The physics of metal oxide varistors

Lionel M. Levinson and H. R. Philipp

Citation: Journal of Applied Physics 46, 1332 (1975); doi: 10.1063/1.321701

View online: http://dx.doi.org/10.1063/1.321701
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 The physics of metal oxide varistors
Lionel M. Levinson and H. R. Philipp
General Electric Corporate Research and Development, Schenectady, New York i2301
(Received 9 August 1974)

This paper outlines our present understanding of the conduction mechanisms and physical processes
relevant to the performance of ZnO-based ceramic varistors. Varistor behavior is determined by the
gross ceramic microstructure of the device as well as by the localized conduction processes which
occur between grains. We show that the qualitative features of the highly nonlinear conductivity are
largely independent of the details of varistor composition or processing but rather appear to be a
general effect engendered by a microstructure of conducting grains surrounded by thin insulating
oxide barriers. Evidence is presented from a variety of sources that this intergranular layer is -100
A in thickness resulting in grain-to-grain fields of F - 106 VIcm. The conduction mechanism at
breakdown is consistent with a Fowler-Nordheim tunneling process obeying a current-density-vs-field
relation given by J 0: exp( -yIF), where y is a constant. At somewhat lower fields (prebreakdown
region) the conduction process follows a thermally activated Schottky-type law of the form
J 0: exp( -(E i -f3v'F)/k T], where E i ;::;0.8 eV. Analysis of measured current-voltage characteristics
at various temperatures in terms of these processes is a good representation of the data. The
empirical power law behavior J = (FIK )U often used to describe varistor performance is shown to be
an approximation of the Fowler-Nordheim relation.

I. INTRODUCTION the binary systems has been developed by Matsuoka

et al. 12.13 These varistors, and those presently pro-
Metal oxide varistors are novel ZnO-based ceramic
duced by General Electric 14 under the trade name
semiconductor devices with highly nonlinear current-
GE-MOV™, possess an extremely high nonlinearity in
voltage characteristics similar to back-to-back Zener
their current-voltage characteristic (30 '.S (11 '.S 50) and
diodes, but with much greater current and energy
are characterized by an excellent energy absorbing
handling capabilities. 1 The study and use of these ma-
capability. A typical multicomponent varistor of this
terials represent a rapidly developing field in the
type has a composition comprising13 97 mole% ZnO,
technology of electronic oxide ceramics.
1 mole% Sb20 3, and 1 mole% each of Bi20 3, CoO, MnO,
The varistors are produced by a ceramic sintering and Cra03, and is prepared by standard ceramic
process which gives rise to a structure comprised of techniques. 13
conductive ZnO grains surrounded by thin insulating
For the remainder of this paper we will in general
oxide barriers. In this study the physical properties of
restrict our attention to GE-MOyTM varistors .14 The
the phases constituting the resulting three-dimensional
varistor composition involved (largely ZnO with Bia0 3
series-parallel junction network will be discussed, and
and a number of other oxide additives) is proprietary.
the novel electrical properties interpreted in terms of
We believe, however, that our results are generally
the material microstructure_
applicable 15 to a variety of other multicomponent highly
Early work on ZnO-based varistors was largely
limited to binary systems comprised of ZnO and a few
mole% of a second insulating oxide component. Valeyev
et al. 2 investigated quite extensively the fabrication of
varistors in the ZnO-Si02 , ZnO-Sn02 , and ZnO-Si02 - CURRENT
glass systems. Their work was preceded by a number
ELECTRODES
of publications on the production of metal oxide varis-
tors using mixtures of ZnO-B~03' 3 ZnO-A1 2 0 3,4 and
ZnO-TiOa . 5•6 Even at this stage it was realized that the
origin of the non-Ohmic resistance lay in the occur- n .+-~- ZnO GRAIN
rence of some type of junction phenomenon2.3 between d ~~11i~jJoI.""~-- INTERGRANULAR
the individual conducting ZnO grains. An anomalously --1 MATERIAL
high dielectric constant was observed 7 • 8 in these ma-
terials. Subsequent work 9 ,lO on the ZnO-Bi 20 3 system
has confirmed and extended these ideas.
The above studies of the properties of binary ZnO-
insulating oxide varistors led to materials exhibiting
only a moderate degree of non-Ohmicity in their cur-
rent-voltage relationship. Typical values for the ex-
ponent of nonlinearity (11, defined by 10:: V", lay in the
region 2 '.S (11 '.S 6, which is similar to the nonlinearity FIG. 1. Schematic depiction of the microstructure of a metal
exhibited by thyrite. 11 More recently, however, a oxide varistor. Grains of conducting ZnO. average size d. are
series of multicomponent ZnO-based ceramic varistors completely surrounded by an insulating oxide of thiclmess t.
with properties greatly superior to those attained on Electrodes are attached and current flows as indicated.

