Ceramics International xxx (xxxx) xxx

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Electrical behaviour, dielectric properties, then optical behaviour of nickel,

magnesium doped/codoped zinc oxide along with preparation,
and characterisation
A. Athira a , Bindu P. Nair b,**, A. Chithra Mohan a , Beena Saraswathyamma a,*** ,
G. Sivasubramanian c,e,****, K.M. Sreekanth d,e,***** , K.M. Sreedhar a,*
a
Department of Chemistry, Amrita Vishwa Vidyapeetham, Amritapuri, Kerala, 690525, India
b
Department of Chemistry, V.S.B. College of Engineering Technical Campus, 642109, Coimbatore, Tamil Nadu, India
c
Department of Chemistry, Amrita School of Physical Sciences Coimbatore, Amrita Vishwa Vidyapeetham, 641112, India
d
Department of Physics, Amrita School of Physical Sciences Coimbatore, Amrita Vishwa Vidyapeetham, 641112, India
e
Advanced Multi-Functional Materials and Analysis Laboratory (AMMAL), Amrita School of Engineering, Amrita Vishwa Vidyapeetham, 641112, Coimbatore, India

A R T I C L E I N F O A B S T R A C T

Handling Editor: Dr P. Vincenzini Magnesium and nickel doped, and codoped zinc oxide was produced via the minimal and economical precipi­
tation technique, varying dopant concentrations. To demonstrate the advantages of codoping with nickel and
Keywords: magnesium, zinc oxide microstructure was investigated using X-ray diffraction. The powder sample was also
Zinc oxide characterized by energy dispersive X-ray analysis, Fourier transform infrared spectroscopy, and photo­
Precipitation
luminescence analysis. Spectroscopic measurement of UV–visible diffuse reflectance was used for calculating
Electrical behaviour
optical bandgap of doped and codoped zinc oxide powder. Electrical behaviour then dielectric properties of the
Dielectric properties
materials were also exhaustively investigated.

1. Introduction awareness of ac conductivity and dielectric qualities of semiconductors.

The electrical mobility in semiconductors has been clarified by the
Zinc oxide is an intriguing semiconductor material owing to its use in polaron hopping hypothesis, and the localized charge carriers that
gas sensors, solar cells, ceramics, catalysis, cosmetics, and varistor ap­ accompanying faulty states producing microscopic polarons. The ZnO
plications. At room temperature, ZnO possesses a bandgap of 3.37 eV, lattice is further distorted and disrupted by transition metal dop­
rendering it a broad bandgap semiconductor [1]. In light of the cation ing/codoping, which can drastically change the electrical conductivity
and anion tetrahedral orientation in the c-axis, ZnO exhibits hexagonal of the ZnO semiconductor. Although imperfections are significant fac­
wurtzite organization by a noncentrosymmetric p63mc space group [2]. tors in room temperature ferromagnetism (RTFM), it is imperative to
Zinc oxide in comparison with other similar materials is more reason­ investigate dielectric and ac conducting properties of the materials to
able, comfortable to engineer, also less damaging to the environment gain a thorough grasp of its interior [4]. By combining two dopants at
[3]. As a result of its catalytic, electrical, optoelectronic, and photo­ the same time, there is an exceptional opportunity to maximize their
chemical qualities, it has widespread applications. Understanding the respective contributions while also perhaps discovering completely new
nature of conduction and defect foci in crystalline materials demands an properties that may be used for cutting-edge applications [5].

* Corresponding author.
** Corresponding author.
*** Corresponding author.
**** Corresponding author. Advanced Multi-Functional Materials and Analysis Laboratory (AMMAL), Amrita School of Engineering, Amrita Vishwa Vidyapeetham,
641112, Coimbatore, India.
***** Corresponding author. Advanced Multi-Functional Materials and Analysis Laboratory (AMMAL), Amrita School of Engineering, Amrita Vishwa Vidyapee­
tham, 641112, Coimbatore, India.
E-mail addresses: [Link]@[Link] (B.P. Nair), beenas@[Link] (B. Saraswathyamma), g_sivasubramanian@[Link] (G. Sivasubramanian),
km_sreekanth@[Link] (K.M. Sreekanth), sreedharkm@[Link] (K.M. Sreedhar).

[Link]
Received 7 October 2024; Received in revised form 28 December 2024; Accepted 5 January 2025
Available online 7 January 2025
0272-8842/© 2025 Elsevier Ltd and Techna Group S.r.l. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Please cite this article as: A. Athira et al., Ceramics International, [Link]
A. Athira et al. Ceramics International xxx (xxxx) xxx

Table-1
Mass of the precursor salts used for the synthesis of the samples.
Sample Mass % of the dopant NiSO4.7H2Owith respect Mass % of the dopant MgSO4.7H2Owith respect Mass of Mass of Mass of
code to the mass of ZnSO4.7H2O to the mass of ZnSO4.7H2O ZnSO4.7H2O (g) NiSO4.7H2O (g) MgSO4.7H2O (g)

undoped 0 0 20 0 0
ZnO
K4 2 0 20 0.4 0
K5 2 4 20 0.4 0.8
K6 2 6 20 0.4 1.2
L4 0 2 20 0 0.4
L5 4 2 20 0.8 0.4
L6 6 2 20 1.2 0.4

