J. Am. Ceram. Soc.
, 91 [11] 3593–3598 (2008)
Journal
An AFM/EFM Study of the Grain Boundary in ZnO-Based
Varistor Materials
Simoni M. Gheno,w,z Ruth H. G. A. Kiminami,z Márcio M. Morelli,z Jusmar V. Bellini,y
and Pedro I. Paulin Filhoz
z
Department of Materials Engineering—DEMa, Federal University of São Carlos—UFSCar Rod. Washington Luiz,
y
Department of Physics—DF, State University of Maringa, UEM, Maringa 87020-900, PR, Brazil
Zinc oxide (ZnO)-based varistors are metal oxide varistors
whose nonlinear properties are characterized by electrical resis-
tance that decreases as the applied field increases. The multi-
phasic nature of varistors leads to the formation of Schottky
barriers, which are responsible for the materials’ nonlinear be-
havior. The objective of this work was to image the potential
barriers in ZnO doped with 0.5 mol% Cu and x wt% G (G is a
frit and x 5 0, 1, and 5 wt%). The frit served to form a glassy
insulating layer around the grain boundaries. Samples were sin-
tered at 10501C and the microstructures were analyzed using a
Nanoscope IIIa atomic force microscope. The results of the
electric force microscopy experiments map the electric field dis-
tribution on the surface of CuO–ZnO-based ceramics.
I. Introduction
T ODAY’S demand for electrical/electronic components re-
quires the development of materials with controllable prop-
erties, which include varistor ceramics.1–6 Varistor ceramics are
gaining increasing technological importance because of their
highly nonlinear electrical characteristics. They are used to pro-
tect electrical circuits from voltage surges and exhibit highly
nonlinear I–V characteristics.3,5–11 Over the last few decades,
varistor behavior has been improved through advances in pro-
cessing, including the type, quality, and quantity of reagents
used.8,12–17
An important factor that must be kept in mind is that va-
ristors are polycrystalline ceramics with high concentrations of
structural, surface, and electronic defects. The type and quantity
of defects are related directly to the processing stages used in the
production of the ceramic. Therefore, the main feature of these
systems is the presence of grains connected at their interfaces.
This is considered a determining factor of the systems’ electrical
properties, i.e., their stability after a transient voltage surge is
directly related to the stability of the electrical barriers in the
grain boundaries.3,4,9,17 This stability is affected by the choice of
dopants, and it is also conditioned to the uniformity of the do-
pants’ distribution at the grain boundaries and to the chemistry
at the boundaries. If the dopants are distributed uniformly at
numerous grain boundaries, more borders will be active and the
current will be conducted uniformly through the device. Greater
homogeneity leads to improved reproducibility of the process,
and enhances and equalizes the material’s properties.5,17–20
L. M. Levinson—contributing editor
Manuscript No. 24643. Received May 7, 2008; approved August 8, 2008.
This work was financially supported by the Brazilian agencies FAPESP and CAPES the
LNLS (Brazilian National Laboratory of Synchrotron Light) in Campinas, SP, Brazil for
the AFM/EFM analyses.
w
Author to whom correspondence should be addressed. e-mail: gheno@dema.ufscar.br
3593
DOI: 10.1111/j.1551-2916.2008.02704.x
r 2008 The American Ceramic Society
São Carlos 13565-905, SP, Brazil
Zinc oxide (ZnO), one of the various types of ceramic va-
ristors, is a semiconducting electroceramic material commonly
used in commercial varistors to protect electrical/electronic com-
ponents from transient overvoltages. Furthermore, ZnO ceram-
ics have long been used as varistors because of their highly
nonlinear current–voltage (I–V) characteristics.3–12
ZnO varistor ceramics have a highly complex structure, which
makes it difficult to control their morphology and electrical
characteristics. The main factor for the success of the technology
is the discovery of various dopants that impart the desired elec-
trical properties to ZnO, while also allowing for the necessary
microstructural control.3,9–18
The complexities of the microstructure, electrical response,
processing, and synergistic effects have made defining the role(s)
of specific additives elusive. The energy states in the microstruc-
ture of ZnO-doped ceramics are created by dislocations and
dangling bonds arising from the crystallographic mismatch be-
tween adjacent grains. Free carriers, usually electrons present in
the slightly n-type ZnO material, are trapped, leading to the
creation of electrostatic barriers at the interface. The potential
barrier prevents current conduction, yielding large impedance at
relatively low voltages and nonlinear characteristics.11,13,18 The
doped grain boundaries trap electrons and create an electrostatic
barrier against charge transport. The release of electrons at the
breakdown voltage gives the material its nonlinear characteris-
tics, which are essential for the varistor function and have been
attributed to phenomena that occur in grain boundaries.21,22
Varistors act as insulators until they reach the breakdown
voltage, whereupon they act as conductors. This voltage is pro-
portional to the number of barriers formed between parallel
sides of the varistor. The conduction mechanism through
Schottky barriers may be due to thermionic emission from the
ZnO-doped grain conduction band to the isolating film conduc-
tion band. Eda,23 who studied doped ZnO, reported that
Schottky-type barrier voltages are separated by an insulating
film of finite width. He proposed an energy band model at the
grain boundary and a conduction mechanism mainly governed
by field emission and thermionic emission at the reverse-biased
Schottky barrier.
