Journal of Alloys and Compounds 817 (2020) 152700

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Journal of Alloys and Compounds

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Influence of CaO doping on phase, microstructure, electrical and

dielectric properties of ZnO varistors
K. Hembram a, b, *, T.N. Rao a, M. Ramakrishana a, R.S. Srinivasa b, A.R. Kulkarni b
a
Center for Nanomaterials, International Advanced Research Center for Powder Metallurgy & New Materials (ARCI), Balapur PO, Hyderabad, 500005, A.P,
India
b
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India

a r t i c l e i n f o a b s t r a c t

Article history: In present study, impact of CaO doping on microstructure and phase electrical properties of a ZnO
Received 31 May 2019 varistor is being reported. The doped ZnO nanopowders were prepared by solution combustion followed
Received in revised form by conventional sintering. The ZnO particle size of powders decreased from 22 to 17 nm with CaO doping
7 October 2019
was noted. Decrease in grain size of the sintered samples from 4.54 to 1.19 mm with CaO doping was
Accepted 15 October 2019
Available online 16 October 2019
observed. This is attributed to Ca4Bi6O13 and Ca0.89Bi3.11O5.58 secondary phase formations apart from
pyrochlore and spinel phases. A breakdown field as high as 21 kVcm
1 in X ¼ 1.00 sample was obtained.
The Coefficient of nonlinearity (a) decreased from 95 to 42 is due to decrease in carrier concentrations.
Keywords:
ZnO
Increase in resistivity with CaO doping and decrease in resistivity beyond X ¼ 2.5 were noted. The electric
Doping modulus plots yielded two relaxations at a temperature in the range 100e300  C and frequency in the
Sintering range 0.1 Hz-1MHz. Activation energy (Ea) decreased from 0.65 to 0.50 eV for a region I and from 0.89 to
Electrical properties 0.75 eV for region II with CaO doping was observed.
Varistor © 2019 Elsevier B.V. All rights reserved.
Dielectric

1. Introduction The high performance varistors are achieved by getting a ho-

Polycrystalline ZnO ceramic varistor behaves like Zener diode,
however with a better coefficient of nonlinearity and much higher
energy absorption capacity. It is used in wide range of surge pro-
tection applications; starting from electronic circuit to large current
transmission line [1e3]. In general, commercial ZnO varistors
breakdown field are reported in the range 2-3kVcm
1 and coeffi-
cient of non-linearity in the range 30e90, these devices are pre-
pared by conventional powder metallurgy route having a
composition containing more than five oxides such as Bi, Sb, Co, Cr
and Mn oxides to name a few, and are used in limited to the rela-
tively low-voltage applications [3e5]. When these varistors are
used in high surge voltage applications which needed higher
numbers of discs resulting increase in residual voltage in the
varistor discs leading to catastrophic failure of the device. A varistor
having breakdown field of >10 kVcm
1 is recommended to over-
come such problems [4,5].
* Corresponding author. Center for Nanomaterials, International Advanced
Research Center for Powder Metallurgy & New Materials (ARCI), Balapur PO,
Hyderabad, 500005, A.P, India.
E-mail address: kaliyan@arci.res.in (K. Hembram).
mogeneous microstructure and uniform dopant distribution, small
grain size with a narrow size distribution and highly dense discs. It
is well documented that the varistor made from nanopowders
exhibited superior properties compared to commercial [6e9].
Breakdown voltage is proportional to the number grain boundaries
in a given volume. There are reported of controlling of grain size
and size distribution by using advanced sintering methods e.g. SPS
[10], hot press [11]. However, controlling of grain growth by
advanced sintering techniques is quite expansive and also required
post heat treatment to get required varistor properties [10]. Engi-
neering the grain growth by addition of dopants is comparatively
inexpensive. Dopants play an important role to control most of the
electrical properties of the varistor; Sb2O3 [12], SiO2 [13]ZrO2 [14]
and Al2O3 [15] are added as a grain growth inhibiter in ZnO varistor.
ZnO grain growth is retarded by pinning mechanism. Generally,
antimony oxide is used as a grain growth inhibiter in a ZnO varistor,
however, regulation of antimony oxide due to environmental
concern, novel dopants are needed to be identify for grain growth
inhibiter which could provide above challenges and possible better
properties of a varistor. There is hardly any literature available
exclusively study on effect of CaO doping on ZnO varistor system to
best of our knowledge. In our previous study simple

https://doi.org/10.1016/j.jallcom.2019.152700
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2 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700

ZnOeBi2O3eCaO and ZnOeBi2O3eCaOeCo3O4 varistor system, an
excellent combination of electrical properties was obtained [16]. In
this study, ZnO varistors are fabricated from doped ZnO nanpow-
ders, and the effect of CaO doping on varistor properties are stud-
ied. The density, microstructure and phase of ZnO varistor are
studied and structure-property correlation is established. The
electrical properties of ZnO varistors are studied by VeI and com-
plex impedance measurement.
2. Experimental and characterization techniques
with emery papers of different grades (600 and 1000). A dimple of
3 mm diameter was produced by an ultrasonic cutter (GATAN,
Model 601) followed by thinned down to 50e60 mm by polishing
with 2000 emery paper. The sample was kept in an ion milling
(GATAN, Model No # 691) for 8e10 h, with an energy at 4 KeV
(current 11 mA) for both the guns and an angle at 11 till small hole
was formed. Before putting into TEM for analysis, sample was
cleaned with 1.5 KeV energy for 15 min. Selective elemental
composition analysis of the microstructure was studied by energy-
dispersive X-ray spectroscopy attached to TEM (EDS, EDAX, USA).

