INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS

J. Phys. D: Appl. Phys. 35 (2002) 1884–1888 PII: S0022-3727(02)31698-X

The dimensional effect of breakdown field

in ZnO varistors
Shengtao Li1 , Jianying Li1 , Fuyi Liu1 , M A Alim2 and G Chen3
1
State Key Laboratory of Electrical Insulation for Power Equipment, Xi’an Jiaotong
University, Xi’an 710049, People’s Republic of China
2
Department of Electrical Engineering, Alabama A & M University, PO Box 297, Normal,
Alabama 35762, USA
3
Department of Electronics and Computer Science, University of Southampton,
Southampton, SO17 1BJ, UK
E-mail: sli@xjtu.edu.cn, lijy@xjtu.edu.cn, fyliu@xjtu.edu.cn, maalim@juno.com and
gc@ecs.soton.ac.uk

Received 7 December 2001, in final form 23 April 2002

Published 16 July 2002
Online at stacks.iop.org/JPhysD/35/1884

Abstract
The relationship between the breakdown electric field EB (electric field
corresponding to the current density 1 mA cm−2 ) and thickness d for three
types of Zinc oxide (ZnO) varistors were investigated. The geometric
dimensional effect, observed in these varistors, is referred to as the
responsible parameter for the change in EB with the variation in the
thickness of the varistor samples. The variation in the diameter of the ZnO
grains and the corresponding aspect ratio due to the irregularity of each ZnO
grain shape are used to characterize the microstructural heterogeneity of the
resulting ZnO grain size distribution. The distribution of the ZnO grain size
is statistically analysed, and thereby a model of the microstructure is
proposed. The thickness dependence of the breakdown field, EB , obtained
via computer simulation shows a similar dimensional effect to the one
observed experimentally. It was found that the critical thickness, dc ,
increases linearly with the dispersive ratio of the ZnO grain length, and the
corresponding slope (b2 ) in the large thickness domain is directly
proportional to the aspect ratio of the ZnO grains.

1. Introduction The explanation of the nonlinear I–V characteristics of

Zinc oxide (ZnO) varistors are multi-component devices
with highly nonlinear current–voltage (I–V) characteristics.
These are produced employing sintering technology for the
polycrystalline ZnO powder together with small amounts of
other cationic oxide additives such as Bi2 O3 or Pr6 O11 , Sb2 O3 ,
Co2 O3 , NiO, MnO2 , etc. The resultant structure contains
semiconducting n-type ZnO grains surrounded by insulating
electrical barriers at the grain boundaries. Due to the excellent
nonlinear electrical properties at high currents and energy
absorption capabilities, ZnO varistors are widely used as surge
protectors (arresters) for transient protection against surge
over-voltage in the electronic circuits and electrical systems.
Matsuoka’s demonstration of the multi-component device [1]
has revolutionized the electrical power industries. A broad
review of fabrication, composition, microstructure, electrical
properties, and application methods of these varistors are
available elsewhere [2, 3].
the varistors supported by various models is available in the
literature. These are not listed here. However, the back-
to-back double Schottky barrier across the grain boundaries
responsible for the highly nonlinear behaviour is noted by
Levine [4]. The role of these back-to-back double Schottky
barriers were experimentally demonstrated by Morris [5].
These barriers are complicated in nature due to their frequency-
dependent behaviour. Such a complexity of these barriers have
been studied by Alim et al [6, 7]. Mahan et al [8] proposed
that the high nonlinear coefficient in the breakdown region
was generated by minority carrier creation in the Schottky
barrier region of the ZnO grains. It is suggested that the
holes were formed by impact ionization [9], while energetic
electrons surmounting these barriers formed the electron–hole
pairs. Several studies [3, 10–12] of the microstructure strongly
support the above model.
It was generally accepted that the breakdown voltage of
each grain boundary is finite and may be assumed to be near