The barrier voltage of ZnO-doped varistors can be electri-
cally, chemically, and thermally degraded during use, leading to
the reduction of barrier voltage height and, consequently, to the
increase of leakage current, which could be catastrophic for
surge arresters. The degradation of this barrier has been studied
extensively.22–27 However, little effort has focused on its imag-
ing, and its real dimensions are not well known, although this
information is crucial in ZnO varistor technology.
The durability of varistors is related directly to the state of ion
polarization at the grain boundaries, which create the potential
barrier. This polarization state is produced by ion diffusion.
This study used electrical force microscopy (EFM) to image and
dimension the potential barrier in ZnO–CuO–frit varistors. The
investigation and mapping of the potential barrier distribution
3594 Journal of the American Ceramic Society—Gheno et al.
across the ZnO–CuO–frit surface was carried out using atomic
force microscopy (AFM/EFM), varying the potential applied on
the surface.
The purpose of the use of the varistor system based on CuO-
doped ZnO was to confirm the results obtained previously by
Chiou and Chung28 and Kutty and Raghu.29 These authors
showed that the presence of CuO in ZnO varistors conferred to
the ZnO–CuO varistors the same properties as those that have
several dopings such as those proposed by Matsuoka and col-
leagues12,20 However, Lee and Tseng30–33 showed that due to the
poor sinterability of this system and in an attempt to densify the
material (CuO doped ZnO), the frit used had the following
composition: 26 wt% SiO2, 62 wt% PbO, 7 wt% B2O3, and
5 wt% ZnO. Previous studies on ZnO–CuO–frit varistor sys-
tems have been reported by Bellini et al.34–37 They showed that
the addition of a large percentage of frit (5%) led to a low
breakdown electric field and a low leakage current.
II. Experimental Procedures
Varistor powders of CuO-doped ZnO were prepared by the
freeze-drying process as per Bellini et al.34 Two pellets were ob-
tained by pressing the powders at 75 MPa in a uniaxial press
without pressing additives and sintering in air at 10501C for 1 h.
Pellet (a) was used for AFM/EFM characterization with 5 mm
diameter and 3 mm thickness and pellet (b) was used for analysis
of electrical properties with the same diameter but with a 1 mm
thickness.
For the purposes of identification, the samples were given the
following specific names: ZC: ZnO10.5 wt% Cu, ZCF1:
ZnO10.5 wt% Cu11 wt% frit, and ZCF5: ZnO10.5 wt%
Cu15 wt% frit. The frit was prepared as follows: a batch of pre-
cursor oxides and isopropyl alcohol was mixed in a ball mill mixer
with zirconia mixing media for 4 h. The oxide powders were
batched in the following proportions: 26 wt% SiO21
62 wt% PbO17 wt% B2O315 wt% ZnO. The powder mixture
was dried at 1101C for 24 h and unaggregated before being melted
at 9001C in a conventional furnace and fritted in distilled water.
The ZnO, ZnO10.5 wt% Cu powders and the crystalline
phases of sintered ZC, ZCF1, and ZCF5 samples were analyzed
by X-ray diffraction (XRD) using a Siemens D5005 diffracto-
meter with Cua radiation, at 50 kV voltage and 100 mA current.