2.1. Processing of the powder 2.3. Electrical properties measurement

Zn (NO3)2.6H2O (99%, Alfa Asear), Cr(NO3)3.9H2O (99%, Loba 2.3.1. IeV characteristics
Chemical), Co (NO3)2 .6H2O (99%, Sigma-Aldrich), Mn(NO3)2.6H2O The sintered pellets having diameter of ~8 mm and thickness of
(99%, Sigma-Aldrich) and Ca (NO3)2 .4H2O (99.9%, Alfa-Asear) were ~1 mm were studied IeV characteristics. Silver was applied both
dissolved in de-mineralized water followed by heating at the faces of a pellet as a contact electrode. The IeV characteristics of
50e100  C to make a solution (Solution 1). Bi (NO3)3 .5H2O (99%, the pellets were measured by breakdown voltage tester (5 kV DC,
Sigma-Aldrich) was mixed in dilute-nitric acid (99.9%, Loba) (So- Rectifier Electronics, India). The coefficient of nonlinearity (a) was
lution 2) and Sb2O3 (99%, Loba) was dissolved in citric acid (99%, SD estimated by using equation: a ¼ (log J2-log J1)/(log E2-log E1),
Fine) (Solution 3). The solution 2 and 3 were mixed into the solu- where E1 is the field at current density J1 (0.1 mAcm
2) and E2 is
tion 1. Sucrose was added to the solution as a fuel. The solution was field at current density J2 (1 mAcm
2). The breakdown field (Eb)
heated ~200  C and stirred till the solution completely dried up and was estimated at a reference current density of 1 mAcm
2. A
catch fire. As-synthesized powders were calcined at 750  C for 1 h. voltage drop per barrier (Vg) per grain boundary was calculated
The composition used for present study was ZnO: 88 wt%, Bi2O3: using the equation: Vg ¼ V (d/t-1), where, V is the breakdown, d is
5.00 wt%, Sb2O3: 3.50 wt%, Co3O4: 1.50 wt%, MnO2: 1.00 wt% and the average grain size, t is the thickness of the sample. The leakage
Cr2O3: 1.00 wt%. To understand the impact of CaO doping on phase, current density (Lc) was estimated at 75% of the Eb (1mA).
microstructure and properties of a varistor, a different concentra-
tions of CaO 0.00 (X ¼ 0.00), 0.25 (X ¼ 0.25), 1.00 (X ¼ 1.00), 2.50
2.3.2. Dielectric and impedance study
(X ¼ 2.50) and 5.00 (X ¼ 5.00) wt. % were synthesized. The calcined
AC electrical properties of the sintered pellets at different
powders were blended by pot milling for 4 h. A 2.0 wt% PVA dis-
temperature and frequency were studied with an impedance
solved in water was used a binder and powder to ball ratio was kept
analyzer (Alpha-High Resolution Novocontrol, Germany) in the
1:4 during the bending. The mixture slurry was dried in an oven at
wide range frequencies (mHz-MHz) and temperatures (25e500  C
150  C for 6 h in open atmosphere. The pellets was made in 10 mm
at 25  C intervals). Silver was used as an electrode.
stainless steel die with pressure of 160 MPa. The pellets (~50% of the
theoretical density) were debineded at 600  C-3h (heating rate 1
 Cmin-1). Two-step sintering cycle was used for sintering the pel- 3. Results and discussion
lets: first heated to 1000  C and held for 0.5 h followed by cooled to
925  C and held for 4 h. The rates of cooling and heating was kept at 3.1. X-ray diffraction of powders
2  Cmin-1 till 925  C followed by furnace cooling.
Fig. 1 shows the XRD patterns of undoped (UDVP) and CaO
2.2. Phase and microstructure characterization doped varistor ZnO nanopowders (CDVP) samples. The red vertical
lines are the Bragg position of the ZnO phase (JCPDS No.: 36-1541,
Phase of powder samples were analysed by X-ray diffractometer P63mc/186). In all the samples a negative shift in 2q is observed
(XRD, Bruker D8 Advance) using Cu Ka radiation. The crystallite size
of powder samples was calculated by using Scherrer equation. The
composition of the calcined powder samples was studied by ICP-
OES (Varian, Liberty Series II) whereas surface chemistry of the
powders was analysed by XPS (Omicron, Nano Technology, UK).
Differential scanning calorimetry (DSC) analysis of the powder
samples were carried using thermal analyser (Netzsch, STA 449 F3
Jupiter, Germany) in air. The morphology and particle size of the
powder samples were studied by transmission electron microscopy
(TEM, TECNAI, 200 KV, FEI, Netherlands). The powder was
dispersed by sonication in an ethanol solvent around 10e15 min, a
drop of dispersed nanopowders was put on a copper grid for TEM
analysis. An average particle size of the powders was estimated
from dark field TEM images. Porosity and density of sintered
samples were measured by ASTM-C373-88. The phase of sintered
samples was confirmed by X-ray diffractometer. The microstructure
of thermally etched sintered samples was studied by SEM
(Se3400 N, Hitachi, Japan). An average grain size was estimated by
the linear intercept technique [17]. The TEM sample was prepared
of sintered (X ¼ 0.00 and X ¼ 1.00) samples which were thinned Fig. 1. Comparison of XRD patterns for with and without CaO doped ZnO varistor
down by Isomet and then reduced thickness to 200 mm by polishing powders calcined at 750  C for 1 h.
 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700
compared to the Bragg position of ZnO. A small peak corresponding
to Ca4Bi6O13 (JCPDS No.: 13-7122) was observed in CDVP samples
having X  1.00 (a weak single peak is observed in the present case,
identification has been substantiated later in phase study of sin-
tered pellet samples). The lattice parameters and crystal volume
decreased up to X ¼ 1.00 CaO doping, after that it remains constant
(Tables Se1). A decrease in lattice constant and crystal volume is
attributed to the formation of Ca4Bi6O13 precipitates on the pow-
ders for the higher concentration of CaO doped samples. XPS
analysis of X ¼ 1.00 CDVP sample shows a presence of Zn2þ, Sb3þ
and Bi3þ but no Ca species spectrum is observed, indicating that
ZnO powder surface is coated with Bi2O3 and Sb2O3; ZnO is doped
with Co2þ, Cr2þ, Mn2þ and Ca2þ ions species (Figure S-1). It has
been demonstrated in earlier HRTM studies that the big ionic
diameter species like Sb3þ and Bi3þ precipitates out on the surface
of ZnO during the calcination and sintering process [5,60]. Increase
in lattice constant and crystallite volume by ~0.30% for varistor
powder samples compared to pure ZnO. The lattice expansion of
ZnO crystal is due to doping of higher ionic diameter species
Sb3þ ¼ 0.76 Å, Bi3þ ¼ 1.03 Å and Ca2þ ¼ 1.06 Å [18]. The Ca2þ may
occupy the interstitial site of Zn2þ in the lattice of ZnO. It is known
that the solubility limit of dopants is improved due to the size
reduction of the materials [19]. Solid solubility of calcium in ZnO is