Many studies are available on the production, using different tech­

Table-2
niques, of transition metal-doped zinc oxide [6–11]. In both bulk besides
Detailed description of the as-prepared samples.
nano dimensions, some describe the presence of ferromagnetism,
whereas others report the absence. Ferromagnetic nature of Mn doped Sl. No. Sample code Description

zinc oxide is influenced by preparation characteristics such as the 1 K4 2% Ni doped ZnO

technique, reaction rates, shape, dimension, and concentration of 2 K5 2% Ni, 4 % Mg codoped ZnO
3 K6 2% Ni, 6 % Mg codoped ZnO
intrinsic and extrinsic defects, as well as by transition metal ion incor­
4 L4 2% Mg doped ZnO
poration, distribution, and post-synthesis treatments. Moreover, uncer­ 5 L5 4% Ni, 2 % Mg codoped ZnO
tainty surrounds the dispersion of transition metals within the ZnO 6 L6 6% Ni, 2 % Mg codoped ZnO
matrix [12]. The choice of dopant has an enormous effect on the specific
features of zinc oxide nano structures, such as bandgap, optical prop­
erties, besides electrical conductivity. Introduction of transition metals stirred 15 min. This mixture was stirred well, and a calculated amount of
in zinc oxide also leads to development of ferromagnetic properties at sodium hydroxide was used as the precipitating agent. After completion
room temperature [13]. Quenching method at high temperature can be of reaction, the precipitate was cleaned by deionized water using a
used to synthesis ZnO nanorods with manageable surface defects vacuum pump till the washings were free from sodium ions and impu­
thereby the recombination of photogenerated electron-hole pairs can be rities originating from the precursor salts. The washed precipitate was
considerably suppressed, thus significantly enhancing the photo­ later rinsed with acetone and dried at 70 ◦ C for 2 h in the oven. The
catalytic reactivity [14]. Ferroelectric ceramics form another group of synthesized Zn(OH)2 was annealed at 650 ◦ C for 2 h to get undoped ZnO.
materials extensively studied for their electrical properties [15]. Ferro­ The calcined samples were crushed into fine powder with the help of
electric materials find widespread applications in brake systems due to agate mortar and was used for further studies.
their ability to convert electrical energy into mechanical energy [16]. For synthesising Ni, Mg doped/codoped zinc oxide, similar proced­
There are ceramics materials designed for capacitor applications at high ure was followed. All samples were formulated as detailed in Table-1.
voltage [17]. Detailed description of synthesized samples is included in Table-2.
In this work, ZnO is doped and codoped with Ni and Mg in different
concentrations. The synthesized doped and codoped ZnO were differ­ 2.3. Characterization
entiated by diverse methodical procedures including PXRD to realize the
crystal system and to calculate the crystallite size. Ultraviolet–visible Bruker D8 advance X-ray powder diffractometer with Cu-Kα radia­
diffusive reflection (UV–Vis DRS) spectroscopy was employed to tion at λ = 1.5418 Å was employed to study phase composition besides
examine optical characteristics. PL (photoluminescence) spectroscopy crystal configuration of Ni, Mg doped, and codoped ZnO. The 2θ values
provides imperative information about defective emissions and match­ were varied between 20◦ and 80◦ in this experiment. Using Jeol 6390LV,
ing dopant interactions on these intrinsic entrapment states and is an chemical composition of the samples was investigated. PerkinElmer
efficient method for identifying imperfections in semiconducting ma­ Lambda 365, 200 nm–1000 nm, was used to determine UV–visible
terials. FESEM was utilized for evaluating surface morphology. Elec­ diffuse reflectance spectra of as-produced samples. FESEM of Carl Zeiss-
trical then dielectric properties of the materials were studied by broad- Sigma with the software SMARTSEM was employed. Horiba Fluoromax
band dielectric spectrometer (BDS) (NOVOCONTROL Technologies Spectrofluorometer was used for photoluminescence analysis. For the
GmbH & Co., Germany, Model: Concept 80). dielectric study, broad-band dielectric spectrometer (BDS) (NOVO­
CONTROL Technologies GmbH & Co., Germany, Model: Concept 80)
was used.
2. Experimental

3. Results and discussion

2.1. Materials used

3.1. Energy-dispersive X-ray (EDX) investigation

Precursor salts, zinc sulphate heptahydrate, nickel (II) sulphate
heptahydrate, and magnesium sulphate heptahydrate were procured
Presence of zinc then oxygen in undoped ZnO was confirmed by EDX
from Merck, and sodium hydroxide pellets from Nice. They were utilized
analysis. Additionally, a peak representing sulphur was also seen in the
as gained, without any further cleansing. Deionized water was employed
EDAX of undoped ZnO, and it is originated from the precursor salt zinc
during the formulation then purification of samples.
sulphate heptahydrate. No additional peaks associated with any con­
taminants have been found throughout the whole scanning range for
2.2. Synthesis of undoped then Ni, Mg doped and codoped zinc oxide doped and codoped ZnO, Figure-1. The weight and atomic percentage of
all materials are included in Table-3 then Table-4, respectively.
Undoped, doped and codoped ZnO were prepared by precipitation/
coprecipitation method. The precursor salt used for synthesising undo­
ped zinc oxide is zinc sulphate heptahydrate. For undoped ZnO, neces­
sary quantity of this salt was included in 100 mL deionized water, then

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Figure-1. EDAX spectra of undoped, doped, and codoped ZnO.

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Table-3
Weight percentage from EDAX of undoped, doped, and codoped ZnO.
Sample code Weight percentage of oxygen Weight percentage of zinc Weight percentage of nickel Weight percentage of magnesium Weight percentage of sulphur

undoped ZnO 16.31 78.64 ​ ​ 5.05

K4 21.45 77.18 1.38 ​ ​
K5 18.65 78.4 1.22 1.73 ​
K6 20.49 75.52 1.31 4.28 ​
L4 26.68 71.06 ​ 2.26 ​
L5 19.51 77.11 2.52 0.85 ​
L6 14.91 81.39 2.31 1.39 ​

Table-4
Atomic percentage from EDAX of undoped, doped, and codoped ZnO.
Sample code Atomic percentage of oxygen Atomic percentage of zinc Atomic percentage of nickel Atomic percentage of magnesium Atomic percentage of sulphur

undoped ZnO 42.83 50.55 ​ ​ 6.62

K4 52.68 46.4 0.92 ​ ​
K5 47.45 48.82 0.84 2.89 ​
K6 49.87 44.98 0.87 4.28 ​
L4 58.56 38.18 ​ 3.26 ​
L5 49.24 47.62 1.73 1.41 ​
L6 41 54.76 1.73 2.51 ​

Figure-3. Shift in peak upon doping/codoping in samples K4, K5, and K6.

Figure-2. XRD pattern of undoped, doped then codoped ZnO.