1332 Journal of Applied Physics, Vol. 46, No.3, March 1975 Copyright © 1975 American Institute of Physics 1332

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PORES
T--'-:'-"-~INT£RGRANULAR
10 JL
nonlinear ZnO-based ceramic varistors (e.g., the
composition1 3 listed above).
As will become apparent in Sec. II, metal oxide
varistors are extremely complex multicomponent multi-
phase ceramic devices. In view of this complexity we
have felt it unwise to attempt to interpret the behavior
of these materials on the basis of an overly detailed
theory. We have therefore adopted the approach of
seeking a general (and preferably simple) description of
the more striking features of the varistors. In particular
the extreme Zener diodelike electrical nonlinearity of
this device merits attention.
II. VARISTOR MICROSTRUCTURE
Before proceeding to a description of the electrical
characteristics of metal oxide varistors we will briefly
describe the ceramic microstructure of this material.
A highly schematic diagram of the varistor microstruc-
ture is given in Fig. 1. The device consists of conduc-
ting ZnO grains, size d, surrounded by a thin insulating
oxidic layer of thickness t. Current flows between the
electrodes as indicated. The varistor action is cor-
PARTICLES
INTERGRANULAR
PHASE
10 I'
1333 J. Appl. Phys., Vol. 46, No.3, March 1975
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FIG. 2. Optical photomicrograph of a
polished and etched section of a GE-
MOV™ varistor. The straight lines
evident in some ZnO grains presuma-
bly correspond to twin boundaries de-
lineating different ZnO crystal planes
with different etch properties. The
white regions correspond to bulk ag-
GRAINS
glomerates of the intergranular com-
position. The various phases present
are discussed in the text.
PHASE
related with processes occurring at a ZnO-ZnO grain
boundary.
The actual microstructure of a metal oxide varistor
is considerably more complex than the somewhat ideal-
ized depiction of Fig. 1. In Figs. 2 and 3 we give
photomicrographs of polished and etched sections of a
GE-MOV™ varistor. Three phases, (1) grains, (2)
intergranular material, and (3) particles, are evident.
In addition some porosity can be seen in Fig. 2.
The "grains" are the pred0minant phase in these
varistors and consist of relatively small conducting
ZnO crystals. The straight lines evident in some of the
ZnO grains presumably correspond to twin boundaries
delineating different ZnO crystal planes having different
etch properties. The whitish areas lying largely be-
tween the ZnO phase have been labeled "intergranular
material". However, as will become apparent in Sec.
IV, the true intergranular interface which controls the
varistor action is believed to be extremely thin (-100
A) and is either highly microcrystalline or amorphous
in GE-MOV™ varistors (see Sec. III). This barrier is
neither visible in Figs. 2 and 3 nor capable of detection
GRAINS
FIG. 3. Scanning electron micro-
graph of a polished and etched
GE-MOyTM varistor.
L.M. Levinson and H.R. Philipp 1333
 E
.....u 104 --r----,-~--~ ~-T--- I-~~
1
<f)
.....
..... GE-MOV rM VARISTOR
0 ROOM TEMPERATURE CHARACTERISTIC
>
SLOPE: 1I<l1
Q
..... Fe UPTURN
..... -----------
u:: 10 3
<..)
a:.....
<..) ~=
J2
(~r
F2
L. COBS ex: fOBS (F,wl ~ ~
fil 102i _---L- . ___ 1
:::; ~_~
I
a..
a.. 10- 8 10-6 10- 4 10-2 100 10 2 104
«
CURRENT DENSITY (AMPERES /an 2)

FIG. 5. Current density versus applied field for a typical

GE-MOyTM varistor. The symbols F B and 01 are defined in
the text.

FIG. 4. Simplified equivalent circuit for GE-MO\J'l'M varistors.

