Applied Physics A (2021) 127:492

https://doi.org/10.1007/s00339-021-04640-4

Dielectric and magnetic variance in ­NiCo2O4 spinels mediated

by Zn‑substitution for efficient data and energy storage
Muhammad Mubashar Munir1 · Ali Raza Khan1 · Ghulam M. Mustafa1 · S. Kumail Abbas1 · M. Akram Raza1 ·
Shahid Atiq1 · Shahzad Naseem1

Received: 19 November 2020 / Accepted: 28 May 2021

© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2021

Abstract
The presence of multiferroic behaviour in any material makes it exceptionally important for its possible significant role in
technological developments. The combination of dielectric and magnetic orders in a single device has become an intriguing
topic for material scientists in recent days. In this context, sol‒gel auto-combustion technique was utilized to synthesize
Zn-substituted ­NiCo2O4 to exploit its energy and data storage pursuits. Spinel-based cubic structure of metal cobaltites
was affirmed using X-ray diffraction technique. Enhancement in grain size mediated by Zn substitution was visualized.
Furthermore, elemental analysis confirmed the required stoichiometric contents in the samples. Koop’s theory, consistent
with Maxwell–Wagner model, elaborated the decrease in dielectric constant by enhancing the frequency. An energy loss in
dielectric relaxation was probed by measuring the loss tangent. In addition, the substitution of Zn also caused a decrease in
resistive behaviour of the samples. Magnetic analysis revealed that when Ni was replaced with Zn, the saturation magnetiza-
tion decreased which was attributed to the relative magnetic dipole moments of Zn and Ni.

Keywords Spinel cobaltites · Multiferroic properties · Dielectric characteristics · Impedance analysis · Electric modulus
study

1 Introduction order or magnetic order below a certain temperature [6]. The

type I of multiferroic materials is generally known as old
Due to fast reduction in common and traditional energy multiferroics that have different origins for ferroelectric and
sources, like oil and coal [1], some sustainable, efficient magnetic behaviours [6] and are nearly independent of each
and clean energy sources are the necessity of the hour other in a single material [7]. Such materials exhibit weak
[2]. In addition, smart and efficient materials with better coupling of ferroelectricity [8] and magnetism, exhibiting
mutual control of electric and magnetic characteristics can large spontaneous polarization and transition temperatures
provide an additional degree of freedom to multifunctional- [9]. On the other hand, the type II multiferroic materials are
ity of newly designed devices. In this context, the search also known as magnetic or new multiferroics [10], mainly
for a single device that includes minimum of two ferroic due to their strong coupling order between magnetism and
orders, commonly known as multiferroic behaviour, has ferroelectricity [11]. More significantly, ferroelectric and
been desired in the last few decades [3]. Improved perfor- ferromagnetic combination plays prominent role in various
mance of technological gadgets and versatility of electronic properties [12] like conductivity, resistivity, polarization
equipment ensure the increased efficiency of materials [4]. and magnetoresistance [13]. Therefore, these materials can
So far, multiferroic materials have been classified into two be utilized in the field of nanoscale technology, spintron-
categories, i.e. type I and type II [5], based on their sponta- ics, information storage devices [14], spin values, quantum
neous symmetry breaking appearance in switchable dipole electromagnetic devices [15], microelectronic devices, elec-
tromagnetic sensors [16], supercapacitors, electrochemical
* Shahid Atiq immune sensors [17], water splitting materials [18] and drug
[email protected] delivery [19].
Recently reported different materials like transition metal
1
Centre of Excellence in Solid State Physics, University oxides ­(BiMnO3, ­LuFe2O, ­TbMn2O5, ­YMnO3, ­HoMn2O5
of the Punjab, Lahore 54590, Pakistan

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492 Page 2 of 11 M. M. Munir et al.

