and R is the resistance associated with the
respective phases, which is also confirmed in the modulus
plot (Fig. 7).
In ceramics on the basis of resistance, grains are con-
sidered as electronically or ionically conducting in applied
temperature range in this system while grain boundaries
(GBs) usually behave as a barrier to charge carriers mobility.
The resistive behavior of grain boundaries can be under-
stood by the depletion of space charge layers produced by
the repulsion of charges in the grain boundary regions [42].
Table 5 shows a decrease in the diameter of semicircular
arcs (corresponding to reduction in RG and RGB) with the

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Arabian Journal for Science and Engineering
rise of temperature; this implies the presence of a thermally
triggered conduction mechanism in grain and grain bound-
aries. Generally in most of the oxides, resistance of grain
boundaries is higher than grains due to uneven distribution
of oxygen atoms and bond linkage which plays as the car-
rier’s traps and generates a barrier layer. Additionally, the
capacitance of grain boundaries (10–10 F to 10–8 F) is higher
than the grains (~ 10–12 F).
The deviation from ideal behavior of capacitance is set-
tled by the constant phase element (CPE). Z-view computer
software is used to best fit experimental data as shown in
Fig. 5a–d, the electrical components R1 (CPE1 ) and R2 (CPE2 )
both are coupled in parallel to best fit the high- and low-
frequency arcs, while Rs  Ohmic resistance is used in
Fig. 5d to fit temperature range (398–433 K). The fitting of
impedance plane plots of R1  RG , R2  RGB , CPE1 , CPE2 ,
ng, and ngb is within 2–3% fitting error. Impedance plots show
two clear semicircular arcs in the applied temperature range
278–373 K, and with further rise in temperature (398–433 K)
both arcs diffuse to single one, and an applied equivalent cir-
cuit model applied in each temperature set is shown in inset
of Fig. 5d. The arrow points toward increase in the frequency,
and the corresponding equivalent circuits that try to adapt the
observed data are shown in inset of Fig. 5a–d. The CPE can
be convoluted into capacitive/resistive elements using for-
mula (C  R(1−n)/n CPE1/n ) where “n” is a measurement of
divergence from ideal behavior whose values lie within (0
< n < 1), where 0 implies pure resistive and 1 implies pure
capacitive behavior [43].
Distribution of relaxation times (DRT) is an effective tool
used for deconvolution of impedance spectroscopic data.
This analysis predicts the most accurate equivalent circuit
models, in order to analyze impedance data in time domain
[41]. The significance of this method is to resolve different
relaxations present in electroactive regions by transforming
the data from frequency (f ) domain to time (τ ) domain. The
main goal of DRT analysis is to estimate γln(τ ) at the applied
temperature range. The experimental data Z exp measured at
given frequencies are “fitted” against a model Z DRT , which
is expressed in Eq. 5 as under [44].
 ∞
g(τ )
Z DRT ( f )  R∞ + dτ (5)
0 1 + iωτ
where R∞ is the ohmic resistance and g(τ ) is a suitable func-
tion that describes the time relaxation characteristics of the
system being studied. To accommodate the frequency data
usually collected on a logarithmic scale, Eq. 5 can be rewrit-
ten as:
 ∞ γ (lnτ )
Z DRT ( f )  R∞ + dlnτ (6)
−∞ 1 + iωτ
Figure 5a is evident in DRT analysis which corresponds
to two equivalent circuits that respond to two main relaxation
peaks present as shown in 278–373 K. While Fig. 5b shows
DRT study of 398–423 K, third relaxation at high frequency
endorses series resistance R1 in the equivalent circuit (is stand
for the displacement of high-frequency arc from origin as
shown in Table 5).
Figure 7a shows the plots of Z" plotted against the log f for
sample ZnO-600 at various temperatures. These spectra can
be used to examine the characteristic of the sample’s most
resistive phase. Here with the rise of temperature, peaks shift
gradually toward higher frequency side. The higher values
of frequency at upper temperatures range are evident for the
temperature-dependent carrier mobility in grains and at grain
borders. This implies that charges may hop between the con-
fined locations (Zn+2 –O−2 ) responsible for the conductivity.
Grain growth creates more defect free grain interiors, related
to dipoles (Zn+2 –Vo ) relaxation at high-frequency side [45].