reported in nano and bulk by a few researchers [20]. The ZnO lattice
volume expansion of ~0.2 mol % is demonstrated with calcium
doping in earlier work [20]. However, the solubility of calcium in
ZnO is contradicted by a few other researchers. Immiscibility of
calcium in ZnO is explained by the fact that the ionic diameter of
Ca2þ (1.06 Å) is too large compared to Zn2þ (0.63 Å). Secondly, the
crystal structure of these two species is not the same [21,22]. Till
date, solid solubility of calcium in ZnO is a debatable issue.
3.2. TEM study of the powders
To understand better, the influence of CaO doping on
morphology and crystallite size, dark field TEM on powder samples
were taken; the crystallite size is compared with XRD. Fig. 2 (a) and
(b) show dark field TEM images and insets are crystallite size dis-
tribution histograms of UDVP and X ¼ 1.00 CDVP samples, respec-
tively. A log-normal crystallite distribution was observed in all
powder samples with an unnoticeable difference in morphology.
Effect of CaO doping on ZnO crystallite size (XRD and TEM) of the
powder samples is depicted in Fig. 2 (c). The graph clearly shows
decrease in ZnO crystallite size with CaO doping. Mean particle/
crystallite size (TEM) was decreased from 19.60 ± 0.30 nm to
17.00 ± 0.30 nm (X ¼ 5.00) with CaO doping. A similar trend was
observed crystallite size measured using Scherrer equation
(decrease from 24 ± 0.4 nm to 17 ± 0.4 nm) with CaO doping. ZnO
Wurtzite phase was confirmed by both TEM electron diffraction
patterns and XRD techniques. The particle size measured from dark
field TEM is very close to crystallite measured from the Scherrer
equation which suggest that each particle corresponds to a crystal.
A decrease in crystallite size may be due to segregation of Ca4Bi6O13
and Bi3Zn2Sb3O14 phases on the ZnO surfaces of the powders. The
grain growth retardation is due to the Zener drag effect as observed
in classical alumina-zirconia system [23,24].
3.3. Compositional and thermal analysis of the powders
The quantitative compositions (ICP-OES) of powder samples are
given in the Tables Se2. It can be seen that the compositions were
retained to an experimental error limit in all powder samples.
However, deviation of Bi2O3, CaO, and Sb2O3 additives was
observed to some extent in the powder samples which is attributed
to segregation of Bi2O3 and Sb2O3. A comparative DSC analysis of
3
X ¼ 0.00 and X ¼ 1.00 samples is shown in Figure S-2. It can be seen
a small peak (first endothermic reaction) for X ¼ 0.00 sample
at ~ 600  C which could be corresponding to melting of ZnO, Bi2O3
and Sb2O4 phases. The pyrochlore (Bi3Zn2Sb3O14) phase formation
takes place at >500  C by reacting ZnO, Bi2O3 and Sb2O4 phases and
an eutectic temperature of ZnOeBi2O3 is 740  C [2]. The peaks at
~875  C and ~980  C are corresponding to Zn2.33Sb0.67O4 and Bi2O3
phases formation, and peak at ~1110  C is indication of evaporation
of Bi2O3 for X ¼ 0.00 sample. The first peak at ~830  C could be
corresponding to Ca4Bi6O13 phase formation for X ¼ 1.00 sample.
The peaks at ~905  C and ~1000  C are for phase formation of
Zn2.33Sb0.67O4 and Ca0.89Bi3.11O5.58 (Figure S-2). The detail discus-
sion will be carried out again in following section. During the
calcination process a liquid phase forms by reaction among all these
phases resulting in segregation of the oxides. A small deviation of
dopants of transition metal oxides e.g. Co3O4, Cr2O3 and MnO2 were
observed in the powder samples. This indicates that these transi-
tion oxides are homogeneous distributed throughout the matrix
phase of ZnO.
3.3.1. Phase analysis of sintered pellets
Comparison of overall XRD patterns of undoped (UDV) and CaO
doped ZnO varistor (CDV) samples is shown in Fig. 3 (a) and close
view of secondary phases formation in Fig. 3 (b). ZnO (JCPDS No.:
36-1451) along with secondary phases of d-Bi2O3 (JCPDS No.: 52-
1007), Zn2.33Sb0.67O4 (JCPDS No: 15-0687) and Bi3Zn2Sb3O14 (JCPDS
No.: 36-0114) were yielded in UDV and X ¼ 0.25 CDV samples. For
X ¼ 1.00 CDV sample, Ca0.89 Bi3.11O5.58 (JCPDS No.: 040-0317) and
Ca4Bi6O13 (JCPDS No.: 048-0217) phases were observed apart from
the above phases. However, for X ¼ 2.50 and X ¼ 5.00 CDV samples
the majority of grain boundary phases were of Ca4Bi6O13 and
Ca0.89Bi3.11O5.58 instead of d-Bi2O3, Bi3Zn2Sb3O14 and Zn2.33Sb0.67O4
phases (Fig. 3 (b)). It is necessary to understand the phase forma-
tion in commercial ZnO varistors before going into a discussion of
CDV samples. During the initial stages of sintering, Sb2O4 and Sb2O5
phase formation takes place from Sb2O3 in the temperature range
600e800  C. Bi3Zn2Sb3O14 and Zn2.33Sb0.67O4 formation take place
by decomposition of ZnO, Sb2O5 and Bi2O3 in the temperature range
700e900  C, while orthorhombic spinel (Zn7Sb2O12) and bismuth
oxide formation takes place by decomposition of the ZnO, cubic-
spinel and pyrochlore in the temperature range 900e1050  C
[2,25,26]. The spinel composition of Zn2.33Sb0.67O4 and Zn7Sb2O12
exists in ZnO varistor, and high temperature orthorhombic
Zn7Sb2O12 phase is thermodynamically stable [27]. Bi2O3 helps in
densification and wetting of ZnO grains. Bi2O3 exists in five poly-
morphic phases viz. a, g, d, b and ε. In ZnOeBi2O3 varistors only g,
d and b Bi2O3 phases have been reported by researchers [28]. The d-
Bi2O3 is known to be the fastest ionic conductor among all the other
Bi2O3 phases. Pyrochlore and spinel (both cubic and orthorhombic)
phases are known as ZnO grain growth retarder [29],122]. Gener-
ally, spinel are present near the triple junction and grain boundary
as well as inside the ZnO grains in the form of inverse grain
boundary [3,26]. In the present study, major contributions to
decrease in ZnO grain size is due to the formation of Ca4Bi6O13 and
Ca0.89Bi3.11O5.58 phases along with Zn2.33Sb0.67O4 and Bi3Zn2Sb3O14
phases in the CDV samples. To understand the phase formation in
CDV samples the ½ Bi2O3eCaO phase diagram was studied closely
in detailed [30,31]. It can be seen in the phase diagram that for
10 mol % CaO composition the CaBi2O4 and Bi2O3 phases are
formed, and above 10 mol% the Ca3Bi8O15, Ca4Bi6O13, and Ca2Bi2O5
phases are reported. Non-stoichiometric Ca0.89 Bi3.11O5.58 phase
formation is favored for the specific composition and heating above
1000  C followed by quenching to room temperature (JCPDS No.
040-0317) [69]. Stoichiometric Ca4Bi6O13 phase is favored at a
temperature below 800  C (JCPDS No 048-021) which could be seen
4 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700