The current density versus electric field (J–E) curves were plot-
ted from the I–V data of ZnO–CuO-doped varistors measured
with a high-voltage 60 Hz ac power supply (Keithley) whit GPIB
interface. Electrodes (0.385 cm2) of conductive silver paste were
deposited on the pellets’ surface as-fired and heat treated at
1101C for 10 min. The nonlinear coefficient a is considered the
quality factor of a varistor, and is defined by the empirical
equation I 5 kVa, where I is the current flowing through the
sample, V is the voltage across the sample, k is a constant value
of ZCF1 and ZCF5 samples, which are 2.73
1032
mA  (V  m)1 and 7.93
1027 mA  (V  m)1 respectively,
and a is the nonohmic exponent. For the sake of comparison,
the nonlinear coefficient a can be estimated by the equation
a 5 1/log (E5/V1) using two electric field values, E5 and E1, at
5 and 1 mA/cm2 settings of the current density, respectively.36
The potential barrier was analyzed with a Nanoscope IIIA
AFM (Digital Instruments) operating in the EFM mode, which
was equipped with an electronic extension module (Veeco Instru-
ments, Veeco Metrology Inc., Santa Barbara, CA). Topograph-
ical measurements and electrical data were obtained by the two-
pass technique (Lift Mode). In this configuration and operating
in the Tapping Mode, the probe scans a topographical line during
the first pass. In the second scan, the cantilever is lifted to a pre-
defined distance (75 nm) in order to minimize the effect of the
Van der Waals forces, while the probe detects variations in the
electric force gradient over the same line and the influence of
surface topography is ruled out.38–41 An NSC15 tip (Mi-
kroMasch) was used in all the experiments. Electrostatic force
gradient images were obtained by monitoring the phase and
Vol. 91, No. 11
frequency shifts between the oscillations of the bias, the canti-
lever, and the piezoelectric driver as a function of bias voltages
applied to the cantilever. The initial EFM imaging conditions
were: interleaved frequency drive, 25 Hz; integral gain, 0.35; and
proportional gain, 2.5. The images of surface potential and bar-
rier layer were obtained by applying 0, 4, 8, and, 12 V in situ to
the sample. Before the EFM imaging, metal electrodes (conduc-
tive Ag ink) were applied to the bottom and the sides of the
samples and kept in contact with the AFM scanner throughout
the measurements. Imaging of these samples as fired was carried
out at room temperature.
III. Results and Discussion
Figure 1 shows the typical XRD patterns of the pure ZnO (bot-
tom) and ZnO–CuO (top) powders. Figure 2 shows the XRD
patterns of ZC (bottom), ZCF1 (middle), and ZCF5 (top) va-
ristor pellets. Based on the powder diffraction files of the Joint
Committee on Powder Diffraction Standards all the diffraction
planes of the maximum relative intensity of the crystalline
phases are contained within the range of 101o2yo801, and
only the ZnO phase is visible in Figs. 1 and 2.
No Cu peak is visible in Figs. 1 or 2 due to the low Cu content.
In Fig. 1, the unexpected XRD peaks appear at about 2y 5 19
and 28.7, which is likely due to impurities or remnants of cupper
acetate although they were not detected in the sintered samples
(Fig. 2). In Fig. 2, the XRD peaks (2y 5 26.71 and 341) show a
new phase: Zn2SiO4 from the reaction of the vitreous phase at a
high temperature with the zinc grain for both ZCF1 and ZCF5.
However, the amount of the Zn2SiO4 phase developed was not
sufficient to modify the properties of the ZnO–CuO–frit varistor
system. In Fig. 2, a decrease in the intensity of the peaks with an
increase in the frit content was observed and attributed to the
‘‘diluting effect’’ of the amorphous phase introduced.
Figure 3 presents the current density versus applied electric
field (J–E) curves of the ZC, ZCF1, and ZCF5 varistors, showing
that the a value of ZCF1 (a 5 8.1) was greater than ZCF5
(a 5 7.0). It is worth mentioning that variations in the frit con-
centration affected the nonlinear coefficient (a), improving the
overall varistor material behavior. The ZCF1 resistance is higher
than ZCF5 at high voltages. At low voltages, the resistance is
almost the same for all materials, as it should be expected for
varistors (high resistance at low voltages).
Based on these results, an analysis was performed of the mi-
crostructural and electrical properties by scanning probe micros-
copy (SPM), i.e., AFM combined with EFM. The results were
analyzed and interpreted using the Digital Instruments software,
which is specific for analyzing SPM images. Figures 4–6 show
images of 15 mm
15 mm scanned areas of the ZC, ZCF1, and
ZCF5 samples obtained via AFM/EFM.