In the present system, two distinct relaxations occurred
here: the larger intense peak created at lower frequency side
is credited to the relaxation process linked with the grain
boundaries (GBs) and the second peak is connected with
the grains (Gs). Figure 7a shows, at 2 kHz, a larger peak
which is credited to the relaxation process at grain bound-
aries, while the second shoulder emerged around 200 kHz
corresponds to the relaxation process at grains. Decrease in
Z peak intensities of spectra along with the shift of peaks
toward high-frequency side with the improvement in tem-
perature shows the increase in dipoles created due to thermal
activation [14]. Above 343 K, two peaks merge to single one
due to growth of space charge polarization as shown in inset
of Fig. 7a. The Arrhenius expression (Eq. 2) is used to esti-
mate activation energy (E a ) of charge carriers through the
material which is estimated by using peak frequency being
0.36 eV (± 0.01) [46].
Figure 7b shows dependence of frequencies on modulus
(M") at given temperature range, and only one broad peak
exists which corresponds to the grains. Contact contributions
can be ruled out based on the very low modulus values at
low frequencies. With increasing temperature, the position
of the M" peak shifts to the high-frequency side. The value
of M"(0.039) shows maximum at 1.4 × 106 Hz, which tends
to decreases gradually at high-frequency range (> 107 Hz).
Corresponding activation energy (Ea ) derived from peak fre-
quency is 0.3 eV (± 0.02) [35].
The electrical conduction process is investigated in depth
by employing (i) small polaron hopping (SPH) and (ii)
Mott’s variable range hopping (M-VRH). Using polaronic
model, temperature dependence of resistance of material
(RG , RGBs, and through the material RT ) is expressed using
relation R/T  Ao exp (E a /KT), where Ao , K, and E a are the
pre-exponential factor, Boltzmann constant, and activation
energy, respectively. Figure 8a shows experimental data that
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Fig. 8 Temperature dependence
against RG , RGB, and total
resistance RT using a SPH and
b M-VRH Model
Fig. 9 a Z’ plotted against log (f), b average normalize change with temperature
best fitted to the adiabatic SPH model, and the corresponding
activation energies obtained above 343 K are 0.66 ± 0.01 eV,
0.68 ± 0.02 eV, and 0.7 ± 0.02 eV for the conduction at
Gs, GBs, and through the bulk, respectively. Change in lin-
ear behavior tells change in conduction mechanism observed
below 343 K where activation energy of carrier is about 0.3
± 0.01 eV [35].
Figure 8b illustrates charge transport through electroac-
tive region at low temperature (278 K) is explained on the
basis of M-VRH. Hopping length is estimated using rela-
tion ln(R/Ro )  (T /T o )1/4 where T o is the temperature factor
and is given by T o  18α 3 /K B N(E F ). Here N(E F ), 1/α, and
K are the density of states, confinement length, and Boltz-
mann constant, respectively. The confinement length  1/α 
measured from the above-mentioned equations is 0.2 Å. Hop-
ping length decreases with the rise of temperature which is
in good agreement with the earlier reported results [39]. In
comparison with M-VRH model, the SPH model governed
the conduction as best fitted in whole temperature range due
to its better reliability factor [45].
123
Arabian Journal for Science and Engineering
Figure 9a shows variation in real part Z of impedance with
the rise of frequency at various temperature ranges. Each tem-
perature plot follows a frequency-independent region where
impedance gradually decreases with the rise of frequency. At
high frequency, (Z’) appears to merge for all plots, demon-
strating the possible release of the space charges. There are
two main causes of decrease in real impedance (Z’) value
with increase in temperature: the first one is the increase in
the kinetics of the charge carriers and the second is decrease
in the density of the trapped charges. Figure 9b shows average
normalized change (ANC) with temperature, where ANC is
expressed as (Z’/f )/Z’o [47]. Here Z’ is based on Z l -
Z h , where Z l  and Z h  are the respective values of imagi-
nary impedance Z’ at lowest (f l ) and highest (f h ) frequencies,
respectively. The ANC expression may divide into two por-
tions: the first one is low temperature side which is less than
343 K (where ANC has a temperature independent region
recorded up to 1.0 × 10−7 Hz−1 ). This region is followed by
a second or frequency-dependent region where a sudden drop
starts 343 K which pointed out change in conduction mecha-
nism as already discussed. Characteristic decrease in average
Arabian Journal for Science and Engineering
Fig. 10 Bode plots for electrical conductivity
normalized changes from 9.65 × 10−8 Hz−1 at 343 K to 7.8
× 10−8 Hz−1 at 428 K. This confirms the presence of more
than one conduction mechanism in subject material at whole
temperature range [48].