0022-3727/02/151884+05$30.00 © 2002 IOP Publishing Ltd Printed in the UK 1884

 Dimensional effect of breakdown field in ZnO varistors

a constant [13–16]. The total breakdown voltage along the 3. Results and discussion
single thread direction of the current flow in the ZnO varistor
is the product of breakdown voltage of each grain boundary and The results are noted systematically in the following sections.
the number of grain boundaries. According to this proposition, These are based on the observations made in the laboratory.
if the same material system is adopted, the breakdown strength
of EB (defined as the electric field corresponding to the
current density 1 mA cm−2 ) should have nothing to do with 3.1. The dimensional effect of breakdown field EB
the thickness of the samples as it is normalized with the
The relation between the breakdown field EB and the
thickness and electrode area. However, this cannot be the
thickness d of various samples are shown in figure 1. In this
case because the varistor microstructure is not an ideal system.
plot it is clear that with respect to the increasing breakdown
Because of the uncertainty of both chemical composition and
field of the samples, the curves are drifting toward the high
phases in grain boundary regions, the electrical property of
fields. However, there is an inflection or turning (critical) point
a grain boundary depends on the type of the interface [17],
for each of these curves. This turning point determines two
and its breakdown voltage can be 0, 0.4, 0.6, 0.9, 3.2, 3.6, or
critical parameters that can be defined as
4.1 V [18].
In this paper, the geometric dimensional effect has been (a) critical thickness dc ; and
proposed based on the observed change in the breakdown (b) critical (or transition) breakdown field Ec .
strength with respect to the thickness of the ZnO varistor
Just before reaching the critical point, where d is smaller
sample. The origin of the dimensional effect is studied by using
than dc , the logarithm of the breakdown field EB (EB < Ec )
the microstructural information of the commercial samples
increases linearly with an increase in d. Then above the critical
having identical recipe/formulation/chemistry and consistent
point when the thickness of the sample keeps increasing, the
processing variables in the manufacturing set-up. It is found
increase in the logarithm of EB (EB > Ec ) is very slow
that the dimensional effect is an intrinsic property of the
making the entire curve very much nonlinear. Although device
ZnO varistors that can be referred to the other polycrystalline
processing methods and the adjustment of the varistor recipe
ceramic devices based on the grain boundary effects as in
have significantly improved the performance characteristics
the positive temperature coefficient of resistance (PTCR)
of the resulting product during the past two decades, this
devices and ceramic resistors/capacitors.
observation is still quite obvious for most modern commercial
devices. Nevertheless, such a behaviour can be empirically
2. Experimental termed in the following equation:

Three types of samples were used to study the dimensional EB ∝ exp(bd), (1)
effect of the breakdown electric field EB and nonlinear
coefficient α. The size of these samples are noted in diameter× where the exponent b represents the transitional behaviour for
length. These samples are: (a) low breakdown field samples L the entire curve. However, before the inflection in figure 1 in
with original dimension 14.0 mm × 1.71 mm; (b) intermediate the small thickness domain this exponent may be denoted as
breakdown field sample M with original dimension 7.42 mm × b1 and after the inflection in the large thickness domain this
0.705 mm; and (c) high breakdown field sample H with original exponent may be denoted as b2 . Table 1 shows the values of
dimension 7.41 mm × 1.98 mm. The first type of the samples b1 , b2 , dc , and Ec for the three types of varistors. It is clear
is the prototype device. The later two types of samples are the that b2 decreases as Ec increases, while b1 increases as Ec
commercial devices. increases except for the sample H. Such an effect is described
Larger sampling of all these devices (minimum 10 per as the dimensional effect.
type of device such as L or M or H) was used in the present
investigation. Only three types of the aforementioned devices
are reported. Careful coarse grinding and then fine lapping
operations in the laboratory were adopted to achieve the
variation in the thickness of the samples. The electrode
was applied using silver paste on the opposite faces of each
sample having a specific area and then dried in the oven. The
breakdown electric field, EB , was determined by measuring
the electric field applied to the device when the current density
corresponded to 1 mA cm−2 .
For the microstructure studies, the samples were polished
and etched with hydrofluoric (HF) acid solution, and then
cleaned and dried. The microstructure was monitored using a
scanning electron microscope (SEM: Hitachi S-2700). Since
most of the grains exhibited elliptic shape, the longest distance
was measured first and defined as the horizontal distance. Then
the vertical distance was measured. The number of grains Figure 1. The relation between the breakdown field, EB , and the
measured was 172 for sample L, 226 for sample M, and 191 —sample L, •—sample M, and
thickness d of various samples: 
for sample H. —sample H.