Fig. 1. Powder X-ray diffraction pattern of samples sintered in air at
10501C for 1 h: ZnO (a) and ZnO10.5 mol Cu (b).
November 2008 AFM/EFM Study in ZnO-Based Varistor 3595

Fig. 3. Current density versus. applied electric field (J–E) curves of the
ZC( & ), ZCF1 (J), and ZCF5 (W) samples. The breakdown fields for
the ZCF1 and the ZCF5 are 2500 and 4050 V/cm, respectively.

Fig. 2. X-ray diffraction patterns of samples sintered in air at 10501C

for 1 h: ZC (a), ZCF1 (b), and ZCF5 (c).
Figures 4(a), 5(a), and 6(a) show the topographic AFM in-
formation about the respective microstructures, whose grains
differ considerably in geometry and size probably due to the
presence of frit but reveals no chemical specificity or phase in-
formation. Besides, in Figs. 4(a) and 5(a), the heterogeneous
microstructure exhibits grains and subgrains due to the low sin-
terability of the mixture and residual porosity due to incomplete
densification during the sintering process. Porosity can increase
the leakage current, favoring electrical degradation. This degra-
dation causes heating during the operation of the device, leading
to its failure. However, the nonlinear coefficient (a) remains un-
affected, as shown in Fig. 3.
The EFM results presented in Figs. 4(b)–(e), 5(b)–(e), and
6(b)–(e) of ZC, ZCF1, and ZCF5 samples, respectively, show
details of the variations in the electric field gradient across the
area scanned on the sample. The EFM images indicate that an
increase in the applied voltage leads to an increase in the con-
centration of negative charges at the grain boundary, whose be-
havior signals the effective presence of the potential barrier.
The increased conductivity resulting from doping was con-
firmed by the EFM images, which recorded the potential bar-
riers present at the grain boundaries. Figures 4(b)–(e) to 6(b)–(e)
show the EFM images obtained using a dc bias voltage of
0–12 V. In 4 V increments, the grain boundaries are already
visible, in line with the topographic image. The call-out regions,
which were attributed to semiconducting material, indicated
that the grains were conductive. The bright regions, especially
at the grain boundaries, could be ascribed to the electrostatic
charge produced by the potential barrier.
In all EFM images, the surface potential is dependent on the
local electric field. Besides, the surface potential clearly identifies
a grain boundary contour. Potential profiles were extracted
from various positions along the grain boundaries in all the
samples and, based on these profiles, the dimensions of potential
barriers at the grain boundaries were determined to be 250 nm
for ZC and ZCF1 and 750 nm for ZCF5 as shown in Fig. 7.
These results indicated that increasing the frit content to 5%

Fig. 4. Atomic force microscopy (AFM) and electric force microscopy (EFM) profiles of a 15
15 mm area of a pure ZC varistor sample. In (a), an
AFM topographic scan is shown. In (b) through (e), EFM profiles of the same region as (a) are shown but at 0, 4, 8, and 12 V dc, respectively. Grain sizes
are visible (I) as well as the grain boundaries/intergranular regions (II) and porosity (III).
3596 Journal of the American Ceramic Society—Gheno et al. Vol. 91, No. 11

Fig. 5. Atomic force microscopy (AFM) and electric force microscopy (EFM) profiles of a 15
15 mm area of a pure ZCF1 sample. In (a), an AFM
topographic scan is shown. In (b) through (e), EFM profiles of the same region as (a) are shown but at 0, 4, 8, and 12 V dc, respectively. Grain sizes are
visible (I) as well as the grain boundaries/intergranular regions (II).

tripled the potential barrier. The width of the resistive layer is a
function of the material’s chemistry and processing and is not
expected to be very sensitive to the voltage applied (Fig. 7). One
possible explanation for this behavior is that the contribution to
the conductivity of the glassy phase increases with an increase in
its amount. The width of the potential barrier increases for the
same reason while the conductivity at the breakdown voltage
decreases due to a substantial contribution of the glassy phase
toward the conductivity.