3.2. Structural analysis using powder XRD

Figure-2 shows XRD pattern of undoped, doped, then codoped zinc

oxide with different doping concentrations. They have crystal planes
(100), (002), (101), (102), (110), (103), (200), (112), and (201), cor­
responding to 2θ of 31.68◦ , 34.44◦ , 36.14◦ , 47.54◦ , 56.46◦ , 62.89◦ , Figure-4. Shift in peak upon doping/codoping in samples L4, L5, and L6.
66.42◦ , 67.99◦ , and 68.92◦ , respectively. All the diffraction crystal
planes are matched well with hexagonal wurtzite crystal configuration occurrence of sulphur in the undoped ZnO. Figs. 3 and 4 represent the
of zinc oxide obtained with JCPDS card number 05–0664, and 36–1451 peak shift that occurred upon doping/codoping. In all cases, the shift in
[18]. In XRD pattern, except in undoped ZnO, no peaks for dopants or the peak occurred towards right, higher 2θ values. However, the samples
other compounds/phases were found. In the case of undoped ZnO, there K4, K5, and K6 produced very less shift compared to that produced by
are peaks below 30◦ at 2θ of 18.94◦ , 22.45◦ , 24.02◦ , 25.33◦ , 26.44◦ , and the samples L4, L5, and L6. The peak shift exposed that the process of
27.34◦ . They show the formation of the phase Zn3O(SO4)2 (JCPDS card doping/codoping occurred successfully. From Bragg’s relation nλ =
number 000321475). Remember that the EDAX result confirmed the 2dsinθ, it is clear that d, the spacing between the planes in the crystal, is

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Figure-5. W-H Plot for undoped, doped and codoped ZnO.

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Table-5 3.4. Photoluminescence studies

Crystallite size by Scherrer method then Williamson-Hall method.
Material Crystallite size (nm) Figure-11 depicts photoluminescence (PL) spectra of undoped,
doped, then codoped zinc oxide with an excitation wavelength of 325
Scherrer method Williamson-Hall method
nm at room temperature. There are usually two emission bands in the PL
undoped ZnO 22.5815 38.515 spectra of zinc oxide, one is in UV region and second, in visible region.
K4 29.2841 53.4378
K5 32.3073 64.3628
Former is due to near band edge emission via exciton-exciton collision
K6 31.6528 48.27 and latter is from electron-hole recombination caused by intrinsic de­
L4 18.9613 21.172 fects as well as surface defects. The emission band at 560 nm is a
L5 20.5225 33.2148
L6 21.2986 25.3176

inversely proportional to the angle θ so that as θ decreases, d increases

and vice versa. In the present study, θ increases, peak-shift towards
higher 2θ values, so that d, the spacing between the planes, decreases
upon doping/codoping. Hence, compressive strain developed in the
crystals of ZnO upon doping/codoping. Since the samples K4, K5, and K6
produced very less shift towards higher 2θ values than that produced by
the samples L4, L5, and L6, it could be confirmed that K4, K5, and K6
developed less, and L4, L5, and L6 developed greater compressive strain.
The crystallite size was computed employing Scherrer formula D(hkl)
= kλ/βcosθ, here k = 0.9, λ, wavelength of CuKα radiation (0.15406
nm), θ, Bragg angle of XRD peak then β, FWHM of diffraction peak [19].
Another option used to compute crystallite size is the Williamson-Hall
(W-H) method, Figure-5, which is more precise than Scherer method. Figure-6. Absorbance spectra of undoped ZnO, K4, K5, then K6.
The crystallite size calculated from both methods is tabulated in Table-5.
It is evident that sample L4 has the least crystallite size among all the
samples. The samples K4, K5 and K6 produced more crystallite size, and
the samples L4, L5 and L6 produced less crystallite size than the undo­
ped ZnO. Lattice parameters of all samples are presented in Table-6,
along with dislocation density and micro strain. Material K4, K5, and K6
developed less, and L4, L5, and L6 developed greater micro strain,
compared with undoped ZnO. It is in consistent with XRD results.

3.3. Optical analysis

To investigate their potential uses, transmittance and absorbance

spectra of the undoped, doped besides codoped zinc oxide were exam­
ined. The absorption margin of samples ranges from 389 nm to 399 nm,
Figure-6 and Figure-7. The absorption behaviour of undoped ZnO con­
forms to the published data in the literature [4]. For undoped ZnO, the
absorption edge is at 392 nm which increased on doping and codoping
except for sample L4, 2 % Mg doped ZnO. For sample L4, the absorption Figure-7. Absorbance spectra of undoped ZnO, L4, L5, then L6.
edge decreased to 389 nm. The maximum absorption peak was observed
with samples K5 (2 % Ni, 4 % Mg codoped ZnO) and L6 (6 % Ni, 2 % Mg
Table-7
codoped ZnO), Table-7.
λmax values of samples.
Plotting Tauc’s curve from absorbance data enables accurate band
gap analysis, Figure-8 and Figure-9. Tauc’s equation was employed for Sample code λmax

determining bandgap energy values of ZnO and doped and codoped ZnO undoped ZnO 392
[20]. Kubelka-Munk plot, K-M plot, was also employed for determining K4 398
K5 399
bandgap energies of all samples, Figure-10. The band gap energies ob­
K6 397
tained with Tauc’s curve and K-M plot are summarised in Table-8. L4 389
L5 399
L6 399

Table-6
Lattice parameters and microstrain in undoped, doped and codoped ZnO.
Sample a (Å) c (Å) c/a Volume (Å) Dislocation density Micro strain

undoped ZnO 3.2489 5.2049 1.6020 47.58 0.0196 3.8299 × 103

K4 3.2489 5.2049 1.6020 47.58 0.0117 2.9727 × 103
K5 3.2489 5.2049 1.6020 47.58 0.0096 2.6801 × 103
K6 3.2509 5.2067 1.6016 47.65 0.01 2.7371 × 103
L4 3.2489 5.2049 1.6020 47.58 0.0278 4.6422 × 103
L5 3.2468 5.2019 1.6022 47.49 0.0237 4.3065 × 103
L6 3.2468 5.2019 1.6022 47.49 0.022 4.1383 × 103

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Figure-8. Tauc’s plot for undoped ZnO, K4, K5 then K6.

Figure-9. Tauc’s plot for undoped ZnO, L4, L5, then L6.