3.5 AC Conductivity
Figure 10 shows frequency dependence of real part of con-
ductivity (σac ) of sintered pallet at the whole temperature
range [49]. Low-frequency (or plateau) regions at each tem-
perature plot follow a region where conductivity increases at
high-frequency side (f > 104 Hz). This dispersion with rise of
frequency can be explained by Koop’s theorem [50] (1951),
which states that the materials composed of two layers: grain
with high conductivity and grain boundary with low conduc-
tivity. Grain boundaries are effective at lower frequencies,
with strong resistance and steady conductivity. Jonsher uni-
versal law proposed the relation for the hopping conduction
of the conductivity [51].
σT (ω, T )  σo (T ) + σ (ω, T ) (7)
The first term is the conductivity σo (T ), where ω →
0 corresponds to dc conductivity. The second term is the
frequency-dependent and pure ac due to hopping process
at octahedral site. AC conductivity follows universal power
law σ (ω)  Aωs ; here ω is angular frequency, and A
and s are temperature-dependent parameters. The frequency
range above which the slope changes is called hopping
frequency [52]. Figure 10 indicates the development of sec-
ondary frequency-independent region (II) around 343 K,
followed by frequency-dependent region as conductivity
plot shifts high to low temperature side. This confirms the
presence of single, bi-well, and multiple activation barriers
present at high and low temperature side, respectively, in
the opted frequency range [53]. The dc conductivity σo (T )
is temperature-dependent region originating from the ther-
mally activated charge carriers growing with the rise in
temperature. This confirms that there are multiple activation
barriers present in this frequency range; Table 6 shows bar-
rier height at different temperatures at 100 Hz. AC conduction
mechanism explains on the basis of different available con-
duction models like overlapping of large polaron tunneling
(OLPT), non-overlapping small polaron tunneling (NOSPT),
and correlate barrier hopping (CBH) [32]. CBH model holds
when value of exponent  s decreases with temperature,
which confers movement of localized charges responsible
for conduction mechanism. Table 6 illustrates comparison
of different trapping parameters like binding energy (W m ),
minimum hopping length (Rmin ), and barrier height (W ω )
at different temperatures. Binding energy (W m ) of hopping
polaron can be measured using slope (s) by the following
relation [45]:
6T K B
Wm  (8)
1−s
where T is the applied temperature and K B is the constant
and already explained above. Binding energy also helps to
measure hopping distance Rω and minimum hopping dis-
tance Rmin (1 MHz) as follows [54]:
Rω  (e2 /εo )/(Wm + K B T ln(τo ω)) (9)
Rmin  (2e2 /Wm εo ) (10)
where  e is the electronic charge, εo is the permittivity of free
space, and τo is the relaxation time of carrier and is equivalent
to inverse of phonon frequency (10−13 s). Hopping distance
(Rω ) at various temperatures is calculated for 100 Hz, 2 kHz,
and 1 MHz. The physical picture which has emerged from
the above discussion implies that binding energy and hop-
ping distance, which are AC frequency-assisted phenomena,
decrease with the rise of temperature as shown in Table 6;
these results are in agreement with the already reported
ceramics.
Here a, b, and c depict the selected frequencies like 100 Hz,
10 kHz, and 1 MHz, respectively.
3.6 Optical Study
Band gap of semiconducting material is defined as minimum
amount of energy required to release electron from its bound
state [55]. Figure 11 demonstrates DRS spectrum of ZnO-
600 sample, where optical reflectance is measured in range
of 200–700 nm. Optical band gap (E g ) is derived from the
famous Kubelka–Munk (K-M) function F(R) [15]:
(h F(R))2  A(h − E g ) (11)
(1 − R)2 1
F(R)  (12)
R 2
123

Table 6 AC research used to
estimate various conductivity Temp.(K) Slope (s) W m (eV)
parameters
283 0.80 0.73
323 0.66 0.49
363 0.62 0.48
403 0.56 0.47
Fig. 11 Kubelka–Munk function versus band gap energy (eV)
where R is the reflectance and A is the proportionality con-
stant. The slope intercept of curve to the horizontal axis
provided the band gap (E g ) value. The band gap is essentially
the least amount of energy required to energize an electron to
a condition band where it can participate in conduction. The
band gap of ZnO-600 sample is measured by inducing the
curve between (hv) and (F(R) hv)2 . We can measure band
gap (E g ~ 3.21 eV) by extrapolating the curve, due to the for-
mation of point defects and oxygen vacancies created during
the hydrothermal process; the band gap of sintered ZnO is
lower than the defect-free ZnO (3.37 eV) [8]. Optical char-
acteristics of ZnO material are based on band gap that lies
between 3.2 and 3.3 eV, and is mostly employed in integrated
sensors and photo-conductors [56].