Several theoretical studies and some scanning probe technical
studies are found in the literature and can be used to quantify
the interfacial properties associated whit local transport prop-
erties, grain boundaries, or potential barrier; there are also
some references that associate these properties with different

Fig. 6. Atomic force microscopy (AFM) and electric force microscopy (EFM) profiles of a 15
15 mm area of a pure ZCF5 sample. In (a), an AFM
topographic scan is shown. In (b) through (e), EFM profiles of the same region as (a) but at 0, 4, 8, and 12 V dc, respectively. Grain sizes are visible (I) as
well as the grain boundaries/intergranular regions (II).
November 2008 AFM/EFM Study in ZnO-Based Varistor
Fig. 7. Dimension of potential barrier at 12 V dc: ZC(n), ZCF1 (&),
and ZCF5 (J) samples.
dopants.2–5,9–13,17,24–27,34,42–44 Shao et al.43 made an important
contribution by analyzing the grain boundary behavior in a
commercial polycrystalline ZnO using a nanoimpedance micros-
copy/spectroscopy technique that is based on impedance spec-
troscopy with a conductive AFM tip. Through this technique,
which monitors the tip-to-surface interaction, these authors
showed that the electrical properties of polycrystalline ZnO
are dominated by the resistive grain boundary effect and con-
cluded that all grain boundaries between the tip and the bottom
electrode were probed simultaneously.
Vasconcelos et al.44 studied another electroactive grain
boundary of a highly dense metal oxide SnO2-based polycrys-
talline varistor using electrostatic force microscopy (EFM). As
demonstrated by these authors, the EFM images in the grain
boundary region indicated the presence of active potential bar-
riers or active grain junctions.
In addition, the EFM images provide information about how
the electrical current in varistors follows the path of least resis-
tance, i.e., routes with fewer borders (or larger grains) and those
with smaller grain boundary barriers. If the grain size is homo-
geneous, more electric current passes through many parallel
paths. The effects of porosity and inhomogeneous grain distri-
bution should be avoided, as illustrated in Fig. 4.
Over the years, a number of models have been developed for
the barriers to electrical conduction at the interfaces. The first
model, which was proposed by Matsuoka in 1971,12 considered
a space-charge-limited current in the bismuth-rich intergranular
layer. In CuO-doped ZnO varistors, the barrier associated with
the nonohmic properties of doped-ZnO ceramics can be attrib-
uted to the high-resistance intergranular layer between the low-
resistance CuO-doped ZnO grains, as indicated by the ideal
model proposed by us in Fig. 8, which shows that superficial
donor states are able to donate electrons. This figure is com-
patible with the nonlinear coefficient and the EFM results, be-
cause the basic concept underlying varistor action is that the
current/voltage characteristics are controlled by electrostatic
barriers at the grain interfaces.
Fig. 8. Ideal energy band model of ZnO–CuO-doped ceramics.
3597
The formation of defects in the ZnO matrix presumably gives
rise to potential barriers at the grain boundaries. Potential bar-
rier height and width are both associated with an increase in the
number of electrons and holes in the grain and grain boundary
regions, and increases in the potential barrier can be attributed
to effectively increased grain boundary states, which have been
found to give rise to nonlinear current/voltage characteristics
through the formation of barriers against electrical conduction.
Moreover, Eda23 demonstrated that Schottky barrier deforma-
tions may occur, which can be attributed to the nonuniform
distribution of spatial charges that are necessarily symmetrical
to the Schottky barriers. In other words, the Schottky barriers
symmetrical to the grain boundary must necessarily be sepa-
rated by an intergranular layer of finite distance, thus causing
the asymmetrical deformation of the Schottky barrier.
The results presented in Figs. 4–6 indicate that the frequency
gradient height is strongly dependent on the applied voltage and
the Schottky barrier is proportional to the applied field. The
width of the region over which the voltage changes near an in-
terface is a function of the material’s parameters and is not ex-
pected to be very sensitive to the applied voltage. The depletion
of free charge carriers applies equally to volume and barrier
layers. Sato et al.42 who studied the effect of Pr doping on the
formation of double Schottky barriers at ZnO single grain
boundaries, proposed that the formation of potential barriers
is strongly governed by atomic scale factors, such as the grain
boundary atomic structure, dopant segregation, and/or forma-
tion of native defects. Another important explanation for the
variation in thickness was proposed by Heywang,27 who postu-
lated that the interface charge changes the Fermi level in the
vicinity of the grain boundary. The potential barrier height and
width are both associated with an increase in the number of
electrons and holes in the grain and grain boundary regions. In
the grain boundary regions, the number of trapped electrons
resulting from the segregation of dopants at the grain bound-
aries, as well as the creation of positive defects in the depletion
layer and negative defects at the interfaces (metallic vacancies),
are also related to the characteristics of the potential barrier.