Table-8
Band gap energy of undoped, doped, and codoped ZnO.
Sample code Band gap energy after Tauc’s plot Band gap energy from K-M plot
(eV) (eV)

undoped 3.0548 3.0994

ZnO
K4 3.0803 3.0750
K5 3.0862 3.1418
K6 3.0992 3.1145
L4 3.0877 3.1650
L5 3.0815 3.0702
L6 3.0846 3.0848

characteristic peak of ZnO [21]. The presence of a narrow green emis­

Figure-10. Kubelka-Munk plot for all samples.
sion band at 560 nm can be explained by the presence of surface oxygen
defects [22]. These defects cause quenching of UV emission. When
compared to undoped ZnO, the samples K4, K5, and K6 exhibited
increased PL intensities, indicating increased oxygen vacancy defects on

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to Zn-Ni-O octahedral coordination was detected at 523, 537, besides

584 cm− 1 [26]. Presence of a signal at 502 cm− 1 in Ni doped ZnO can be
credited to incorporation of Ni2+ into ZnO host. This peak is absent in
undoped ZnO nanoparticles. The slight variation observed in the
measured values can be ascribed to elongation of Zn-O-Ni bond. Ab­
sorption at 498, 496, besides 495 cm− 1 is due to ZnO, and Mg doped ZnO
[27,28]. The observations obtained from FTIR spectroscopy are consis­
tent with the findings from the XRD analysis.

3.7. Exploration of electrical behaviour then dielectric properties

To examine the electrical behaviour then dielectric properties of

doped and codoped zinc oxide nano particles, the samples were pellet­
ized to a diameter of 13 mm. The thickness and surface area of pellets
were assessed employing a digital calliper with a precision of 0.001 mm.
Figure-11. PL spectra of undoped, doped, then codoped ZnO. Employing broad-band dielectric spectrometer (NOVOCONTROL Tech­
nologies GmbH & Co., Germany, Model: Concept 80), measurements for
the surface upon doping and codoping. For L4, L5, and L6, a decrease in dielectric constant (ε’), dielectric loss (ε”), loss tangent (tan δ), capaci­
PL intensity was observed, that is, low surface oxygen defects, and the tance (Cs), and ac conductivity (σac) were obtained from 1 Hz to
least for sample L6 (6%Ni and 2%Mg codoped ZnO). The reason for the 1000000 Hz at room temperature. Figure-14 is the frequency versus
low surface oxygen defects is due to the effect of dopants, the dopants real, and Figure-15 is the frequency versus imaginary part of dielectric
incorporated well into the lattice of zinc oxide. Blue emission band at constant graph for the nano particles. Recall that Figure-15 demon­
467 nm of undoped ZnO is a deep-level emission (DLE) originating from strates a relaxation process, defined by the maximum dielectric loss,
oxygen vacancy or interstitial zinc ions of zinc oxide lattice [23]. Sample driving the dielectric constant to grow with decreasing frequency. It can
L4 (2 % Mg doped ZnO) shifted to 472 nm with decreased intensity be from the quick change in electric field or the uneven distribution of
indicating that there is less Zn2+ vacancy in L4. All other samples dis­ charge carriers. Another explanation for this is the Maxwell-Wagner (M
played an increased intensity showing more Zn2+ vacancies in these − W) mechanism [29]. Nanomaterials are thought to consist of good
materials. Also, blue-green emission at 481 nm is preferably due to conducting particles that are separated from poor conducting ones via
transition from a shallow donor of interstitial zinc to a band of top-level the M − W process. With the introduction of an external electric field,
valence. K4, K5, and K6 exhibited an increase in intensity compared to the charge carriers can bring grain boundaries together. A small amount
the undoped ZnO. Defects resulting from doping with Ni, and codoping of polarisation at a high frequency hence causes a low dielectric con­
with Ni and Mg could increase the radiating recombination centres. In stant. When dipoles cannot spin quickly enough for a prolonged period
sample K5 and K6, the percentage of Mg is 4 % and 6 %, respectively, of time, they will begin to oscillate through the field. As a result, when
which is higher than the percentage of Ni in both samples, being 2 %, frequency increases enough, dipoles will no longer be able to follow the
which caused an increase in surface recombination effect and oxygen field, and the pattern of polarisation will disappear. As a result, it starts
vacancy. Such type of increase in intensity was reported in thin films of to decrease and ultimately reaches a constant value. Theoretically,
Mg doped ZnO [24]. Enhanced quality of the crystal and the decreased variation in resistance that the charge carriers encounter causes the
stress resulting from Mg doping are also responsible for the rise in charges to accumulate at distinct limits. This results dielectric constant
intensity. to increase [30].
Figure-16 illustrates properties of frequency-dependent loss tangent.
Measurement of dissipative nature of a material in presence of an
3.5. Surface morphology study external electric field is called loss factor. For undoped ZnO, there is no
observable change, but for K4, K5, and K6, there is an increment in loss
Figure-12 clarifies morphology of undoped, doped, then codoped tangent with frequency. This increase in loss tangent can be due to
zinc oxide. From FESEM images, it could be observed that the particles presence of charge carriers and the arrangement of defects [31].
fall in the nanoscale dominion. It is obvious from all the pictures that the Figure-17 illustrates the frequency dependent ac conductivity of
particles got agglomerated. Morphology of undoped ZnO is nanoflake. undoped, doped and codoped ZnO. Two crucial parameters utilized
When ZnO was doped the 2 % Ni, there was more agglomeration while describing the dielectric properties of materials include transport
compared to that of Ni, Mg codoped ZnO. There is nanorod formation in characteristics and ac conductivity. Although defect centres are crucial
Ni, Mg codoped ZnO. Sample L4, 2 % Mg doped ZnO, developed nano for the conduction process, measurement of ac conductivity of semi­
disc-like structures. The agglomeration is less compared to 2 % Mg, 4 % conductors has been widely employed to comprehend the transport
Ni codoped ZnO, and 2 % Mg, 6 % Ni codoped ZnO. The high doping mechanism in these materials, and also to explore the nature of the
concentration of Ni than Mg might be end with nano disc formation defect centres. The interior area of the material with relatively low
[25]. conductivity can be learned by ac measurements. Another asset of this
measurement is differentiating free and localised band conduction.
3.6. FTIR investigations Sample L4 (2 % Mg doped ZnO) and undoped ZnO displayed same
amount of increase in σac with ascending frequency. In general, the in­
FTIR, Fig. 13, is a scientific method for gathering precise details on crease in ac conductivity with frequency accounts for presence of small
the chemical bonding, crystalline structure, chemical content, also polaron [32]. The thermal activation energy for tunnelling enhances
morphology [26]. Absorption peak observed at 3604 and 3260 cm− 1 is conductivity with frequency. Thus, charge carriers with enough energy
suggestive of vibrational mode of O-H present in adsorbed H2O. Ab­ can overcome potential barrier at a certain frequency, increasing con­
sorption at 3436 cm− 1 is caused by O-H stretching from the ductivity quickly [33].
surface-adsorbed H2O molecules. The presence of adsorbed CO2 caused Figs. 18 and 19 illustrate the variation of electric modulus with
the absorption observed at 2318, 2352, 2371, 2393, then 2344 cm− 1. frequency. In general, variation of electrical modulus of a material with
Absorption bands observed at around 873, 866, 859, then 864 cm− 1 are frequency indicates a complex interaction of ionic and electronic con­
due to vibrational frequency from Ni-O. Absorption band corresponding duction pathways, dielectric properties, and defects that affect its