Fig. 2. Dark field TEM images and insets are the crystallite size distribution of ZnO (a) (X ¼ 0.00) and (b) (X ¼ 1.00) ZnO varistor powders. (c) Influence of CaO doping on crystallite
size of the ZnO powders.

in DSC as well (Figure S-2). Above phases are within the range of
present compositions and processing temperatures. The above
phases are similar to that of SiO2 and WO3 doped ZnO varistors. The
grain boundary secondary phases of ZnSiO4, Bi2SiO5, and Bi24Si2O40
were reported in case of SiO2 doped ZnO varistor samples [13,32].
The secondary phases of ZnWO4, Bi2WO6 for WO3 doped ZnO
varistor were reported [33]. These secondary phases are known to
be oxygen generators at grain boundary interfaces and grain
growth retarders resulting in better electrical properties in ZnO
varistors.

3.4. Microstructure analysis

3.4.1. SEM study of sintered pellet

Fig. 3. (a) Comparison of XRD patterns, (b) close view of secondary phase with and
without CaO doping sintered samples.
SEM images of thermally etched and grain size distribution plots
of X ¼ 0.00 UDV and X ¼ 1.00 CDV samples are shown in Fig. 4. It
can be seen that a wide grain size distribution (2e7 mm) with an
average grain size of 4.54 mm was obtained for (X ¼ 0.00) UDV
sample, whereas a narrow grain size distribution in the range
0.5e2.0 mm with an average grain size of 1.25 mm for (X ¼ 1.00) CVD
samples was obtained. Density of 5.62 and 5.49 ± 0.05 gcc
1 (99-
97% of theoretical) for X ¼ 0.00 and X ¼ 1.00 samples was obtained,
respectively. Effect of CaO doping on density and grain size is
depicted in Fig. 4(c). It can be seen in the plot that the grain size and
density decreased with CaO doping. A decrease in density could be
due to the presence of CaO whose theoretical density is 3.34 gcc
1
and is the lowest among all the dopants and matrix phase. Another
factor for decrease in density of sintered samples could be the
presence of higher amount of pyrochlore and lesser liquid Bi2O3
phase formation during sintering [34]. However, it is difficult to
estimate the actual theoretical density of the sintered samples due
to the presence of complex phases, the theoretical density of 5.67
gcc
1 is considered of the varistor samples for approximation [35].
The porosities in these samples were less than the 1e3% which
 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700
Fig. 4. SEM images and insets are the grain size distribution of (a) pure (X ¼ 0.00) and (b) CaO doped (X ¼ 1.00) varistor samples. (c) Influence of CaO doping on grain size of the
sintered samples.
means that the samples densities were greater than 97% of
theoretical.
3.4.2. TEM study of sintered pellet
To confirm the phase formation and to locate the calcium rich
phase in the microstructure TEM, SAED and EDS studies were car-
ried out on (X ¼ 0.00) UDV and (X ¼ 1.00) CDV samples. EELS
mapping was carried out on a (X ¼ 1.00) CDV sample. Bright field
TEM image along with EDS and SAED patterns at different locations
namely matrix, triple point, and grain boundary areas of (X ¼ 0.00)
UDV sample are shown in Fig. 5(aee). EDS studies confirmed that
ZnO is doped with Co2þ whereas bismuth rich and spinel phases are
heavily doped with transition ions of Co, Mn, and Cr as shown in
Fig. 5(b). SAED patterns confirmed a Wurtzite ZnO matrix phase
along with secondary phases of d-Bi2O3 and Zn2.23Sb0.67O4 in the
UDV sample as shown in Fig. 5(c)(d) and (e), respectively which are
in good agreement with XRD result. Phases obtained in the above
samples are well known in ZnO varistors [1,3,4]. Bright field TEM
image, EDS spectrum at different location of the microstructure,
bright and dark (insets) field TEM images at grain boundary and
SAED pattern of grain boundary phase for X ¼ 1.00 CDV sample are
shown in Fig. 6(aef). EDS spectrum confirm presence of Zn and Co
at core ZnO grain and Zn, Ca, Bi, Sb, Cr, and Mn at triple point;
however, overlapping of Sb and Ca energy peaks were observed, as
shown in Fig. 6 (b), (c) and (d). EDS at grain boundary interface and
grain boundary area shows the presence of Bi, Ca and Sb species.
The twin/stacking faults within the ZnO matrix grains were dis-
cerned. Bi3Zn2Sb3O14 phase formation at grain boundary area was
confirmed. Surprisingly, spinel Zn2.23Sb0.67O4 phase could not be
detected by SAED patterns in X ¼ 1.00 CDV sample; it may be
because the amount of spinel is less than pyrochlore phase. Even
after repeated efforts, the Ca0.89Bi3.11O5.58 and Ca4 Bi6O13 phases
could not be established by SAED technique; it is because more
than one phases are present at the grain boundary and triple
5
junction points and the SAED diffraction patterns are interfering
among neighboring phases resulting in mixed electron diffraction
patterns. Another experimental problem faced was detecting cal-
cium species by EDS, and it was because EDS energy spectra of Sb
and Ca are very close to each other, making it difficult to differen-
tiate between them. EELS mapping at the grain boundary and the
triple junction was carried out to locate calcium in the micro-
structure. Bright field TEM image, EDS spectrum and EELS mapping
at the triple junction are shown in Fig. 6(gei) for X ¼ 1.00 CDV
sample. EELS mapping confirming the calcium species (white)
segregated at the triple junction which is shown in Fig. 6(h). EELS
mapping has an energy resolution of ~1 eV whereas for EDS it is
over 20 eV; therefore, it is easy to detect low atomic weight ele-
ments by EELS compared to EDS. However, SAED studies are unable
to confirm the phases present at triple points due to the complexity
and limitation of experiments involved. At this point, XRD, EDS, and
EELS mapping studies indicated that Ca0.89Bi3.11O5.58 and Ca4Bi6O13
phases are located at triple point and grain boundary area. These
phases are responsible for ZnO grain growth retardation due to
Zener drag [23,24].
3.5. Electrical properties
3.5.1. Varistor properties
Fig. 7 (a) shows the comparison of IeV characteristics for UDV
and CDV samples, and Table 1 summarizes their electrical proper-
ties. Effect of CaO doping on ZnO varistor properties are displayed
in Fig. 7 (b-e): (b) breakdown field, (c) barrier voltage, (d) leakage
current density and (e) coefficient of nonlinearity. Breakdown field
increased with CaO doping, reaches a maximum at 20.3 ± 1 kVcm
1
in X ¼ 1.00 CDV sample, after that decreased and then remain
almost constant. Increase in breakdown field is due to a decrease in
ZnO grain size. The barrier voltage was found to be in the range
2.51-1.82 ± 0.25 V for all the samples. Barrier voltage decreased
6 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700
Fig. 5. TEM studies of sintered (X ¼ 0.00) sample. (a) Bright field TEM image, (b) EDS at different locations, (c) SAED on ZnO grain (d) triple junction and (e) secondary phase.
slightly with CaO doping. However, it does not change significantly.
In general, for ZnO varistor, the barrier voltage per grain boundary
is in the range 2e4 V [2,3,36,37]. Leakage current density increases
from 1.15 to 170 ± 0.5 mA/cm2 with CaO doping, it is due to decrease
in the relative density of the samples. The coefficient of nonline-
arity decreased from 95 to 42 ± 5 with CaO concentration and it is
due to reduction in carrier concentration, increase in resistivity of
ZnO grain and decrease in bulk density for the higher CDV samples
[38]. It is well known that the breakdown field is inversely pro-
portional to ZnO grain size of a varistor [5,6,8]. Bi2O3 rich liquid
phase wets the ZnO grain boundaries during sintering and forms a
few nanometer thin insulating layer between the ZnO grains which
is responsible for Schottky barrier formation. Bi2O3 and Sb2O3
segregate at the depletion layer lead to an increase in charge carrier
density of the ZnO varistor. The best electrical properties is found in
a device where an excess of oxygen with a monolayer of Bi2O3 are
present at the grain boundaries [25,39,40]. Abnormal increase in
breakdown field in CDV samples compared to UDV sample is due to
ZnO grain refinement and presence of oxygen-rich secondary grain
boundary phases of Ca0.89 Bi3.11O5.58 and Ca4Bi6O13 at the interface
between grains apart from the spinel and pyrochlore phases
[33,41]. As demonstrated by XRD and SAED patterns, secondary
phases of d-Bi2O3, Zn2.23Sb0.67O4, Bi3Zn2Sb3O14 were observed in
the X ¼ 0.00 UDV and X ¼ 0.25 CDV samples. The d-Bi2O3 is known
to be a highly oxygen-ion conductor due to the presence of oxygen
vacancies which is responsible for a better coefficient of nonline-
arity. A decrease in coefficient of nonlinearity is due to doping of
CaO into ZnO matrix and Bi2O3 phases resulting in a reduction in
carrier concentration (equations (1)e(3)). However, XRD, TEM, EDS,
and EELS analysis suggested that the major grain boundary phases
are Ca0.89Bi3.11O5.58, Ca4Bi6O13 along with d-Bi2O3, Zn2.23Sb0.67O4
and Bi3Zn2Sb3O14 for X  1.00 CDV samples which are responsible
for altering electrical properties.
In the case of monovalent metal oxide doping, the metal ions
substitute the Zn2þ site in ZnO lattice, acts as acceptors and leads to
a decrease in the coefficient of nonlinearity [42]. For trivalent metal
oxides, the metal ions substitute the Zn2þ site of ZnO lattice
releasing electrons by ionization and acting as donors, increasing a
[15,43]. In case of CaO doping, the ionic diameter of Ca2þ (1.06 Å) is
too big compared to Zn2þ (0.63 Å) to substitute, therefore, it pref-
erable moves to Bi3þ site position of Bi2O3. Substitution and inter-
stitial doping of Ca2þ into Zn2þ ion in the lattice of ZnO at the
vicinity of the depletion region are possible. On CaO doping, three
possible defect reactions can occur as described by [44,45]:
Bi2 O3
.
2CaO
