Thus, potential barrier increases can be associated with effec-
tively increased grain boundary states.
Grain boundaries have been found to give rise to nonlinear
current/voltage characteristics by forming barriers against elec-
trical conduction. In polycrystalline materials in general, most
grain boundaries grow randomly and are low-symmetry, high-
angle grain boundaries. The basic concept underlying varistor
action is that the current/voltage characteristics are controlled
by the existence of electrostatic barriers at the interfaces between
grains. The origin of these barriers is the interface charge stem-
ming from lattice mismatches, defects, and dopants at the grain
boundary. The interface charge changes the Fermi level in the
vicinity of the grain boundary, resulting in band bending. The
electronic charges stored in an interface represent a repulsive
potential for the majority carriers—the electrons in the case of
an n-doped semiconductor—across the interface.
III. Conclusions
CuO-doped ZnO varistors are highly disordered materials and
their grain boundaries are nonhomogeneous, showing structural
variations along the interface. Our EFM results showed that the
height and width of potential barriers in all the samples were
dependent on the bias voltage. Moreover, the potential barriers
associated with the increased number of electrons and holes in
the grain and at the grain boundary may be related to a resistive
layer. This layer may be associated with spatially charged re-
gions resulting from charge redistribution, indicating that the
segregated atoms of the dopant (frit) may stabilize the ZnO
grain boundary that is rich in disordered oxygen species, thereby
enhancing the varistor properties.
3598 Journal of the American Ceramic Society—Gheno et al.
Acknowledgment
The authors gratefully acknowledge the LNLS (Brazilian National Laboratory
of Synchrotron Light) in Campinas, SP, Brazil for the AFM/EFM analyses.
References
1
M. R. Cássia-Santos, V. C. Sousa, M. M. Oliveira, F. R. Sensato, W. K.
Bacelar, J. W. Gomesa, E. Longo, E. R. Leite, and J. A. Varela, ‘‘Recent Research
Developments in SnO2-Based Varistors,’’ Mater. Chem. Phys., 90 [1] 1–9 (2005).
2
M. R. Cássia-Santos, V. C. Sousa, M. M. Oliveira, P. R. Bueno, W. K. Bacelar,
M. O. Orlandi, C. M. Barrado, J. W. Gomes, E. Longo, E. R. Leite, and J. A.
Varela, ‘‘SnO2 and TiO2 Based Electronic Ceramics,’’ Cerâmica, 47, 136–43 (2001).
3 28
V. C. Sousa, J. W. Gomes, P. R. Bueno, M. R. Cássia-Santos, A. L. Araujo,
E. R. Leite, E. Longo, and J. A. Varela, ‘‘Effect of the Addition of ZnO Seeds on
the Electrical properties of ZnO-Based Varistors,’’ Mater. Chem. Phys., 80, 512–6
(2003).
4
S. L. M. Brito, D. Gouvêa, and R. Ganzella, ‘‘Study of Polyacrylate Adsorp-
tion in a Commercial Varistor System: Characterization of the Physical–Chemistry
Properties,’’ Cerâmica, 51, 30–6 (2005).
5 31
L. Hozer, Semiconductor Ceramics: Grain Boundary Effects. Ellis Horwood:
Polish Scientific Publishers, West Sussex, UK, 1994.
6
C.-C. Hwang and T.-Y. Wu, ‘‘Synthesis and Characterization of Nanocrystal-
line ZnO Powders by a Novel Combustion Synthesis Method,’’ Mater. Sci. Eng. B,
111 [2, 3] 197–206 (2004).
7
T. K. Gupta, R. E. Tressler, G. L. Messing, C. G. Pantino, and R. H. Newhan
(eds.) Tailoring Multiphase and Composite Ceramics, pp. 439–507. Plenum Press,
New York, 1986.
8
T. K. Gupta, ‘‘Application of Zinc Oxide Varistors,’’ J. Am. Ceram. Soc., 73 [7]
1817–40 (1990).