and ­NiCo2O4), chromites (­ FeCr2O4, ­NiCr2O4 and C ­ oCr2O4), Using these reagents in stoichiometric amounts, a series of
perovskite ferrites and manganites of rare earth (Bi and Pb) ­Ni1−xZnxCo2O4 (x = 0.0, 0.2, 0.4, 0.6 and 0.8) was prepared.
[20], double perovskites of transition metal ions with d0, d4,
-d6 electron, mixed manganese oxides [21], organics and 2.2 Stepwise description of sample’s synthesis
halides [22] are found to exhibit multiferroic behaviour [23].
So far, Ni cobaltites, having cubic spinel structure, is the In order to synthesize the required composition, a facile
most studied as electrode materials for supercapacitors due chemical route named as sol‒gel auto-combustion has been
to their low cost, high specific capacitance, broad range of employed. The selection of this method was because of its
preparation methods and environmental-friendly character- credibility of time efficiency and cost effectiveness. In addi-
istics [24]. The cobaltites can be prepared by a variety of tion, this method provides better control of composition and
synthesis methods. For instance, Yang et al. in 2019 utilized gives self-purification during combustion process. This tech-
sol–gel method and deposited mesoporous carbon nano-fib- nique belongs to the mixing of various materials in appropri-
ers (MCNs) on Ni-substituted cobaltites nano-sheets. The ate solvents. Analytical precision balance was used to meas-
researchers reported their electrochemical properties by ure the accurate weights of metal nitrates and fuel agents.
which they revealed their use as an energy storage device These nitrates were then dissolved in de-ionized water with
[25]. Also in 2019, Kumar and Mariappan [26] fabricated chelating agents (urea and glycine) for the formation of gel.
Zn-substituted ­NiCo2O4 mesoporous rods through hydro- Magnetic stirrer was used for continuous stirring to assure
thermal process. Su et al. [27] fabricated spinel N ­ iCo2O4 the homogeneity of solution. Afterwards, the solution was
nano-wire arrays (NWAs) via facile free solution method placed on a hotplate at 95 °C for 1 h while stirred continu-
and reported their magnetic behaviour at a very high applied ously using a magnetic stirrer. The stirrer was removed when
field of 70 kOe. solution became thick and started hindering the rotation of
In the past few years, not only multiferroics but also die- stirrer. The emission of bubbles had confirmed the start of
lectric nano-composites, due to their broad range of appli- gel formation in the beaker. The temperature of the hot plate
cations, have gained much attention due to their use in the was gradually increased up to 350 °C which led to the self-
field of electronic industry. As energy density (U) is given ignition of the gel. After the completion of auto-combustion
by U = ε˳εrE2/2, so in order to achieve high energy densities, process, a black-coloured fluffy powder was obtained. The
great efforts were made to enhance the electric breakdown synthesized material was then placed in an open air to cool it
strength or relative permittivity of the dielectric materials down. An Agate mortar and pestle was used to homogenize
[28]. Moreover, enhancing the relative permittivity would the powder samples. This was followed by the calcination
make them suitable not only for the electrode materials of of the samples at 400 °C for 2 h in a muffle furnace. The
highly efficient supercapacitors but also for other energy ­NiCo2O4 sample was tagged as NCO while Zn-substituted
storage gadgets and equipment. In addition, a lot of work samples were named as NZCO. The schematic of sample
has already been devoted to the effect of Zn substitution in preparation is shown in Fig. 1.
­NiCo2O4 on gas sensing properties, as an electrocatalysis,
electrodes in batteries and supercapacitors [29–31]. So far, 2.3 Characterization
there are limited reports on the effect of Zn substitution on
the dielectric and magnetic properties of N ­ iCo2O4. Hence, The crystalline nature, crystallite size, lattice parameters
to enhance the conductivity of N ­ iCo2O4, Zn was substituted and phase formation of the samples were evaluated using
at Ni site for subsequent impedance spectroscopic and multi- a Bruker D8 Advance, X-ray diffractometer (XRD) using
ferroic analysis to exploit their potential as an efficient mate- Cu Kα radiations of wavelength 1.5406 Å. The patterns
rial for energy and data storage devices. were recorded between 2θ values of ­15ο and ­85ο. A Nova
NanoSEM-450, field emission scanning electron microscope
(FESEM) coupled with energy-dispersive X-ray spectro-
2 Experimental scope (EDX) was used to analyse the surface morphology
and the chemical composition of the specimens. FESEM
2.1 Materials images were further analysed by Java-based ImageJ software
in order to measure the grain sizes [32]. Dielectric properties
The metal nitrates like nickel nitrate hexahydrate including the dielectric constant, tan loss, real and imaginary
[Ni(NO3)2·6H2O], zinc nitrate hexahydrate [Zn(NO3)2·6H2O] part of electric modulus, impedance and ac conductivity of
and cobalt nitrate hexahydrate [Co(NO3)2·6H2O] were used cobaltites were analysed using Wayne Kerr Precision Imped-
as precursors, and glycine [­ C2H5NO2] and urea [­ CH4N2O] ance Analyser (6500B) in the frequency range of 20 Hz to
were used fuel agents. All these reagents were of analytical 20 MHz. For measuring the magnetic behaviour of the sam-
grade with purity ≥ 99% and purchased from Sigma-Aldrich. ples at room temperature (RT), LakeShore 7407, vibrating