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Li Shengtao et al

Table 1. The exponents b1 and b2 , the critical thickness dc and the

transition breakdown field Ec of three types of ZnO varistors.
dc Ec
Sample b1 b2 (mm) (V mm−1 )
H 9.4 0.21 0.19 185
M 18.6 0.31 0.28 110
L 6.0 0.36 0.98 33

In an earlier study [19], it has been reported that the

dimensional effect is noticed for the samples with various
as-grown (as-sintered) thickness. This study was in addition
to the variation of the sample thickness achieved by the
grinding and lapping operations of the device. From such
extensive studies in conjunction with present investigation, it is
reasonable to consider that the dimensional effect is an intrinsic
characteristic of the ZnO varistors. Again, b1 , b2 , dc , and Ec
are the determining parameters for the dimensional effect in
these varistors.

3.2. Structural dependence of the dimensional effect:

distribution of grain size and shape
The SEM micrographs of three samples (H, M, L) described
above are depicted in figure 2. Sample H indicates well-
formed microstructure via repetitively ordered shape of the
identical grains having much less porosity. Since the electrical
behaviour of the commercial devices is always very much
identical and satisfies the quality requirements the degree of
porosity, the degree of porosity is not considered to be a
critical factor. Within the consistent level of porosity the
performance of the devices is satisfactory and meets quality
standards. Based on the previously conducted unpublished
results [20], the level of porosity is reasonably estimated to be
consistent and less than 0.5% with respect to the theoretical
density of the ZnO varistor block. In modern days, this level
of porosity is considered to be a saturated flat observation and
has very little effect on the protective characteristics of the
ZnO varistors. This flat level porosity has been achieved as
the processing technology matured since its evolution in Japan
[1]. The grains in the sample M are slightly elongated and Figure 2. Scanning electron micrographs of the three samples:
dispersed containing identical degree of porosity with respect H, M, L.
to the sample H. The grains in the sample L are slightly skewed
in shape, possessing non-uniform size distribution having a
little more porosity when compared to the samples H and M.
This enhanced level of porosity is in no way detrimental to the
resulting performance of the device as the variation is estimated
to be too small from the microstructural evaluation.
From the SEM micrographs, the horizontal and vertical
distances of minimum 170 grains were measured for every
sample. The aspect ratio (defined as the ratio of long diameter
and short diameter for a single grain which is regarded as an
ellipse in this paper) of the ZnO grains was also calculated. An
extra kind of sample with a breakdown field of 18 V mm−1 was
investigated in order to study the microstructure dependence
of the dimensional effect in detail. The corresponding values
of b1 , b2 , dc are 2.4, 0.43, and 1.34 mm. Figure 3 shows
the linear relation between the critical thickness dc and the
dispersive ratio (defined as the ratio of standard deviation of Figure 3. The linear relation between the critical thickness dc , and
the grain length and average value of the grain length) between the dispersive ratio.

1886
 Dimensional effect of breakdown field in ZnO varistors

Figure 4. The relation between b2 and the average aspect ratio.

the standard deviation and the average of the longer diameters. Figure 5. Microstructural model of ZnO varistors for computer
A similar investigation indicates that dc also depends linearly simulation.
on the dispersive ratio along the shorter diameter of the ZnO
grains. Such pieces of information provide a concept of critical The average of the grain size in the vertical axial grain series lˆ
thickness dc that is connected to the dispersive ratio of the ZnO is also the stochastic variable and follows normal distribution.
grain size. The deviation of lˆ is σ 2 /(d/µ) as the average grain number of
Figure 4 depicts an approximate linear relationship a vertical axial grain series is d/µ. Therefore, rearranging the
between the large thickness domain exponent b2 and the distribution function, it is found that [24]
average aspect ratio. It appears that b2 increases with an  
increase of average aspect ratio. This indicates that the 1 (lˆ − µ)2
ˆ =√
f (l) √ exp − . (4)
thickness dependence of the breakdown field EB is enhanced 2π (σ/ d/µ) 2(σ 2 /(d/µ))
as the grain shape transforms from the regular ordered shape
to the skewed shape. When the average grain size locates within the region demar-
ˆ lˆ + l,
cated by l, ˆ the number of grain series ρn(l) ˆ can be
3.3. Statistical analysis and computer simulation expressed by
ˆ = Nf (l)
n(l) ˆ l.ˆ (5)
The experimental results show that the distribution of the grain
size follows a normal distribution function [21] and is given When the applied voltage on the vertical axial grain series
V is greater than (d/l)Vˆ GB , the grain boundary can be
by the probability density function f (l). This is expressed
as [22, 23] segmented among each vertical axial series leg so that the
relation between the current (Ii ) and voltage (V ) is given by