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Figure-12. FESEM of undoped and doped/codoped ZnO.

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Figure-13. FTIR of undoped, doped, then codoped ZnO.

Figure-17. Change of ac conductivity against frequency.

Figure-14. Deviation of ε′ against frequency at room temperature.

Figure-18. Deviation of real part of electric modulus against frequency.

Figure-15. Change of ε” against frequency at room temperature.

Figure-19. Change of imaginary part of electric modulus against frequency.

electrical behaviour. In the study of electrical properties of undoped,

doped, then codoped zinc oxide nano particles, real and imaginary part
of electrical modulus versus frequency play an important role. Relaxa­
tion process which involves localised movements of charge carriers can
be explained by scaling the electrical modulus [32]. It is clear after the
graph that undoped ZnO, and Ni doped ZnO show a rise in real part of
electrical modulus with frequency indicating a good conductive nature
of the samples, while the rest of the samples show fewer amount of in­
Figure-16. Frequency versus loss tangent (Tan δ). crease in real part of electric modulus (M’). Imaginary part of electrical

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Figure-23. Capacitance in series versus frequency graph.

Figure-20. Cole-Cole plot.

Figure-24. Specific resistance versus frequency graph.

could be exhibited a capacitance of about 1.4 × 10− 8 F, and 3 × 10− 7 F

Figure-21. Capacitance versus frequency graph. in series. In parallel connection, sample K4 could be presented 4 × 10− 9
F and other samples could be exhibited values below 1 × 10− 9 F. Coming
to the capacitance in series, sample L4 and K6 have almost the same
capacitance of about 5 × 10− 8 F. The energy storage, capacitance, de­
creases with frequency, which is due to the migration of intrinsic charge
carriers and the weakening of the interaction force between cations and
anions [35].
One feature that characterizes how strongly materials can oppose
flow of electric current is specific resistance, often known as resistivity, a
crucial indicator of the electrical behaviour of doped/codoped ZnO.
Figure-24 presents specific resistance versus frequency graph, which
reveals that undoped ZnO exhibits high resistivity, and the sample K4
also, but very much less than that by undoped ZnO. All other samples are
stable at all frequencies. This means that doping/codoping decreased
the resistivity of ZnO. Sample K4, which is Ni doped ZnO, shows a bit of
specific resistance but codoping with Ni and Mg, that is, when Mg is also
added as in K5 and K6, decreased the resistivity.
Figure-22. Capacitance in parallel versus frequency graph. Important details about the electrical characteristics of any material
can be learned from real and imaginary component of ac conductivity.
modulus (M”) is related to the capacitance of the material. Figure-20 The in-phase reaction of the material with the electric field of ac is
represents the Cole-Cole plot. The semi-circle arc formed by sample K4, represented by the real component of ac conductivity. It has a direct
K5, and K6 explains the relaxation contributed by the grain boundaries. bearing on how well the substance can conduct electricity. Conversely,
A discernible shoulder-like characteristic for undoped ZnO, L4, L5, and the imaginary component denotes the out-of-phase reaction of the ma­
L6 indicates the resistance of grains only [34]. terial with the electric field of ac. It has to do with how dielectric the
From Figure-21, it is clear that the doped/codoped samples show material is and how much electrical energy it can hold and release. The
increased capacitance whereas the undoped ZnO shows no visible real component of ac conductivity speaks about the conductive path­
change or activity. The maximum capacitance can be observed with ways and the efficiency of the material to carry electric current. This can
sample K5 whereas with sample L5 and L6, the least. Figure-22 and provide insights into the effect of doping/codoping on concentration
Figure-23 represent capacitance in parallel versus frequency graph, and and mobility of free charge carriers in ZnO. Because of reduced
capacitance in series versus frequency graph, respectively. Sample K5 dispersion at higher frequencies and increased availability of charge
could be exhibited the highest capacitance value in both parallel and carriers, the actual component of ac conductivity often increases with
series when compared to all other samples. In parallel arrangement, K5 frequency in many materials. Complex component of ac conductivity

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Figure-25. Imaginary part of ac conductivity against frequency.

Figure-29. Impedance in series versus frequency.

offers valuable information about dielectric loss and ability of the ma­
terial to store and release energy in response to an alternating field. It
frequently mirrors the polarisation processes and relaxation phenomena
of the material. It is evident from Figure-25 that undoped samples have
the ability to store energy and doping/codoping increases the ability.
Sample L5 and L6 possess higher σ’’ values compared to undoped ZnO.
From the σ′ values, Figure-26, it is clear that doping/codoping can create
charge carriers. Sample L4, L5, and L6 show increased σ′ values.
Figure-27 illustrates plot of real part against imaginary part of
impedance. There are no semi circles which makes it clear that the
resistance is not offered by the grain boundaries. Sample L5 and L6 show
a slight arc formation which can be due to resistance contributed by the
Figure-26. Real part of ac conductivity against frequency graph. grains [36–38].
Figure-28 presents impedance in parallel versus frequency plot, and
Figure-29, impedance in series versus frequency plot. In both cases,
undoped sample has the maximum value of impedance. In parallel
connection, except the undoped sample, all other samples show no ac­
tivity while in series, where the individual impedance of the grains
contributes to the total impedance, an increased impedance can be
observed in sample K4, L5, and L6.