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Dielectric and magnetic variance in ­NiCo2O4 spinels mediated by Zn-substitution for… Page 3 of 11 492

Fig. 1  Schematics of synthesis process of Zn-substituted Ni cobaltites

sample magnetometer (VSM) was used at a magnetic field [33]. It was observed that when Zn was substituted at Ni site,
of ± 10 kOe. the lattice parameter is slightly increased with no significant
change in their intensity positions. At maximum Zn concen-
tration, the stability of spinel cubic structure was maintained
3 Results and discussion and confirmed by matching these indexed peaks with ICSD
reference no. 00-023-1390 for pure ZCO with lattice param-
3.1 Structural analysis eter 8.09 Å. This structural analysis confirmed the stability
of spinel cubic structure with a slight reduction in lattice
XRD patterns of N­ i1−xZnxCo2O4 (x = 0.0, 0.2, 0.4, 0.6 and parameters. This stability of crystal structure with tuneable
0.8) are shown in Fig. 2. The diffracted intensities were lattice parameter could provide a variety of accommodative
indexed according to the indexing method given by B.D. lattice sites which may be very crucial for energy storage
Cullity. When indexed peaks of pure NCO were matched performance of the material. Using this structural data, a
with ICSD reference no. 00-002-1074, it confirmed the for- number of parameters like unit cell volume, crystallite size,
mation of cubic spinel structure with space group Fd-3 m. X-ray density and porosity were calculated, as summarized
The lattice constant for pure NCO was noticed as 8.10 Å in Table 1.

13
 492 Page 4 of 11 M. M. Munir et al.

and well-dispersed grains with an average size of 83 nm

can be observed in Fig. 3a that have adopted a roughly
spherical shape, as this image constitutes the pure sample
of Ni cobaltites. Furthermore, well-distinct grain bounda-
ries with considerable porosity are found to exist in these
micrographs. When Zn contents were introduced in Ni
cobaltites, it was noticed that the grain boundaries have
lost their distinctness with no sharp boundary between
them and are diffused to some extent with an average grain
size of 167 nm, respectively (Fig. 3b). The grain size was
continuously increased by the substitution of Zn and the
coalescence or agglomeration of small grains into larger
ones can be perceived in Fig. 3c, d, respectively. This
shows synthesis of a dense material which is favourable
for the dielectric characterization. Electrical and dielec-
tric properties of the samples can be affected due to this
coalescence which in turn reduces the effective surface
area. As density is inversely proportional to porosity, all
the specimens of Zn-substituted samples in N­ i1-xZnxCo2O4
(NZCO) had higher density and well-grown layers of par-
ticles. The small particles to be seen via FESEM micro-
graphs were Ni oxides having smaller radii than Co oxides.
The shapes of nanoparticles were similar to the grains of
stone and these could be favourable for the energy storage
devices. The average particle size of cobaltites increased
from 83 to 216 nm by increasing the concentration of Zn
in NCO, as summarized in Table 2. The variation in grain
size not only depends upon the preparation parameters for
Fig. 2  XRD patterns of ­Ni1-xZnxCo2O4 at x = 0.0, 0.2, 0.4, 0.6 and 0.8 example heat treatment but also on the quantity of sub-
stituents in the parent matrix [34].
Table 1  Variation of lattice constant (a), crystal size (D), bulk den-
sity (ρb), X-ray density (ρx) and porosity (P) in N­ i1-xZnxCo2O4 with
x = 0.0, 0.2, 0.4, 0.6 and 0.8
3.3 Elemental analysis
Parameters x = 0.0 x = 0.2 x = 0.4 x = 0.6 x = 0.8
The EDX spectra of whole series are shown in Fig. 4.
a (Å) 8.168 8.177 8.185 8.195 8.196
EDX spectrum of pure NCO shows peaks corresponding
D (nm) 121.51 287.94 132.27 136.02 196.94
to Ni, Co and O which confirmed the formation of NCO.
ρb (g/cm3) 3.550 3.739 2.627 2.738 3.451
The transition energies observed for Ni are 0.8, 7.46 and
ρx (g/cm3) 5.843 5.899 5.806 5.90 5.932
8.24 keV, for O it is 0.52 keV and for Co, it is 0.84 and
P (%) 39 36 54 53 41
6.92 keV. As Zn was substituted, the peaks corresponding
to Zn at energies 1.02 and 8.62 keV increased while peaks
corresponding to Ni get suppressed. When Zn is substi-
3.2 Morphological analysis tuted up to 0.8 concentration, the dominant peaks of Zn
appeared along with peaks of Co and O which confirmed
For the morphological analysis, FESEM images were the replacement of Ni with Zn. From these spectra, one can
recorded at magnification of 200,000 × with accelerating also observe a peak representing the presence of Au. This
voltage of 5 kV. These images are very helpful in deter- is because before morphological analysis, samples were
mining the shape and size of the particles. In addition, coated with Au to enhance their conductivity to achieve a
these images also provide a clear idea about the surface better contrast. The weight percentages along with atomic
roughness, texture and porosity of samples. The FESEM percentages of all the elements when estimated from these
images of all the samples are shown in Fig. 3. Momen- spectra were found in good agreement with the empirical
tous variations can be observed in the microstructure of formulae of the samples. The weight percentages of all the
Ni cobaltites when Zn was substituted in it. Homogeneous elements are shown in Table 3.