!2Ca’Bi þ V::o þ 1 2O2 (1)
ZnO
CaO




!Ca::i þ V }Zn þ 2OXo (2)
ZnO
CaO




!Ca}Zn þ V ::o (3)
The first reaction is Ca2þ substituting Bi3þ in the Bi2O3 lattice
and generating O2 and oxygen vacancies V::o which act as an
acceptor resulting in decreasing electron trap density at the grain
boundary interface (reaction 1). The second reaction is Ca2þ going
at interstitial of Zn2þ
i in ZnO lattice, with generation of two extra
holes, as shown in defect reaction 2. These holes in the valence
band behave like acceptors. The third possible reaction is the Ca2þ
substituting Zn2þ in ZnO lattice and generating V ::o in the vicinity of
depletion regions of grains, as described in reaction 3. The V ::o acts
as acceptor which decrease the carrier density resulting in a
 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700 7

Fig. 6. TEM studies of sintered (X ¼ 1.00) sample. (a) Bright field TEM image, (b-d) EDS at different locations, (e) Bright field TEM image and inset is the dark field TEM image of
secondary phase and (f) SAED of secondary phase; (g) Bright field TEM image, (h) EELS mapping and (i) EDS at triple point of sintered (X ¼ 1.00) sample.

decrease in coefficient of nonlinearity for CDV samples [44,46]. In
particular, for X ¼ 0.25 CDV sample, reduction in the coefficient of
nonlinearity is due to a decrease in density of traps at the interface
as explained in Eqn 1. For X  1.00 CDV samples, the trap density at
the interface is more due to the presence of oxygen absorption
Ca0.89 Bi3.11O5.58 and Ca4Bi6O13 phases at grain boundary interface.
However, the carrier concentration at the vicinity of depletion is
less which reduce the net charge carrier concentration resulting in
a decrease in coefficient of nonlinearity.
3.5.2. Impedance, dielectric and conductivity studies
To verify the IeV results and to understand the effect of CaO
doping on grain and grain boundaries resistance, dielectric prop-
erties of ZnO varistor the complex impedance results are analysed.
A complex impedance is written as [16,47].
 
1  
1
1 1
Z* ¼ Z’
Z} ¼þ juCg þ þ juCgb1
Rg Rgb1
 
n 
1
þ 1 Rgb2 þ Ao ðjuÞ
where u is the angular frequency, n represents the depression of
impedance graph, Cg is grain capacitance and Rg is grain resistance.
Rgb1and Cgb1 are the capacitance and resistance of grain boundary
type 1. Rgb2 and Cgb2 ¼ YCPE ¼ Ao ðjuÞn are the resistance and
capacitance of grain boundary type 2. Relaxation take place when
product of angular frequency, resistance and capacitance is unity,
uRC ¼ 1. Grain boundary type 1 is allocated to the lowest resis-
tance component whereas grain boundary type 2 to the highest
resistance component. Fig. 8 shows complex impedance plots; the
experimental data are fitted to two parallel RC circuits (insert of
Fig. 8) for UDV and CDV samples. Two parallel RC circuit models
have been used for data interpretation in ZnO varistors by several
researchers [48e50]. Tables Se3 summarized dielectric properties
at 200  C and 50 Hz for all the samples. The high-frequency inter-
cept (1 MHz) values of the Z0 axis were found to be ~100 U-cm at
room temperature for all the samples which are designed as a re-
sistivity of core ZnO (Rg). The Rg was found to be marginally higher
in higher CDV samples compared to the UDV sample. The trend of
Rg is consistent with the coefficient of nonlinearity values. The
impedance of grain may be influenced by the inductive effect
(4) associated with the experimental arrangement; care is needed to
obtain realistic values from the high-frequency intercept. In a few
8 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700

Fig. 7. Influence of CaO doping on varistor properties of sintered samples: (a) IeV characteristics, (b) breakdown field, (c) voltage drop per barrier, (d) leakage current density and
(e) coefficient of non-linearity.

Table 1
Effect of CaO doping on varistor properties of sintered samples.