Pp(F, w) is the frequency- and field-dependent parallel varistor relevant to the discussion of the electrical character-
resistance. COBS is the varistor capacitance and r is the istics of varistors. In Fig. 4 we represent the metal
series resistance of the ZnO grains usually apparent only at oxide varistor by a simple equivalent circuit. The quan-
very high currents. tities Pp and COBS are associated with the intergranular
layer, and r corresponds to the series resistance of the
ZnO grains. These values are in general functions of
by x-ray diffraction methods. The intergranular ma- the field F and the measurement frequency w. The mag-
terial in Figs. 2 and 3 corresponds to fairly well-crys- nitude of r is quite small and is thus important only at
tallized agglomerates of excess intergranular phase 0
very high current levels where it is responsible for the
Structural determinations 16 upon these agglomerates "upturn" in the current-field characteristics (see Fig.
indicated the material to be a bismuth oxide rich 5). For the present its influence will be neglected. The
pyrochlore. equivalent circuit therefore consists of a capacitor
COBS and a parallel resistance of resistivity Pp asso-
In addition to the ZnO grains and the intergranular ciated with the intergranular material. The field- and
material, a third phase labeled "particles" is evident frequency-dependent quantity pp(F, w) is defined by Pp
in Figs. 2 and 3. X-ray studies 16 have demonstrated '" F/ J, where J is the in-phase current density. At very
this phase to have a spinel-type structure with the ap- low fields, Pp is independent of F, i.e., the varistor
proximate formula Z~Sb2012' The spinel particles are behaves in an Ohmic fashion.
insulating and play only a secondary role in determining
the device properties. We will neglect them for the
remainder of this paper.
From micrographs of the type given in Fig. 2 we
determine the mean grain size d of the ZnO grains in
the varistor to be about d == 25 J.L. Noting that the break-
down field in GE-MOyTM varistors is about 1000 Y/ cm
(Sec. ill), we estimate the breakdown voltage per inter-
granular barrier to be Vb'" 2.5 Y/barrier. This value
may be compared with those listed by Matsuoka13 who
also finds ZnO grain sizes some tens of microns and 1500
breakdown voltages per barrier of the order of volts.
This similarity is important, since it implies that
qualitatively similar varistor action is obtained for a
broad range of ZnO plus insulating oxide mixes. Indeed, 1400
Matsuoka et al. 17 have disclosed a large number of
compositions which produce useful ZnO-based varis-
tors. Thus any theory describing the device conduction 1300
mechanism should be generally applicable to a wide
variety of insulating oxide inter granular materials and
thus should be insensitive to certain extrinsic details of
the insulating barrier such as trap density, impurity 1200
content, Fermi level pOSition, etc.
I I I
III. ELECTRICAL MEASUREMENTS J02 103 104
In this section we present results of both dc and ac FREQUE NCY (Hz)
electrical measurements on commercial GE-MOyTM
varistors. As a preliminary we define the parameters FIG. 6. Observed dielectriC constant of a GE-MOyTM varistor.