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Dielectric and magnetic variance in ­NiCo2O4 spinels mediated by Zn-substitution for… Page 5 of 11 492

Fig. 3  FESEM images of ­Ni1-xZnxCo2O4 at a x = 0.0, b x = 0.4, c x = 0.6 and d x = 0.8

Table 2  Average grain size Composition Average i.e. ­Ni1−xZnxCo2O4 (x = 0.0, 0.2, 0.4, 0.6 and 0.8), at RT.
estimated from FESEM images ­Ni1-xZnxC2O4 grain size The plots of dielectric constant versus frequency of the sam-
(nm) ples are shown in Fig. 5a. As the dielectric constant con-
sists of real and imaginary parts, it can be represented as
x = 0.0 83 ± 3
ε* = ε′ + iε″. Here, real and imaginary parts of dielectric con-
x = 0.2 114 ± 3
stant are represented by ε′ and ε″, respectively. The relation,
x = 0.4 167 ± 3
ε′ = Cd/(ε˳A) was used to calculate the real part of dielectric
x = 0.6 198 ± 3
constant, where capacitance is C, thickness of the pellets is
x = 0.8 216 ± 3
d, the permittivity of free space is ε˳ and the area of cylindri-
cal pellets is A [35]. At x = 0.0, the dielectric constant had
the minimum value in low-frequency region and it further
3.4 Dielectric properties decreased with increase in the frequency. With the substitu-
tion of Zn at x = 0.2, the dielectric constant enhanced but still
To analyse the dielectric behaviour of the samples, the speci- showed a decreasing trend with the increase in frequency.
mens in pellet form were placed inside the holder of imped- The value of dielectric constant continuously showed an
ance analyser. increasing trend as the substitution of Zn in Ni cobaltites
elevated and a maximum value of dielectric constant was
3.4.1 Dielectric constant obtained at x = 0.8 by keeping the decreasing trend with the
elevation of frequency, respectively. Hence, variation of
Data obtained from the dielectric analyser explored the die- dielectric constant with the frequency at RT was explored
lectric behaviour of pure and Zn-substituted Ni cobaltites, by these graphs which demonstrated that with the increase in

13
 492 Page 6 of 11 M. M. Munir et al.