4. Conclusion

Synthesis of undoped, doped, and codoped zinc oxide nano particles

by varying amount of dopants, Ni and Mg, produced wurtzite structure.
EDS spectra proved composition of the samples. The XRD spectra
established incorporation of dopants into lattice site of zinc oxide. In all
cases, shift in peak occurred towards right, higher 2θ values. However,
Figure-27. Real part against imaginary part of impedance. the samples K4, K5, and K6 produced very less shift compared to that
produced by the samples L4, L5, and L6. The peak shift exposed that the
process of doping/codoping occurred successfully. In the present study,
θ increases so that d, the spacing between the planes, decreases upon
doping/codoping. Hence, compressive strain developed in the crystals of
ZnO upon doping/codoping. Since the samples K4, K5, and K6 produced
very less shift towards higher 2θ values than that produced by the
samples L4, L5, and L6, it could be confirmed that K4, K5, and K6
developed less, and L4, L5, and L6 developed greater compressive strain.
Crystallite size was estimated by Scherrer formula and also by
Williamson-Hall method. It is evident that sample L4 has the least
crystallite size among all the samples. The samples K4, K5 and K6 pro­
duced more crystallite size, and the samples L4, L5 and L6 produced less
crystallite size than the undoped ZnO. Material K4, K5, and K6 devel­
oped less, and L4, L5, and L6 developed greater micro strain, compared
with undoped ZnO. Tauc plot and Kubelka-Munk plot were employed for
determining bandgap energies of all samples. When compared to
undoped ZnO, the samples K4, K5, and K6 exhibited increased PL in­
Figure-28. Impedance in parallel versus frequency. tensities, indicating increased oxygen vacancy defects on the surface
upon doping and codoping. For L4, L5, and L6, a decrease in PL intensity