Sample ID Density (gcc
1) Grain Size (mm) Bf (kVcm
1) a Leakage Current Density (mAcm
2) Barrier Voltage (Volt)

X ¼ 0.00 5.59 ± 0.05 4.54 ± 0.50 05.53 ± 0.5 95 ± 5 01.1 ± 0.15 2.51 ± 0.50
X ¼ 0.25 5.59 ± 0.05 1.65 ± 0.25 13.83 ± 1.0 65 ± 5 48 ± 5.0 2.30 ± 0.25
X ¼ 1.00 5.49 ± 0.05 1.25 ± 0.25 20.30 ± 1.0 49 ± 5 87 ± 5.0 2.52 ± 0.25
X ¼ 2.50 5.43 ± 0.05 1.32 ± 0.25 16.16 ± 1.0 50 ± 5 171 ± 5.0 2.13 ± 0.25
X ¼ 5.00 5.26 ± 0.05 1.19 ± 0.25 15.85 ± 1.0 42 ± 5 170 ± 5.0 1.80 ± 0.25

instances in literature, the capacitance Cg (10
12-10
13 F) is
neglected, since the frequency needed to resolve is very high for a
small sample [51]. It is well reported that ZnO grain relaxation peak
is a representation of the intrinsic Zni and Vo defects [52e55]. The
extracted Rgb, Cgb1 Cgb2 values are given in Tables Se3. The grain
core resistivity was neglected here since Rg « Rgb1þRgb2. The
capacitance values of Cgb1 was increased from 235 to 530 pF and
Cgb2 decreased from 262 to 101 pF (200  C) with CaO doping. The
Rgb increased with increasing CaO doping up to X ¼ 1.00 CDV
(5.16 MU-cm) and then decreased to 0.593 MU-cm. The trend of Rgb
is consistent with the breakdown field (IeV measurement) of the
samples. Increase in resistivity with increasing CaO doping up to
 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700
Fig. 8. Complex impedance plots at different concentration of CaO for sintered sam-
ples: symbols are experiment data and solid lines are fitted data to two parallel RC
circuit model (inset).
1.00 wt % is due to a decrease in charge carriers which is explained
by defect equations (1)e(3). A decrease in resistivity for X ¼ 2.50
CDV sample and beyond is due to the increase in mobility of the
charge carrier due to the decrease in carrier concentrations. This
observation is in good agreement with earlier studies on CaO doped
ZnO sputtered films [38].
Frequency dependent real part of dielectric constant and tan d
for UDV and CDV samples are presented in Fig. 9 (a) and (b). The
dielectric constant gradually decreases with frequency, however,
beyond 105 Hz the value remains almost constant. The dielectric
constant was found to be in the range 465e3878 ± 5 at 50 Hz and
200  C. The dielectric constant of a boundary-layer capacitor in bulk
ceramic is inversely proportional to the thickness of grain boundary
and directly proportional to the grain size of the material [56]. The
liquid phase at the grain boundary is more in case of X ¼ 0.00 UDV
and X ¼ 0.25 CDV compared to X ¼ 1.00 and X ¼ 2.50 CDV samples.
Therefore, the boundary layer thickness for X ¼ 1.00 CDV sample
would be less compared to X ¼ 0.00 UDV sample. The factors
affecting dielectric constant in the present study are the average
Fig. 9. Effect of CaO doping on (a) dielectric constant and (b) Tan d of sintered samples at 200  C.
9
grain size of ZnO and thickness of grain boundary. The phase for-
mation is not the same for UDV and CDV samples, hence directed
correlation cannot be justified for the present study. As it can be
seen that Tan d decreases drastically with frequencies ~103 Hz and
remains constant thereafter. Tan d value in the range 4.5e39.5 ± 0.5
were obtained at 50 Hz and 200  C. Tan d decreases with CaO
doping up to X ¼ 1.00 and increases after that. Tan d is due to
electric dipole rotation which cause Joule heating by friction [57].
The tan d and leakage current obtained from IeV graphs are com-
plementing each other. Tan d in the range of 5e30 and dielectric
constant of 1000e4000 were reported at 50 Hz and temperature
100e175  C [51,57]. The present study dielectric results are within
the range of reported values.
The frequency dependent AC conductivity temperature in the
range 125e500  C at 25  C interval for all samples. The experi-
mental data were fitted to Jonscher’s power law. The conductivity
spectrum shows two regions viz. (i) The low-frequency plateau and
(ii) the mid-frequency dispersion. This phenomenon is explained
by a modified Jonscher’s power law [58]. The temperature depen-
dent exponent “n” values were found to be in the range 0.34e0.90
as shown in Fig. 10(a). The “n” value in the range 0e1 is attributed
to translational hopping of charge carriers [58]. The charge carrier
movement could be explained by thermally activated hopping be-
tween two grains separated by insulation barrier which is a typical
conduction mechanism observed in dielectric materials [59].
The activation energy of DC conductivity is estimated using
equation:
Ea
sdc ¼ so exp (5)
kT
where so is defined as the pre-exponential factor, Ea is defined as
the activation energy and k is defined as the Boltzmann’s constant.
It can be seen clearly in the Arrhenius plot (Fig. 10(b)) that there are
two stages of DC conductivity, region I (<175  C) and rejoin II
(>200  C) for all the samples which are attributed to shallow and
deeper traps. It may be noted that the activation energy of DC
conductivity decreases with CaO doping which is attributed to a
decrease in barrier strength and carrier concentration (equations
(1)e(3)). The d-Bi2O3 phase forms Schottky barrier between grains
for X < 0.25 CDV samples whereas Ca0.89 Bi3.11O5.58 and Ca4Bi6O13
phases are found to be responsible for barrier formation for
X  1.00 CDV samples [1,60,61]. Decrease in grain size and increase
in breakdown field and resistivity are attributed to the
10 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700
Fig. 10. Impact of CaO doping on (a) conductivity Exponent “n” and (b-c) activation energy of DC conductivity of sintered samples.
Ca0.89Bi3.11O5.58 and Ca4Bi6O13 phases at the grain boundary
interfaces.
Fig. 10(c) shows the Arrhenius plot of t2 and t1 for all the
samples. Activation energy of relaxation peaks were found in the
range 0.79-0.60 for t2 and for t1 ¼ 0.59e34 in all samples. The
activation energy for t2 was found in the range 0.79 eV is due to