At the low frequencies, these charges would change their

Co Zn Co x=0.8 polarity. The variation in the dielectric constant is mainly
O Zn due to the polarization and the presence of Maxwell–Wagner
Co relaxation. Once the relaxation time is achieved, the charges
exhibit a fixed polarity. The polarity of these charges remains
x=0.6 fixed during this time even in the presence of electric field
through the heterogeneous medium. The time required to
orient the dipoles in the direction of applied electric field is
Intensity (arb. units)

called the relaxation time, calculated by τ = 1/(2πfc), where

fc is the relaxation frequency.
x=0.4
3.4.2 Dielectric loss

Loss tangent is defined as the energy dissipation in dielec-

x=0.2 tric materials. The absorption of energy by applying electric
field causes the heat loss. It also explains the damping of
dipole moments. Perfect capacitors have zero loss tangent.
The zero loss tangent means that there is no energy dissipa-
tion in the system. This loss tangent can be calculated by
Co x=0.0 using tan δ = ε″/ε′. The frequency-dependent loss tangent is
Ni
O Co Ni Co shown in Fig. 5b.
Au Ni At x = 0.0, the loss tangent was maximum in the low-
frequency region which gradually decreased when moved
0 2 6 8 10 towards the high-frequency region. The substitution of Zn
caused the reduction in loss tangent at x = 0.2, which can be
Energy (keV) regarded as the fact that the sample can store energy without
heating or appreciable loss of energy. Further substitution
Fig. 4  EDX spectra of Zn-substituted Ni cobaltites of Zn caused the loss tangent of the samples to reduce and
lessen even more while keeping the decreasing trend of the
the Zn concentration, the dielectric constant was enhanced. curve by the elevation of frequency in regular steps. There-
NCO has smaller dielectric constant as compared to ZNCO, fore, high concentration of Zn atoms in Ni cobaltites showed
i.e. the values of dielectric constant increased from 45 to the decreasing loss tangent with the increase in frequency for
2500 at 20 Hz. The substitution of Zn might had provided all the samples. This was due to the relaxation peaks. Such
more resistive medium for the applied electric field. Koop’s peaks were formed when applied frequency and hopping
theory along with Maxwell and Wagner’s model could frequency of charge carriers became equal to each other.
explain the tendency of decrease in dielectric constant with
the increase in the frequency. At lower frequency, the resis- 3.4.3 Electric modulus analysis
tive grain boundaries are more effective than conductive
grains. Therefore, the dielectric constant is higher for the Real (M′) and imaginary parts (M″) of electric modulus of
low frequency. According to the Maxwell–Wagner effect, ­Ni1-xZnxCo2O4 for x = 0.0, 0.2, 0.4, 0.6 and 0.8 were calcu-
the existence of interfacial polarization is due to the disloca- lated by M′ = ε′/ (ε′2 + ε″2) and M″ = ε″/ (ε′2 + ε″2), respec-
tions, voids or pores. The charge on the pore would accumu- tively. The variation of M′ and M″ with Logf is shown in
late by simply applying electric field. Fig. 6. Figure 6a shows that as the frequency increases, the

Table 3  Weight per cent (wt. %) Ni1-xZnxCo2O4 Ni Zn Co O

and atomic per cent (at. %) of
all the elements obtained from wt. % at. % wt. % at. % wt. % at. % wt. % at. %
EDX spectra
x = 0.0 22.40 13.96 0.00 0.00 46.10 28.62 25.11 57.42
x = 0.2 19.41 11.97 5.42 3.0 45.03 27.66 25.36 57.37
x = 0.4 14.48 8.95 10.13 5.62 45.46 28.0 25.31 57.42
x = 0.6 9.12 5.59 16.04 8.83 45.35 27.68 25.75 57.90
x = 0.8 4.77 3.0 21.21 11.98 43.43 27.23 25.03 57.78

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Dielectric and magnetic variance in ­NiCo2O4 spinels mediated by Zn-substitution for… Page 7 of 11 492

(a) (a)

(b)
(b)