12
A. Athira et al. Ceramics International xxx (xxxx) xxx

was observed, that is, low surface oxygen defects, and the least for (21) (2024) 42286–42298, [Link] Part
B.
sample L6. From FESEM images, morphology was found ranging from
[7] Mary John Daphne, Nilesh S. Pillai, Akshay Sivan, P. Lasya, P. Archana, K.
spherical to nanoflakes. FTIR spectra also confirmed that doping and M. Sreekanth, G. Sivasubramanian, K.M. Sreedhar, Ferromagnetic ZnO
codoping occurred. The dielectric study revealed the variation of nanostructures from an organo zinc complex formulated via Piper Longum L-
dielectric properties of the samples with doping and codoping. For assisted green synthesis: multifaceted prospects in photocatalysis, antimicrobial
activity, and cell viability studies, Heliyon 10 (13) (2024) e33360, [Link]
undoped ZnO, there is no observable change, but for K4, K5, and K6, 10.1016/[Link].2024.e33360.
there is an increment in loss tangent with frequency. Sample L4 and [8] N. Amal, M. Athira Chandran, K.M. Sreekanth, G. Sivasubramanian, A. Chithra
undoped ZnO displayed same amount of increase in ac conductivity with Mohan, S.L. Gowri, Rishika Narendran, K.M. Sreedhar, ZnO codoped with Si and
Mn- Preparation, characterization and photocatalytic reduction of hazardous
ascending frequency. Doped/codoped samples show increased capaci­ chromium (VI) by the codoped ZnO, Mater. Today: Proc. 80 (Part 2) (2023)
tance whereas undoped ZnO shows no visible change or activity. The 947–951, [Link]
maximum capacitance can be observed with sample K5 whereas with [9] Malavika Menon, Daphne Mary John, K.M. Sreekanth, G. Sivasubramanian, P.
J. Sajna, Santhy S. Dharan, Silpa Sathyan, L. Devika, S. Aiswarya, Karthik Raja, K.
sample L5 and L6, the least. The samples are found a better candidate for M. Sreedhar, ZnO and Mn doped ZnO generated under three different synthesis
the fabrication of energy storage devices at room temperature. conditions and photocatalytic reduction of hazardous hexavalent chromium by
these photocatalysts, Mater. Today: Proc. 66 (Part 4) (2022) 2374–2380, https://
[Link]/10.1016/[Link].2022.06.333.
CRediT authorship contribution statement [10] K.M. Sreedhar, Sangeeth Sivan, Karthik Raja, Kirti Suresh, R. Sreelekshmi,
Appu Palat, K.M. Sreekanth, ZnO co-doped with Ni and Mg: preparation by co-
A. Athira: Writing – review & editing, Writing – original draft, precipitation, characterisation and effect of amount of the co-dopants on the
bandwidth of ZnO, Rasayan Journal of Chemistry 14 (2) (2021) 1289–1296.
Investigation, Formal analysis, Data curation, Conceptualization. Bindu [11] U. Sachin Varma, P. Gautham, D.V. Ravi Kumar, K.M. Sreekanth,
P. Nair: Writing – review & editing, Validation. A. Chithra Mohan: G. Sivasubramanian, K.M. Sreedhar, Co-precipitation as a tool for effective doping
Writing – review & editing. Beena Saraswathyamma: Writing – review of magnesium in zinc oxide: studies on structural, optical and photocatalytic
properties, Rasayan Journal of Chemistry 11 (4) (2018) 1491–1500, [Link]
& editing, Validation. G. Sivasubramanian: Writing – review & editing, org/10.31788/RJC.2018.1144000.
Validation. K.M. Sreekanth: Writing – review & editing, Validation. K. [12] Iqra Jabbar, Yasir Zaman, Khaled Althubeiti, Sattam Al Otaibi, M. Zahid Ishaque,
M. Sreedhar: Writing – review & editing, Writing – original draft, Nasir Rahman, Mohammad Sohail, Alamzeb Khan, Asad Ullah, Tommaso
Del Rosso, Quaid Zaman, Rajwali Khan, Aurangzeb Khan, Diluted magnetic
Validation, Supervision, Project administration, Methodology, Investi­ semiconductor properties in TM doped ZnO nanoparticles, RSC Adv. 12 (2022) 21,
gation, Data curation, Conceptualization. [Link]
[13] Priyanka Kumari, Kamakhya Prakash Misra, Saikat Chattopadhyay,
Susruta Samanta, A brief review on transition metal ion doped ZnO nanoparticles
and its optoelectronic applications, Mater. Today: Proc. 43 (2021) 3297–3302,
Declaration of competing interest
[Link]
[14] Huiqing Fan Fang, Ma Yuan, Zheng Wang, Chang Qi, Surface defects control for
The authors declare that they have no known competing financial ZnO nanorods synthesized by quenching and their anti-recombination in
interests or personal relationships that could have appeared to influence photocatalysis, Appl. Surf. Sci. 332 (2015) 47–54, [Link]
apsusc.2015.01.139.
the work reported in this paper. [15] Yuxin Jia, Huiqing Fan, Ao Zhang, Han Wang, Lei Lin, Qifeng Quan,
Guangzhi Dong, Weijia Wang, Qiang Li, Giant electro-induced strain in lead-free
relaxor ferroelectrics via defect engineering, J. Eur. Ceram. Soc. 43 (2023)
Acknowledgment 947–956, [Link]
[16] Yuxin Jia, Yongbo Fan, Lei Lin, Gang Li, Yao Su, Yuanbiao Gong, Guangzhi Dong,
The authors acknowledge STIC, CUSAT, Cochin, Kerala, India for Weijia Wang, Qiang Li, Huiqing Fan, Double flipping behavior of domains under
unidirectional electric field and giant electrostrain by defect regulation, J. Mater.
providing characterization facilities EDAX, XRD, UV-DRS, and FESEM.
Sci. Technol. 215 (2025) 15–21, [Link]
Also grateful to CIF, Pondicherry University, Pondicherry, India for BDS [17] Yongbo Fan, Xinzhen Wang, Hongtian Li, Antonio Feteira, Dawei Wang, Ge Wang,
(Broadband dielectric spectroscopy) analysis, and Bishop Moore Col­ Derek C. Sinclair, Ian M. Reaney, Pb, Bi, and rare earth free X6R barium
lege, Mavelikkara, Kerala, India for PL (photoluminescence) studies. titanate–sodium niobate ceramics for high voltage capacitor applications, Appl.
Phys. Lett. 122 (2023) 143901, [Link]
[18] S.S. Ghosh, C. Choubey, A. Sil, Photocatalytic response of Fe, Co, Ni doped ZnO
References based diluted magnetic semiconductors for spintronics applications, Superlattice.
Microst. 125 (2019) 271–280, [Link]
[19] F. Abdullah Al-Naim, A. Sedky, N. Afify, S.S. Ibrahim, Structural, FTIR spectra and
[1] Anika Tun Naziba, Manika Tun Nafisa, Ronia Sultana, Md Fahim Ehsan, A.R.
optical properties of pure and co-doped Zn1-x-yFexMyO ceramics with (M = Cu, Ni)
M. Tareq, Rimi Rashid, Harinarayan Das, AKM Atique Ullah, AKM Fazle Kibria,
for plastic deformation and optoelectronic applications, Appl. Phys. A 127 (2021)
Structural, optical, and magnetic properties of Co-doped ZnO nanorods:
1–20, [Link]
advancements in room temperature ferromagnetic behavior for spintronic
[20] A. Mondal, N. Giri, S. Sarkar, S. Majumdar, R. Ray, Tuning the photocatalytic
applications, J. Magn. Magn Mater. 593 (2024) 171836, [Link]
activity of ZnO by TM (TM = Fe, Co, Ni) doping, Mater. Sci. Semicond. Process. 91
[Link].2024.171836.
(2019) 333–340, [Link]
[2] Albena Paskaleva, Krastyo Buchkov, Armando Galluzzi, Dencho Spassov,
[21] Davood Raoufi, Synthesis and photoluminescence characterization of ZnO
Blagoy Blagoev, Tzvetan Ivanov, Vladimir Mehandzhiev, Ivalina Avramova,
nanoparticles, J. Lumin. 134 (2013) 213–219, [Link]
Penka Terzyiska, Peter Tzvetkov, Daniela Kovacheva, Massimiliano Polichetti,
jlumin.2012.08.045.
Magneto-optical and muliferroic properties of transition-metal (Fe, Co, or Ni)-
[22] M. Silambarasan, S. Saravanan, T. Soga, Raman and photoluminescence studies of
doped ZnO layers deposited by ALD, ACS Omega 7 (47) (2022) 43306–43315,
Ag and Fe-doped ZnO nanoparticles, Int. J. ChemTech Res. 7 (3) (2015), https://
[Link]
[Link]/10.1021/acsami.6b12616, 1644-165.
[3] A. Modwi, M.K.M. Ali, K. Kamal Taha, M.A. Ibrahem, H.M. El-Khair, M.H. Eisa, M.
[23] C. Jayachandraiah, K. Siva Kumar, G. Krishnaiah, N. Madhusudhana Rao, Influence
R. Elamin, O. Aldaghri, Raed Alhathlool, K.H. Ibnaouf, Structural and optical
of Dy dopant on structural and photoluminescence of Dy-doped ZnO nanoparticles,
characteristic of chalcone doped ZnO nanoparticles, J. Mater. Sci. Mater. Electron.
J. Alloys Compd. 623 (2015) 248–254, [Link]
29 (2018) 2791–2796, [Link]
jallcom.2014.10.067.
[4] Rajwali Khan, Sattam Al Otaibi, Abdulrahman J. Babqi, Nasir Rahman,
[24] P. Fermi Hilbert Inbaraj, J. Joseph Prince, Optical and structural properties of Mg
Mohammad Sohail, Rabbim Mixlievich Yusupov, Sherzod
doped ZnO thin films by chemical bath deposition method, J. Mater. Sci. Mater.
Shukhratovich Abdullaev, Alamzeb Khan, Shahid Iqbal, Tommasso Del Rosso,
Electron. 29 (2018) 935–943, [Link]
Thahir, Quaid Zaman, Aurangzeb Khan, Structural, dielectric, and magnetic
[25] Amit Kumar Rana, Yogendra Kumar, Parasmani Rajput, Shambhu Nath Jha,
responses in Doped ZnO magnetic nanoparticles for spintronics, J. Mater. Sci.
Dibyendu Bhattacharyya, M. Parasharam Shirage, Search for origin of room
Mater. Electron. 34 (3) (2023) 169, [Link]
temperature ferromagnetism properties in Ni-doped ZnO nanostructure, ACS Appl.
[5] Muhammad Adil Mahmood, Khaled Althubeiti, Sherzod Sh Abdullaev,
Mater. Interfaces 9 (8) (2017) 7691–7700, [Link]
Nasir Rahman, Mohammad Sohail, Shahid Iqbal, Kashif Safeen, Akif Safeen,
acsami.6b12616.
Aurangzeb Khan, Rajwali Khan, Diluted magnetic semiconductor behavior in Co-
[26] M. Ashokkumar, S. Muthukumaran, Microstructure, optical and FTIR studies of Ni,
and Gd-co-doped ZnO nanotubes for spintronic applications, J. Mater. Sci. Mater.
Cu co-doped ZnO nanoparticles by co-precipitation method, Opt. Mater. 37 (2014)
Electron. 34 (25) (2023) 1784, [Link]
671–678, [Link]
[6] M.G. Gopika, A. Chitra Mohan, Beena Saraswathyamma, K.M. Sreedhar, Designing
a novel electrochemical sensor based on Ni and Mg co-doped ZnO nanoparticles for
the detection and quantification of cysteamine from bodily fluids, Ceram. Int. 50

