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Article history:
Received 3 May 2011
Accepted 4 June 2011
Available online 13 June 2011
Keywords:
ZnO
Varistors
Electrical properties
Defects
a b s t r a c t
In this paper, AC ageing characteristics of high voltage gradient ZnO varistors doped with different Y2O3
concentration were investigated. The voltage gradient of these samples is markedly improved by increasing
Y2O3 content, however, the nonlinear coefcient decreases and the leakage current increases at the same
time.
Y2O3-doped ZnO samples exhibit lower stability under accelerated AC ageing stress of 0.85 1mA/135 C/168 h,
V
compared with samples without Y2O3. Double-Schottky barrier(DSB) parameters before and after ageing
tests indicate that the decrease of barrier height for traditional sample is less than that for high voltage
gradient sample, which should be ascribed to its slight variation in the interface state density.
2011 Elsevier B.V. All rights reserved.
1. Introduction
ZnO varistor behaves high nonlinear currentvoltage characteristic and has been extensively used in metal oxide arresters (MOA) to
protect electrical device against overvoltage surges in power systems
[14]. However, ZnO varistor in-use is usually subjected to a longterm AC or DC voltage stress which may lead to the increase of
leakage current. This is the so-called ageing phenomenon and will
eventually make the
varistors thermally broken down or
destructed [57]. Therefore, the ageing characteristics of ZnO
varistors have attracted massive attention of researchers in this eld
[4,8,9].
In order to shorten the length and reduce the weight of MOA used
in higher voltage level power transmission lines (e.g. 500 kV, 750 kV
or 1000 kV) and gas-insulated substations (GIS), ZnO varistors with
high voltage gradient have been developed [10]. In general, the
voltage gradient of ZnO varistor is proportional to the number of ZnO
grains in series per unit thickness. As a result, high voltage gradient
ZnO varistor could be obtained by decreasing the grain sizes. Recently,
it is reported that several rare earth oxides, such as Y2O3 and Dy2O3,
could be considered as ZnO grain growth inhibitors during the
sintering process. Although the microstructures and compositional
phases of ZnO varistors doped with Y2O3 have been proposed in
several literatures [1113], investigation on the inuence of Y2O3 on
the AC ageing characteristics of ZnO varistors has not been carried out
yet. Since high voltage gradient ZnO varistors are subjected to higher
operation voltage and overvoltage surge stress, the ageing characteristics should be paid more attention to.
In present work, ZnO varistor samples doped with different
content of Y2O3 were prepared and degraded under accelerated AC
ageing stress
of 0.85 V1mA/135 C/168 h. The electrical properties and doubleSchottky barrier (DSB) parameters before and after the ageing tests
were measured and compared. And then, the AC ageing mechanism
was discussed based on the experimental results, as well.
2. Experimental procedure
The compositions of ZnO varistors were (95.05 x) mol% ZnO,
0.70 mol% Bi2O3, 0.50 mol% MnO2, 1.00 mol% Co2O3, 0.50 mol%
Cr2O3,
1.00 mol% Sb2O3, 1.25 mol% SiO2 and x mol% Y2O3, where x = 0,
0.50,
0.75 and 1.00, respectively. These analytical-grade raw reagents were
homogenously mixed, dried and pressed into round discs. And then,
the pellets were sintered at 1200 C for 3 h. Finally, both sides of the
samples were painted with silver paste. The obtained samples were
labeled as ZY000, ZY050, ZY075 and ZY100, respectively. The surface
microstruc- ture graphs of obtained samples were obtained by SEM
(JSM-6460LV, JEOL Inc., USA).
Accelerated AC (50 Hz) ageing tests were carried out under
continuous voltage stress of 0.85 V1mA at 135 C for 168 h. The current
density-electric eld (JE) characteristics were measured by a digital
source meter (Model 2410, Keithley Instruments Inc., USA). The
voltage gradient E1mA is dened as the electric eld where the current
is 1 mA, the nonlinear coefcient is calculated by equation = 1/log
(E1mA/E0.1mA) and the leakage current IL is the current corresponding
to 0.75 E1mA. And then, the ageing rate coefcient KT was calculated by
1/2
equation IL = IL0 + KTt , where IL0 and IL is the leakage current
before and after stress. The capacitancevoltage (CV) characteristics
were measured by a dielectric spectrometer
(Concept 80,
Novocontrol
Technologies GmbH & Co. KG., Germany). The DSB parameters,
including donor density Nd, interface state density Ni and barrier
2
height b, were determined by linearly tting (1/C 1/2C0) Ugb
curves [14].
0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.06.022
2596
Fig. 1. The surface microstructure graphs of ZnO varistors with high voltage gradient.
(a)
b =
(b)
Fig. 2. The JE characteristics of ZnO varistors before and after AC ageing test.
e Ni
20 r Nd
Y2 O3ZnO
2YZn + VZn
+ 2OO X+
1
O2 :
Table 1
Comparison on electrical properties and DSB parameters of ZnO varistors before and
after AC ageing test.
Sample
ZY000
ZY050
ZY075
ZY100
E1mA0 (V/mm)
E1mA (V/mm)
0
IL0(A)
IL(A)
KT(A h 1/2)
17
-3
Nd0 (10 cm )
17
-3
Nd (10 cm )
12
-2
Ni0(10 cm )
12
-2
Ni(10 cm )
b0 (eV)
b (eV)
315.6
316.9
35.1
34.8
0.14
0.35
0.016
1.88
2.13
1.49
1.48
1.25
1.10
402.2
400.5
29.8
29.1
0.54
3.36
0.218
0.44
0.33
0.74
0.45
1.30
0.66
505.5
505.0
21.6
20.6
2.67
3.72
0.081
0.46
0.42
0.68
0.58
1.09
0.87
737.4
719.8
15.4
15.3
9.51
11.1
0.120
0.34
0.30
0.56
0.48
0.99
0.81
2597
(a)
(b)
Zn + V = Zn + V :
i
Zn
i
Zn
Fig. 3. The (1/C 1/2C0) Ugb characteristics of ZnO varistors before and after AC
ageing test.