9
R. C. Buchanan, Ceramic Materials for Eletronics—Processing, Properties, and
Applications, pp. iii. Marcel Dekker Inc, New York, USA, 1986.
10
M.-H. Wang, K.-A. Hu, B.-Y. Zhao, and N.-F. Zhang, ‘‘Electrical Charac-
teristics and Stability of Low Voltage ZnO Varistors Doped with Al,’’ Mater.
Chem. Phys., 100 [1] 142–6 (2006).
11
L. M. Levinson and H. R. Philipp, ‘‘Zinc Oxide Varistors—A Review,’’ Am.
Ceram. Soc. Bull., 65 [4] 639–46 (1986).
12
M. Matsuoka, ‘‘Nonohmic Properties of Zinc Oxide Ceramics,’’ Jpn. J. Appl.
Phys., 10 [6] 736–46 (1971).
13
N. Yamaoka, M. Masuyama, and M. Fukui, ‘‘SrTiO3-Based Boundary-Layer
Capacitor Having Varistor Characteristics,’’ Am. Ceram. Soc. Bull., 62 [6] 698–700
(1983).
14
M. F. Yan and W. W. Rhodes, ‘‘Preparation and Properties of TiO2 Va-
ristors,’’ Appl. Phys. Lett., 40, 536–7 (1982).
15
V. Makarov and M. Tontelj, ‘‘Novel Varistor Material Based on Tungsten
Oxide,’’ J. Mater. Sci. Lett., 13, 937–9 (1994).
16
S. A. Pianaro, P. R. Bueno, E. Longo, and J. A. Varela, ‘‘A New SnO2-Based
Varistor System,’’ J. Mater. Sci. Lett., 14 [10] 692–4 (1995).
17
S. Li, F. Xie, F. Liu, J. Li, and M. A. Alim, ‘‘The Relation Between Residual
Voltage Ratio and Microstructural Parameters of ZnO Varistors,’’ Mater. Lett.,
59, 302–7 (2005).
18
G. Q. Lu, Nanoporous Materials: Science and Engineering, pp. 700. Imperial
College, London, 2001.
19
M. Rittner, ‘‘Market Analysis of Nanostructured Materials,’’ Am. Ceram.
Soc. Bull., 81 [3] 33–6 (2002).
20
M. Matsuoka, T. Masuyama, and Y. Iida, ‘‘Voltage Nonlinearity of Zinc
Oxide Ceramics Doped with Alkali Earth Metal Oxide,’’ Jpn. J. Appl. Phys., 8,
1275–6 (1969).
21
H. C. Ling, M. F. Yan, and W. W. Rhodes, ‘‘Monolithic Device with
Dual Capacitor and Varistors Functions,’’ J. Am. Ceram. Soc., 72 [7] 1274–6
(1989).
Vol. 91, No. 11
22
U. Schwing and B. Hoffmann, ‘‘Model Experiments Describing the Micro-
contact of ZnO Varistors,’’ J. Appl. Phys., 57 [12] 5372–9 (1985).
23
K. Eda, ‘‘Conduction Mechanism of Non-Ohmic Zinc Oxide Ceramics,’’
J. Appl. Phys., 49 [5] 2964–72 (1978).
24
E. R. Leite, J. A. Varela, and E. Longo, ‘‘Barrier Voltage Deformation on of
ZnO Varistors by Current Pulse,’’ J. Appl. Phys., 72 [1] 147–50 (1992).
25
J.-H. Choi, N.-M. Hwang, and D.-Y. Kim, ‘‘Pore–Boundary Separation Be-
havior During Sintering of Pure and Bi2O3-Doped ZnO Ceramics,’’ J. Am. Ceram.
Soc., 84 [6] 1398–400 (2001).
26
H. S. Domingos, J. M. Carlsson, P. D. Bristowe, and B. Hellsing, ‘‘The For-
mation of Defect Complexes in a ZnO Grain Boundary,’’ Int. Sci., 12, 227–34
(2004).
27
W. Heywang, ‘‘Resistivity Anomaly in Doped Barium Titanate,’’ J. Am.
Ceram. Soc., 47 [10] 484–90 (1964).
B.-S. Chiou and M.-C Chung, ‘‘Effect of Copper Additive on the Microstruc-
ture and Electrical Properties of Polycrystalline Zinc Oxide,’’ J. Am. Ceram. Soc.,
75 [12] 3363–8 (1992).