1 (l − µ)2
f (l) = √ exp − , (2) d ˆ d
2πσ 2σ 2 V = VGB + Ii (l) ρg , (6)
ˆl ˆ 2
n(l)µ
where σ is the standard deviation (of l), µ is the mean reading
of the distribution of the grain size, and l is the distribution of where VGB is the breakdown voltage of a single grain boundary
the grain size. The estimated value of µ can be achieved by and ρg is the resistivity of the ZnO grain.
When the applied voltage V is less than (d/l)V ˆ GB ,
analysing the samples.
the vertical axial grain series cannot be segmented and the
Figure 5 shows the model of the ZnO varistors that has the
estimated current through the column is zero. The total
diameter D and thickness d. Three assumptions are made to
current flowing through the vertical axial series column is the
simplify the analysis. These are
summation of the individual current flowing through N grains
(a) each grain on the surfaces is a square of length µ, in that column. This accounts for
(b) each grain on the surface forms a continuous series 
structure in the vertical axial direction, and Itotal = ¯
Ii (l). (7)
(c) current flow through each axial series structure has no
By increasing the applied voltage V , a I–V curve can be
effect on each other.
generated. From this curve, EB can be determined. Also the
Now the number of grains on the surface can be estimated by variation in the thickness d of the samples and its relation with
using [24] EB can be developed. The average grain size µ and deviation
σ 2 of the samples H and M are determined by measuring the
πD 2 grain size distribution. For sample H, µ = 7.45 µm and σ 2 =
N= . (3)
4µ2 7.18 µm2 . For sample M, µ = 10.5 µm and σ 2 = 22.7 µm2 .

1887
Li Shengtao et al
Figure 6. The computer simulation results of the relation between
EB and the thickness d.
The diameter, D, is 7.4 mm for both the samples. The computer
simulation results concerning the relation between EB and d
is shown in figure 6. While developing this plot the measuring
term E1 mA (electric field corresponding to the current 1 mA)
is also used to verify the same behaviour.
It may be further noted that µ and σ 2 represent definite
values in the term 2σ 2 /(d/µ). Therefore, the deviation
changes only with the thickness d. The maximum of the
probability density of lˆ is given by
1 [11] Kemenade J T C and Ejinthoven R K 1979 Direct
f (µ) = √ √ . (8)
2π(σ/ d/µ)
ˆ increases when
Thus, from equation (8) it is observed that f (l)
d increases. This means that the distribution of lˆ is more
centralized. This implies because the probability density is
increased when d is increased, most of lˆ values locate in a
narrow area, which means more centralized. As a result, it
is understood that the dimensional effect originates from the
change of the deviation with thickness d. The dimensional
effect is a macroscopic expression of population behaviour of
varistor units (or blocks or individual devices) that consists of
ZnO grains and grain boundaries.
4. Conclusions
Based on the investigation conducted on the ZnO varistors the
following conclusions can be drawn.
The relationship between the breakdown electric field EB
(or E1 mA ) and sample thickness d shows the dimensional
effect. The critical thickness dc , the transition breakdown field
Ec , slope b1 and b2 are recommended as the characteristics of
the dimensional effect.
The dimensional effect originates mainly from the hetero-
geneity in the ZnO grain size distribution and irregularity of the
ZnO grain shape. The critical thickness dc increases linearly
with the dispersion of the ZnO grain size. The corresponding
slope (b2 ) is directly proportional to the average aspect ratio.
Computer simulation based on a simple microstructural
model indicates the existence of the dimensional effect of
the breakdown electric field EB . Further analysis shows that
the dimensional effect is an intrinsic property of the ZnO
varistors.
1888
Acknowledgment
The authors would like to thank financial support for this
research of the National Natural Science Foundation of China
(Project Number 59507005).
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