Fig. 5  a Dielectric constant and b Loss tangent of Zn-substituted Ni

cobaltites for x = 0.0, 0.2, 0.4, 0.6 and 0.8

Fig. 6  a Real modulus and b imaginary modulus of Zn-substituted Ni

value of M′ also increases, and after reaching a maximum cobaltites for x = 0.0, 0.2, 0.4, 0.6 and 0.8
value, it starts decreasing. This behaviour can be catego-
rized as an asymmetric one that arises due to less range
charge carriers’ mobility. The value of M′ for pure N­ iCo2O4 3.4.4 Impedance analysis
has lower value than Zn-substituted N ­ iCo2O4. The increase
in the concentration of Zn in ­NiCo2O4 showed an increase The electrical behaviour of any material is explored by
in the modulus. The shifting of peak positions in high-fre- examining its impedance. Impedance is also a complex
quency zone and the sturdy dependence of M″ are shown quantity which can be represented as Z = R + iX, where R
in Fig. 6b. The frequency zone has been divided into two and X represent resistance (real part of impedance) and reac-
parts, i.e. the higher one and the lower one depending upon tance (imaginary part of impedance), respectively. Real (Z′)
the sturdiness of the peaks. The carrier mobility at restricted and imaginary (Z’’) parts of impedance for pure NCO and
distances can be seen in the region of higher frequency while ZNCO are shown in Fig. 7a, b. It was clearly observed that
the charge carriers’ mobility at large distances is exhibited with the increase in frequency, the impedance of synthesized
by the low-frequency region. There is a specific relation material decreased. Conducting behaviour of all cobaltites
between space charge polarization and transport of elec- was confirmed by decrease in impedance. At low frequency,
trons in dielectric material. The resistivity decreased due all materials behaved like resistive medium and their resist-
to polarization caused by the interfacial charges on various ance substantially decreased with increase in frequency [38].
sides of the material [36]. Grain boundary played specific Hence, all the samples behaved like the resistive medium in
role in conduction process of charge carriers [37]. low-frequency region moving towards conductive medium

13
492 Page 8 of 11 M. M. Munir et al.

(a) (b)

(c) (d)

Fig. 7  a Real impedance, b imaginary impedance, c Nyquist plot and d ac conductivity of Zn-substituted Ni cobaltites for x = 0.0, 0.2, 0.4, 0.6
and 0.8 against frequency

with the increase in frequency. Furthermore, the impedance of the specimen so, at x = 0.0, highly insulating behaviour
decreased at each step of substitution of Zn in Ni cobaltites. of the compound can be seen. Nevertheless, as the concen-
In order to differentiate grain resistance from grain tration of Zn in the samples increased, the diameter of the
boundary regions, complex impedance measurements pro- semicircles showed a decreasing trend. Hence, it can be con-
vide a suitable way. For this purpose, Nyquist plot is shown cluded that the decrease in diameter depicted the lessening in
in Fig. 7c in which Z′ has been taken along x-axis and Z’’ the resistivity and increment in the conductivity of the speci-
along y-axis. Generally, from these plots the information mens [40]. Using these semicircles, we can calculate the
about three different electroactive regions can be obtained. values of grain boundary resistances (Rgb), capacitance (Cgb)
These different regions involve the conducting grains, insu- and relaxation time (τ). ac conductivity (σac) of the sam-
lating grain boundaries and interface between the samples ple can be calculated using the formula, σac = 2πfεoε′tanδ,
and the electrodes. In current study, one semicircle for each where ε′, f and εο represent real part of dielectric constant,
specimen was observed that corresponded to grain bounda- frequency and permittivity of free space, respectively. ac
ries and which was efficaciously taking part in the electri- conductivity for all compositions is shown in Fig. 7d. It is
cal response of the prepared samples [39]. There is a direct clearly observed that ac conductivity of Zn-substituted Ni
relation between the diameter of a semicircle and resistance cobaltites was higher than the pure Ni cobaltites. At low