13
A. Athira et al. Ceramics International xxx (xxxx) xxx

[27] L. Umaralikhan, M. Jamal Mohamed Jaffar, Green synthesis of ZnO and Mg doped dielectric, electrical and modulus spectroscopic characteristics of ZnFe2O4 spinel
ZnO nanoparticles, and its optical properties, J. Mater. Sci. Mater. Electron. 28 ferrite nanoparticles synthesized via honey-mediated sol-gel combustion method,
(2017) 7677–7685, [Link] J. Phys. Chem. Solid. 110 (2017) 87–99, [Link]
[28] Anindita Samanta, M.N. Goswami, P.K. Mahapatra, Multiferroicity in Mg-doped jpcs.2017.05.029.
ZnO nanoparticles, Mater. Sci. Eng., B 245 (2019) 1–8, [Link] [34] M.H. Nasr, M.M. Elkholy, L.M.S. El-Deen, Gamal M. Turky, M. Moustafa, A.A. EL-
mseb.2019.05.008. Hamalawy, A.S. Abouhaswa, Synthesis, structural, electrical and magnetic
[29] P. Norouzzadeh, Kh Mabhouti, M.M. Golzan, R. Naderali, Comparative study on characteristics of Co–Cd spinel nano ferrites synthesized via sol-gel auto
dielectric and structural properties of undoped, Mn-doped, and Ni-doped ZnO combustion method, J. Sol. Gel Sci. Technol. (2024) 1–13, [Link]
nanoparticles by impedance spectroscopy analysis, J. Mater. Sci. Mater. Electron. 10.1007/s10971-024-06327-7.
31 (2020) 7335–7347, [Link] [35] Nianshun Zhao, Xiaofan Zheng, Feng Huang, Li Wang, Xuzheng Qian, Zheng Li,
[30] M.L. Dinesha, G.D. Prasanna, C.S. Naveen, H.S. Jayanna, Structural and dielectric Xin Jin, Yongli Chen, Huiqing Fan, Enhanced energy storage properties of Sm
properties of Fe doped ZnO nanoparticles, Indian J. Phys. 87 (2013) 147–153, (Mg0.5Ti0.5)O3 modified (Bi0.5Na0.5)0.7Sr0.3TiO3 relaxor ferroelectric ceramics,
[Link] Ceram. Int. 50 (2024) 8325–8331, [Link]
[31] Amit Kumar Bhunia, Sitangshu Sekhar Pradhan, Khokan Bhunia, Ashok ceramint.2023.12.166.
Kumar Pradhan, Satyajit Saha, Study of the optical properties and frequency- [36] J. Sunita Yadav, Sanketsinh Thakor, V. Adhish Raval, Poonam Sharma, V. Dimple
dependent electrical modulus spectrum to the analysis of electric relaxation and Shah, V.A. Rana, Synthesis, characterization, and unveiling dielectric spectroscopy
conductivity effect in zinc oxide nanoparticles, J. Mater. Sci. Mater. Electron. 32 insights of Fe3Se4 and Fe7Se8 nanoparticles, J. Mater. Sci. Mater. Electron. 35 (19)
(17) (2021) 22561–22578, [Link] (2024) 1323, [Link]
[32] T. Das, B.K. Das, K. Parashar, R. Kumar, Harish Kumar Choudhary, A.V. Anupama, [37] Fiaz Ahmad, Asghari Maqsood, Structural, electric modulus and complex
B. Sahoo, P.K. Sahoo, S.K.S. Parashar, Effect of Sr-doping on sinterability, impedance analysis of ZnO at low temperatures, Mater. Sci. Eng., B 273 (2021)
morphology, structure, photocatalytic activity and AC conductivity of ZnO 115431, [Link]
ceramics, J. Mater. Sci. Mater. Electron. 28 (2017) 13587–13595, [Link] [38] P. Norouzzadeh, Kh Mabhouti, M.M. Golzan, R. Naderali, Comparative study on
10.1007/s10854-017-7198-6. dielectric and structural properties of undoped, Mn-doped, and Ni-doped ZnO
[33] Raghvendra Singh Yadav, Ivo Kuřitka, Jarmila Vilcakova, Pavel Urbánek, nanoparticles by impedance spectroscopy analysis, J. Mater. Sci. Mater. Electron.
Michal Machovsky, Milan Masař, Martin Holek, Structural, magnetic, optical, 31 (2020) 7335–7347, [Link]

14