good Schottky junction (R2C2: homo-junction). The activation en-
ergy for t1 was found in the range 0.34 eV is due to Ca0.89 Bi3.11O5.58
and Ca4Bi6O13 phases between the two grains (R1C1: hetero-
junction) for X  1.00 CDV samples [61]. The activation energy of
t1 and t2 of X ¼ 0.25 and X ¼ 1.00 CVD samples are comparable to
X ¼ 0.00 UDV sample. However, as CaO doping increased to
X ¼ 2.50 and X ¼ 5.00 the barrier strength decreased drastically
was due to a decrease in bulk density and carrier concentrations.
4. Conclusion
Influence of CaO doping on phase, microstructures and electrical
properties of ZnO varistor were studied. Decrease in crystallite size
of the powder from 22 to 17 nm with CaO doping was observed.
Grain size of the sintered body decreased from 4.54 to 1.19 mm with
CaO doping. This is attributed to Ca4Bi6O13 and Ca0.89 Bi3.11O5.58
secondary phase formation. Breakdown field as high as 21 kVcm
1
in X ¼ 1.00 CDV sample was obtained in present study. The Coef-
ficient of nonlinearity (a) decreased from 95 to 42 is due to a
decrease in carrier concentration. From IeV and impedance mea-
surements, it can be concluded that the increase in resistivity with
CaO doping is due to the reduction in carrier concentration;
decrease in resistivity beyond X ¼ 2.50 CDV samples is attributed to
increasing in carrier mobility. The electric modulus plots yielded
two relaxations at a temperature in the range 100e300  C and
frequency in the range 0.1 Hz-1MHz. Ea decreased from 0.65 to
0.50 eV for a region I and from 0.89 to 0.75 eV for region II with CaO
doping is attributed to decrease in carrier concentration and trap
density at the interface.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
 K. Hembram et al. / Journal of Alloys and Compounds 817 (2020) 152700
Acknowledgements
This work was partially supported by DST-SERB, Govt. of India
(Grant No. SB/EMEQ-221/2013). Authors would like thanks the
Director, ARCI for giving permission to publish this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2019.152700.
References
[1] M. Matsuoka, Nonohmic properties of zinc oxide ceramics, Jpn. J. Appl. Phys.
10 (1971) 736.
[2] D. Clarke, Varistor ceramics, J. Am. Ceram. Soc. 82 (1999) 485e502.
[3] T.K. Gupta, Application of zinc oxide varistors, J. Am. Ceram. Soc. 73 (1990)
1817e1840.
[4] J. Li, S. Li, P. Cheng, M. Alim, Advances in ZnOeBi2O3 based varistors, J. Mater.
Sci. Mater. Electron. 26 (2015) 4782e4809.
[5] S.C. Pillai, J.M. Kelly, R. Ramesh, D.E. McCormack, Advances in the synthesis of
ZnO nanomaterials for varistor devices, J. Mater. Chem. C 1 (2013)
3268e3281.
[6] P. Dura n, F. Capel, J. Tartaj, C. Moure, A strategic two-stage low-temperature
thermal processing leading to fully dense and fine-grained doped-ZnO va-
ristors, Adv. Mater. 14 (2002) 137e141.
[7] R.N. Viswanath, S. Ramasamy, R. Ramamoorthy, P. Jayavel, T. Nagarajan,
Preparation and characterization of nanocrystalline ZnO based materials for
varistor applications, Nanostructured Mater. 6 (1995) 993e996.
[8] Y. Lin, Z. Zhang, Z. Tang, F. Yuan, J. Li, Characterisation of ZnO-based varistors
prepared from nanometre precursor powders, Adv. Mater. Opt. Electron. 9
(1999) 205e209.
[9] K. Hembram, D. Sivaprahasam, T.N. Rao, Combustion synthesis of doped
nanocrystalline ZnO powders for varistors applications, J. Eur. Ceram. Soc. 31
(2011) 1905e1913.
[10] L.S. Macary, M.L. Kahn, C. Estourne s, P. Fau, D. Tre
mouilles, M. Bafleur, et al.,
Size effect on properties of varistors made from zinc oxide nanoparticles
through low temperature spark plasma sintering, Adv. Funct. Mater. 19 (2009)
1775e1783.
[11] T. Asokan, Grain boundary properties of hot pressed zinc oxide varistors,
Mater. Res. Bull. 28 (1993) 1277e1284.
[12] T. Senda, R.C. Bradt, Grain growth of zinc oxide during the sintering of zinc
oxidedantimony oxide ceramics, J. Am. Ceram. Soc. 74 (1991) 1296e1302.
[13] Z. Wu, J. Fang, D. Xu, Q. Zhong, L.-Y. Shi, Effect of SiO2 addition on the
microstructure and electrical properties of ZnO-based varistors, Int. J. Miner.
Metall. Mater. 17 (2010) 86e91.
[14] Y. Akiyama, M. Takada, A. Fukumori, Y. Sato, S. Yoshikado, Effect of ZrO2
addition on tolerance characteristics of the electrical degradation of ZnO va-
ristors, Electr. Eng. Jpn. 179 (2012) 11e19.
[15] J. Fan, R. Freer, The roles played by Ag and Al dopants in controlling the
electricalproperties of ZnO varistors, J. Appl. Phys. 77 (1995) 4795e4800.
[16] K. Hembram, T.N. Rao, M. Ramakrishna, R.S. Srinivasa, A.R. Kulkarni, A novel
economical grain boundary engineered ultra-high performance ZnO varistor
with lesser dopants, J. Eur. Ceram. Soc. 38 (2018) 5021e5029.
[17] M.I. Mendelson, Average grain size in polycrystalline ceramics, J. Am. Ceram.
Soc. 52 (1969) 443e446.
[18] R.C. Weast, Handbook of chemisty and physics, 49th ed, Am. J. Med. Sci. 257
(1969) 423.
[19] B.B. Straumal, A.A. Mazilkin, S.G. Protasova, A.A. Myatiev, P.B. Straumal,
B. Baretzky, Increase of Co solubility with decreasing grain size in ZnO, Acta
Mater. 56 (2008) 6246e6256.
[20] K.-I. Inoue, M. Miyayama, Chlorine gas sensing properties of ZnO-CaO ce-
ramics, J. Electroceram. 2 (1998) 41e48.
[21] A. Whitaker, D.F. Borton, Phase equilibria in the system CaO-ZnO-B2O3 at
850 C, J. Mater. Sci. 7 (1972) 194e197.
[22] M. Wang, J.-P. Sun, S. Suei, I.G. Hill, Optimizing the photovoltage of polymer/
zinc oxide hybrid solar cells by calcium doping, J. Appl. Phys. 112 (2012)
044511.
[23] J.D. French, M.P. Harmer, H.M. Chan, G.A. Miller, Coarsening-resistant dual-
phase interpenetrating microstructures, J. Am. Ceram. Soc. 73 (1990)
2508e2510.
[24] D. Fan, L.-Q. Chen, S.-P.P. Chen, Numerical simulation of zener pinning with
growing second-phase particles, J. Am. Ceram. Soc. 81 (1998) 526e532.
[25] D.R. Clarke, The microstructure location of the intergrabular metal-oxide