29
T. R. N. Kutty and N. Raghu, ‘‘Varistors Based on Polycristalline ZnO:Cu,’’
Appl. Phys. Lett., 54 [18] 1796–8 (1989).
30
Y.-S. Lee and T.-Y. Tseng, ‘‘Phase Identification and Electrical Properties in
ZnO–Glass Varistors,’’ J. Am. Ceram. Soc., 75 [6] 1636–40 (1992).
Y.-S. Lee and T.-Y. Tseng, ‘‘Influence of Processing Parameters on the
Microstructure and Electrical Properties of Multilayer-Chip ZnO Varistors,’’
J. Mater. Sci.: Mater. Electron., 6, 90–6 (1995).
32
Y.-S. Lee and T.-Y. Tseng, ‘‘Effects of Spinel Phase Formation in the Calci-
nation Process on the Characteristics of ZnO–Glass Varistor,’’ J. Mater. Sci.:
Mater. Electron., 8, 115–23 (1997).
33
Y.-S. Lee and T.-Y. Tseng, ‘‘Correlation of Boundaries Characteristics with
Electrical Properties in ZnO–Glass Varistors,’’ J. Mater. Sci.: Mater. Electron., 9,
65–76 (1998).
34
J. V. Bellini, M. R. Morelli, and R. H. G. A. Kiminami, ‘‘Varistores de ZnO-
CuO-Vidro’’; PI0204858-2, 31/10/2002, INPI, Rio de Janeiro, Brazil.
35
J. V. Bellini, M. R. Morelli, and R. H. G. A. Kiminami, ‘‘Electrical Properties
of Polycrystalline ZnO: CuO Obtained from Freeze-Dried ZnO1Copper (II)
Acetate Powders,’’ J. Mater. Sci.: Mater. Electron., 13 [8] 485–9 (2002).
36
J. V. Bellini, M. R. Morelli, and R. H. G. A. Kiminami, ‘‘Ceramic
System Based on ZnO–CuO Obtained by Freeze-Drying,’’ Mater. Lett., 57,
3775–8 (2003).
37
J. V. Bellini, M. R. Morelli, and R. H. G. A. Kiminami, ‘‘Physical Changes of
Sintered Ceramics Obtained from Freeze-Dried ZnO1(CH3COO)2Cu  H2O Pow-
ders,’’ Mater. Lett., 57, 3325–9 (2003).
38
D. Sarid, Scanning Force Microscopy with Applications to Electric, Magnetic,
and Atomic Forces, pp. 129–51. Oxford University Press, New York, 1991.
39
S. N. Magonov and M. H. Whangbo, Surface Analysis with STM and AFM—
Experimental and Theorical Aspects of Image Analysis, pp. 116–28. VCH,
Weinheim , 1996.
40
E. Meyer, H. J. Hug, and R. Bennewitz, Scanning Probe Microscopy—The
Lab on a Tip, pp. 29. Springer, New York, 2003.
41
S. M. Gheno, H. L. Hasegawa, and P. I. Paulin Filho, ‘‘Direct Observation of
Potential Barrier Behavior in Yttrium–Barium Titanate Observed by Electrostac-
tic Force Microscopy,’’ Scr. Mater., 56 [6] 545–8 (2007).
42
Y. Sato, J. P. Buban, T. Mizoguchi, N. Shibata, M. Yodogawa, T. Yama-
moto, and Y. Ikuhara, ‘‘Role of Pr Segregation in Acceptor-State Formation at
ZnO Grain Boundaries,’’ Phys. Rev. Lett., 67, 106802 (2006).
43
R. Shao, S. V. Kalinin, and D. A. Bonnell, ‘‘Local Impedance Imaging and
Spectroscopy of Polycrystalline ZnO Using Contact Atomic Force Microscopy,’’
Appl. Phys. Lett., 82, 1869 (2003).
44
J. S. Vasconcelos, N. S. L. S. Vasconcelos, M. O. Orlandi, P. R. Bueno, J. A.
Varela, E. Longo, C. M. Barrado, and E. R. Leite, ‘‘Electrostatic Force
Microscopy as a Tool to Estimate the Number of Active Potential Barriers in
Dense Non-Ohmic Polycrystalline SnO2 Devices,’’ Appl. Phys. Lett., 89, 152102
(2006). &