13
Dielectric and magnetic variance in ­NiCo2O4 spinels mediated by Zn-substitution for… Page 9 of 11 492

frequency, material showed the resistive behaviour due to 14.29, 6.40, 4.01, 2.68 and 1.68 emu/g with Zn substitu-
effective grain boundary in this regime and their resistive tion, respectively. In addition to this, the value of rema-
nature decreased. It was also due to the hopping of charge nent magnetization (Mr) was noticed as 3.23, 1.19, 0.77,
carriers in material. Substitution of Zn metal in cobaltites 0.36 and 0.35 emu/g, respectively, in the series. Similarly,
at all concentrations clearly exhibited maximum resistive coercivity (H c) was found to be 300, 350, 375, 400 and
medium at low frequency. Maximum amount of Zn in Ni 435 Oe, respectively, with the increased Zn contents. The
cobaltites showed higher conductive nature of the material. increasing value of Hc indicates that material is becoming
magnetically hard on increasing Zn contents which means
3.5 Magnetic analysis Zn substitution hinders the flipping of magnetic dipole
moment in alternating magnetic field [42]. The values of
Magnetic response of pure NCO and ZNCO at RT is Mr, Ms and Hc are summarized in Table 4. A comparison
shown in Fig. 8. The magnetic behaviour of any mate- of the magnetic properties of these compositions with the
rial is varied by different factors like temperature, shape previous work is summarized in Table 5 [43–47].
or dimension of materials. Nakate et al., (2016) reported
the magnetic behaviour of Zn-substituted Ni cobaltite
nano-plates. They showed the small hysteresis loop for 4 Conclusion
nano-plates of Zn-substituted Ni cobaltite multiferroic
material [41]. Here, the M–H curves of N ­ i 1-xZn xCo 2O 4 Spinel cobaltites ­N i 1-xZn xCo 2O 4 (x = 0.0, 0.2, 0.4, 0.6
with the concentration of x = 0.0, 0.2, 0.4, 0.6 and 0.8 and 0.8) were synthesized using sol‒gel auto-combus-
exhibited maximum magnetization at 10 kOe of applied tion method. XRD confirmed cubic spinel structure of
magnetic field strength. From these M–H loops, the val- Zn-substituted Ni cobaltites. It has been observed that
ues of saturation magnetization (M s) were recorded as lattice constant slightly increased from 8.168 to 8.196 Å
with substitution contents that varied from x = 0.0 to 0.8,
respectively. The growth of grains was witnessed from
15 x=0.0
x=0.2
(a) FESEM images and average grain size was noticed as 83,
Magnetization (emu/g)

10 x=0.4 167, 198 and 216 nm at x = 0.0, 0.4, 0.6 and 0.8, respec-
x=0.6 tively. The proper substitution of Zn at Ni site was probed
5 x=0.8
from their EDX spectra. At the frequency of 20 Hz, the
0 presence of Zn in cobaltites enhanced the value of dielec-
4 tric constant from 44 to 2512 due to the presence of grain
Magnetization (emu/g)

-5 boundaries. Koop’s theory and Maxwell–Wagner model

0

-10 elaborated the decrease in dielectric constant with the

increase in frequency for Zn-substituted Ni cobaltites. ac
-4

-15 -7.0k 0.0

Applied Field (Oe)
7.0k

conductivity of cobaltites was enhanced by the increase

-10k -5k 0 5k 10k in concentration of Zn. Loss tangent was found to be 107,
Applied Field (Oe) 82, 72, 66 and 58 for ­N i 1-xZn xCo 2O 4 (x = 0.0, 0.2, 0.4,
0.6 and 0.8). The magnetic analysis revealed that values
16 (b) 440 of Ms and Mr decreased while Hc increased which shows
the potential of material for permanent memory devices.
12 400
Ms(emu/g)

Hc(Oe)

8 360

4 320 Table 4  Values of saturation magnetization (Ms), remanence magneti-

zation (Mr) and coercivity (Hc) in the samples
0
280 x Ms (emu/g) Mr (emu/g) Hc (Oe)
0.0 0.2 0.4 0.6 0.8 0.0 14.29 3.23 300 ± 5
Substitution Contents (x) 0.2 6.40 1.19 350 ± 5
0.4 4.01 0.77 375 ± 5
Fig. 8  a Variation in M–H loops obtained from VSM and b compari- 0.6 2.68 0.36 400 ± 5
son of Ms and variation in the coercivity for Ni1-xZnxCo2O4 with 0.8 1.68 0.35 435 ± 5
x = 0.0, 0.2, 0.4, 0.6 and 0.8s

13
 492 Page 10 of 11 M. M. Munir et al.

Table 5  Comparison of the Sample Ms (emu/g) Mr (emu/g) Hc (Oe) Year published References
present work with the previous
work NiCo2O4 2.3 0.63 174 2015 [43]
NiCo2O4 1.85 – 119.7 2017 [44]
NiCo2O4 – 1.18 241 2020 [45]
ZnCo2O4 3.75 × ­10–5 3.75 × ­10–5 – 2019 [46]
NiCo2O4 14.29 3.23 300 This work
Ni0.2Zn0.8Co2O4 1.68 0.35 435 This work

Acknowledgements The authors acknowledge the Higher Education 14. R.B. Rakhi, Preparation and properties of manipulated carbon
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