phase in a zinc oxide varistor, J. Appl. Phys. 49 (1978) 2407e2411.
[26] A.T. Santhanam, T.K. Gupta, W.G. Carlson, Microstructural evaluation of
multicomponent ZnO ceramics, J. Appl. Phys. 50 (1979) 852e859.
[27] G.C. Miles, A.R. West, Polymorphism and thermodynamic stability of
Zn7Sb2O12, J. Am. Ceram. Soc. 88 (2005) 396e398.
[28] T. Takemura, M. Kobayashi, Y. Takada, K.E.N. Sato, Effects of bismuth
11
sesquioxide on the characteristics of ZnO varistors, J. Am. Ceram. Soc. 69
(1986) 430e436.
[29] F. Greuter, G. Blatter, Electrical properties of grain boundaries in poly-
crystalline compound semiconductors, Semicond. Sci. Technol. 5 (1990) 111.
[30] E.Y. Vstavskaya, A.Y. Zuev, V.A. Cherepanov, The phase diagram of the
bismuth-calcium oxide system, Mater. Res. Bull. 29 (1994) 1233e1238.
[31] R.S. Roth, N.M. Hwang, C.J. Rawn, B.P. Burton, J.J. Ritter, Phase equilibria in the
systems CaOeCuO and CaO-Bi2O3, J. Am. Ceram. Soc. 74 (1991) 2148e2151.
[32] H.-Q. Shao, X.-H. Gao, Z.-C. Cao, Effect of annealing on phase structure and
degradation of a zinc oxide varistor with Si-additive, J. Eur. Ceram. Soc. 17
(1997) 55e59.
[33] X. Xiao, L. Zheng, L. Cheng, T. Tian, X. Ruan, M. Podlogar, et al., Influence of
WO3-doping on the microstructure and electrical properties of ZnOeBi2O3
varistor ceramics sintered at 950 C, J. Am. Ceram. Soc. 98 (2015) 1356e1363.
[34] M. Peiteado, M. De La Rubia, J. Ferna ndez, A. Caballero, Thermal evolution of
ZnO-Bi2O3-Sb2O3 system in the region of interest for varistors, J. Mater. Sci. 41
(2006) 2319e2325.
[35] S. Hingorani, V. Pillai, P. Kumar, M.S. Multani, D.O. Shah, Microemulsion
mediated synthesis of zinc-oxide nanoparticles for varistor studies, Mater.
Res. Bull. 28 (1993) 1303e1310.
[36] E. Olsson, G.L. Dunlop, Characterization of individual interfacial barriers in a
ZnO varistor material, J. Appl. Phys. 66 (1989) 3666e3675.
[37] J.T.C. Van Kemenade, R.K. Eijnthoven, Direct determination of barrier voltage
in ZnO varistors, J. Appl. Phys. 50 (1979) 938e941.
[38] K.P. Misra, K.C. Dubey, R.K. Shukla, A. Srivastava, Reduction in carrier con-
centration by calcium doping in ZnO thin films. emerging trends in electronic
and photonic devices & systems, in: ELECTRO ’09 International Conference
on2009, 2009, pp. 495e496.
[39] D.R. Clarke, Grain-boundary segregation in a commercial ZnO-based varistor,
J. Appl. Phys. 50 (1979) 6829e6832.
[40] J. Wong, Microstructure and phase transformation in a highly non
Ohmic
metal oxide varistor ceramic, J. Appl. Phys. 46 (1975) 1653e1659.
[41] F. Stucki, F. Greuter, Key role of oxygen at zinc oxide varistor grain boundaries,
Appl. Phys. Lett. 57 (1990) 446e448.
[42] D.J. Binks, R.W. Grimes, Incorporation of monovalent ions in ZnO and their
influence on varistor degradation, J. Am. Ceram. Soc. 76 (1993) 2370e2372.
[43] W.G. Carlson, T.K. Gupta, Improved varistor nonlinearity via donor impurity
doping, J. Appl. Phys. 53 (1982) 5746e5753.
[44] M. Barsoum, M. Barsoum, Fundamentals of Ceramics, CRC press, 2002.
[45] K. Jacobs, F.A. Kro €ger, The Chemistry of Imperfect Crystals. 2nd Revised Edi-
tion, Volume 1: preparation, Purification, Crystal Growth And Phase Theory.
North-Holland Publishing Company - Amsterdam/London 1973 American
Elsevier Publishing Company, Inc. - New York 313 Seiten, zahlreiche Abbil-
dungen und Tabellen, Kunstleder Preis Dfl. 70.00, Krist. Tech. 9 (1974)
K67eK68.
[46] L. Schmidt-Mende, J.L. MacManus-Driscoll, ZnO e nanostructures, defects, and
devices, Mater. Today 10 (2007) 40e48.
[47] R. Tang, C. Jiang, W. Qian, J. Jian, X. Zhang, H. Wang, et al., Dielectric relaxation,
resonance and scaling behaviors in Sr3Co2Fe24O41 hexaferrite, Sci. Rep. 5
(2015) 13645.
[48] P.R. Bueno, S.A. Pianaro, E.C. Pereira, L.O.S. Bulho ~es, E. Longo, J.A. Varela,
Investigation of the electrical properties of SnO2 varistor system using
impedance spectroscopy, J. Appl. Phys. 84 (1998) 3700e3705.
[49] X. Zhao, R. Liao, N. Liang, L. Yang, J. Li, J. Li, Role of defects in determining the
electrical properties of ZnO ceramics, J. Appl. Phys. 116 (2014) 014103.
[50] R Nadar Viswanath, S Nadar Ramasamy, Impedance spectroscopy studies of
nanosturctured ZnO based varistor materials, Mater. Trans. 42 (2001)
1647e1652.
[51] L.M. Levinson, H.R. Philipp, AC properties of metal-oxide varistors, J. Appl.
Phys. 47 (1976) 1117e1122.
[52] P. Cheng, S. Li, L. Zhang, J. Li, Characterization of intrinsic donor defects in ZnO
ceramics by dielectric spectroscopy, Appl. Phys. Lett. 93 (2008) 012902.
[53] P.R. Bueno, J.A. Varela, E. Longo, SnO2, ZnO and related polycrystalline com-
pound semiconductors: an overview and review on the voltage-dependent
resistance (non-ohmic) feature, J. Eur. Ceram. Soc. 28 (2008) 505e529.
[54] X. Zhao, J. Li, H. Li, S. Li, Intrinsic and extrinsic defect relaxation behavior of
ZnO ceramics, J. Appl. Phys. 111 (2012) 124106.
[55] M. Andres-Verges, A.R. West, Impedance and modulus spectroscopy of ZnO
varistors, J. Electroceram. 1 (1997) 125e132.
[56] J. Wu, C.-W. Nan, Y. Lin, Y. Deng, Giant dielectric permittivity observed in Li
and Ti doped NiO, Phys. Rev. Lett. 89 (2002) 217601.
[57] G.H. Chen, J.L. Li, C.L. Yuan, Y. Yang, The nonlinear electrical behavior of ZnO-
based varistor ceramics with CaSiO3 addition, J. Mater. Sci. 49 (2014)
758e765.
[58] A.K. Jonscher, The ‘universal’ dielectric response, Nature 267 (1977) 673e679.
[59] M.M. Costa, G.F.M. Pires, A.J. Terezo, M.P.F. Graça, A.S.B. Sombra, Impedance
and modulus studies of magnetic ceramic oxide Ba2Co2Fe12O22 (Co2Y) doped
with Bi2O3, J. Appl. Phys. 110 (2011) 034107.
[60] H. Cerva, W. Russwurm, Microstructure and crystal structure of bismuth oxide
phases in zinc oxide varistor ceramics, J. Am. Ceram. Soc. 71 (1988) 522e530.
[61] M. Bartkowiak, G.D. Mahan, F.A. Modine, M.A. Alim, Influence of ohmic grain
boundaries in ZnO varistors, J. Appl. Phys. 79 (1996) 273e281.