4 Conclusions
In conclusion, refined XRD (Xray diffraction) structural
profiles for ZnO-300 and ZnO-600 nanostructures confirm
the preparation of a single-phase hexagonal wurtzite struc-
ture via hydrothermal approach. SEM (scanning electron
microscopy) studies reveal growth in microstructures with
temperature while EDX (electron dispersive spectroscopy)
confirms the material’s purity. Due to its high crystallinity
and robust grain growth, ZnO-600 sample is selected for fur-
ther electrical and optical studies. The frequency-dependent
dielectric and impedance studies of sintered pellet are
123
Arabian Journal for Science and Engineering
W ω (eV) Rmin (Å) Rωa (Å) Rωb (Å) Rωc ( Å)
0.61 0.15 50 25 20
0.70 0.23 26 24 18
0.79 0.23 19 24 17
0.87 0.24 14 23 14
carried out using impedance spectroscopy. The frequency-
independent dielectric permittivity at various temperatures
shows colossal behavior (2 ≥ 103 ) with low tangent loss (~
0.3). The dielectric permittivity remains stable within a spe-
cific frequency range across the entire the temperature range,
owing to the absence of phase transition.
The Cole–Cole formalism is applied on frequency-stable
region to estimate the relaxation behavior, indicating an acti-
vation energy 0.7 eV. Complex impedance plots of ZnO-600
illustrate changes in the size and shape of the semicircular arc
with increasing temperature showing changes in the resis-
tive and capacitive values of the materials. These changes
suggest a thermally activated conduction mechanism. The
distribution of relaxation time (DRT) formalism is employed
for deconvolution of impedance data, enabling the resolution
of different relaxations present in electroactive regions. This
approach validates the selection of equivalent circuit models.
By employing polaronic model, the temperature-dependent
fitted resistance reveals a change in the conduction mech-
anism around 343 K, a finding further validated by other
formulations. The frequency-dependent behavior of ac con-
ductivity follows Jonscher’s power law, wherein the correlate
barrier hopping (CBH) model emerges as the most appropri-
ate model that represents universal behavior for the exponent
 s . Electrical parameters such as W (binding energy), R
m min
(minimum hopping distance), and W ω (barrier height) calcu-
lated at various temperatures using the CBH model are found
to be realistic. The strength of binding energy (W m ) associ-
ated with the change in magnitude, i.e., difference of barrier
hopping with minimum hopping distance of (Rω − Rmin ),
indicates that for higher binding energies, charge carriers are
confined to smaller localized areas. Detailed explanations are
provided for the change in hopping distance (Rω ) with tem-
perature at specific frequencies 100 Hz, 10 kHz, and 1 MHz,
respectively. In the present research, the detailed microscopic
and spectroscopic studies about colossal dielectric response
will open up new avenues for power/energy storage appli-
cations. The colossal permittivity (~ 52,072) with reduced
tangent loss (~ 0.3) for ZnO-600 sample makes this material
favorable for high-frequency devices.
Acknowledgements We acknowledge the support of Polymer Com-
posite Group (PCG), PINSTECH Islamabad, Pakistan, for experimental
and impedance analysis.
Arabian Journal for Science and Engineering
Author Contributions MR involved in investigation, experimentation
and writing the original draft. UG took part in supervision, review and
editing. KS involved in methodology, validation and formal analysis,
review and editing. AR took part in resources and formal analysis. MA
took part in resources and reviews validation. MN participated in con-
ceptualization, resources, review and editing.
Data Availability Required data associated with the submitted
manuscript will be available if needed.
Declarations
Conflict of interest The authors declare that no funds, grants, or other
support is received during the preparation of this manuscript.
Ethical Approval Not applicable.
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