1334 J. Appl. Phys., Vol. 46, No.3, March 1975 L.M. Levinson and H.R. Philipp 1334

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 CURRENT
i.,...------...,
l
ELECTRODE
~
t~ ZnO GRAIN
d
, INTERGRANULAR
MATERIAL
L
2-
~ -'l'
FIG. 7. Idealized microstructure of a metal oxide varistor,
having grain size d and intergranular barriers thickness t. D
is the electrode separation.
In Fig. 5 we give the dc current-density-vs-field
relation of a typical GE-MOyTM varistor. (At high cur-
rent levels the data are obtained by a pulse technique to
avoid heating the device. The characteristic is, how-
ever, essentially independent of pulse width.) The data
are presented on a log-log scale since traditionally the
varistor characteristic has been represented by a rela-
tion of the form
J=(F/K)",
where K is a constant and Ci is the exponent indicating
the degree of nonlinearity. The inverse slope of the
curve at any given current density determines the cor-
responding value of Ci. On a plot of this nature, a hori-
zontal straight line (Ci =00) corresponds to a "perfect
varistor", with the breakdown field, F B , constant for
any value of the current density. For any real device
there is clearly some arbitrariness in the choice of F B •
We shall take it as the field where J = 1 mAl cm 2 •
From Fig. 5, we note that while Ci is fairly constant
over a limited range of current, a given varistor is not
characterized by a unique Ci. In Sec. Y we will discuss
the origin of varistor nonlinearity and present a
physically reasonable J-F relation for these systems.
As will be then apparent, Eq. (1) is a fair representa-
tion of the correct relation, especially for high Ci. We
also note at this juncture that K has units which depend
on Ci and that the interpretation of Eq. (1) requires
some care. A mathematically and physically more
transparent version of Eq. (1) is given by
J/ J 2 = (F/ F 2 )" ,
where J 1 and J 2 are the current densities corresponding
to applied fields Fl and F 2 , respectively, and Ci is some
average value in the range J 1 <J<J2 •
In Fig. 6 we give the observed dielectric constant
EOBS as measured on a General Radio type 1615-A
capacitance bridge. The applied rms ac voltage was 1.0
y. The data exhibit a complex structure which will be
the subj ect of a separate publication. 18 The predominant
feature which we wish to emphasize here is the ex-
1335 J. Appl. Phys., Vol. 46, No.3, March 1975
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tremely high value of fOBS' This value can be under-
stood 13 ,19 on the basiS of the microstructure of the metal
oxide varistor which is comprised of conducting grains,
size d, separated by insulating layers of thickness t. In
fact we can use the capacitance data to obtain a crude
estimate of t. This is outlined in the Sec. IY.
I~INTERGRANULARLAYER
The key feature relevant to the understanding of
varistor behavior is the proper estimation of the thick-
ness t of the intergranular barrier. Optical photomicro-
graphs (e.g., Fig. 2) can be quite misleading in this re-
spect since thick agglomerates of the intergranular
phase (= 1 Jl) are evident. Conduction will, however,
occur at regions of minimum t and it is this value which
is of interest. We have estimated t (a) from measure-
ments of the dielectric constant, (b) from data relating
to the composition of varistors, and (c) from trans-
mission electron microscopy.
A. Dielectric constant
The observed dielectric constant fOBS of GE-MOyTM
is given in Fig. 6. For an analysis of these data we
follow Matsuoka13 who idealized the ceramic micro-
structure in the form depicted in Fig. 7. Thus we as-
sume the conducting ZnO grains are cubes of side d
separated by an insulating oxidic layer of thickness t.
Letting A be the electrode area and D the electrode
separation, for a plane-parallel capacitor configuration
(1 ) we have
(3)
where COBS and fOBS are the observed capacitance and
dielectric constant, respectively. Thus
(4)
where n is the number of grains in thickness D. Clearly
the measured dielectric constant fOBS will be anomalous-
ly high, since the true dielectric layer thickness be-
tween the electrodes is nt and not nd. The true dielec-
tric constant of the intergranular ma~erial will be
ftnt=COBsnt/eoAtnp (5)
where A tnt is the average area of close approach be-
tween the ZnO grains and is presumably less than A due
to the rounding of the grain corners.
From Eqs. (4) and (5) we then have
t = d.!!.DL Atnt , (6)
fOBS A
(2) and neglecting for the moment the geometrical factor
A lnt / A, we may estimate t if flnt is known. Since the
exact chemical composition of the intergranular ma-
terial has not been established a direct determination of
flat is not at present feasible. We have made an approx-
imate evaluation of Elnt by sintering separately the metal
oxide additives (Le., no ZnO) compriSing GE-MOyTM
varistors and measuring E for this material. We find e
=16 at 1000 cps.
This estimate of Etnt is crude since we have ignored
the effect on E of any possible microstructural differ-
L.M. Levinson and H.R. Philipp 1335
 ZnO GRAIN

FIG. 8. Electron transmission micro-

INTERGRANULAR graph of a thinned section of a GE-MOyTM
MATERIAL varistor. The intergranular material is
clearly visible between the ZnO grains.

II'
f---/

ences between the sintered additives and the inter-
granular material. It is also possible that the incor-
poration of some Zn into the intergranular layer would
alter the true value of Eint (E for ZnO'" 9 20) somewhat,
and similarly, variations in E int could also arise via the
incorporation of varying proportions of some of the
metal oxide additives into the ZnO grains. These con-
siderations are, however, largely irrelevant. We have
noted in Sec. II that a wide variety 13,17 of materials
comprised of ZnO and other insulating oxides serve to
produce qualitatively similar varistors. Thus the exact
chemical composition of the intergranular material
must vary among the different varistor mixes, and we
expect a corresponding variation in the value of Eln!.
Typical 21 values of E for oxide materials are 4;SE;S 25,
and we feel fairly confident that Elnt lies in this range.
From Fig. 6 we note that EOBS '" 1500 and substituting
into Eq. (6) with d=25 /1,
(7)
Relation (7) gives an upper limit to the thickness of
the intergranular barrier. The geometrical factor Alnti
A is intended to take into account that a good deal of the
grain-grain interface area is separated by regions of
considerably thicker intergranular material which then
plays a diminished role in determining the varistor
capacitance. Moreover, conduction between grains will
take place mainly at the very thinnest regions where the
field is highest. Thus the actual value of t pertinent to
the highly nonlinear conduction mechanism may be con-
siderably lower than the estimate given above based on
the measured capacitance.
B. Varistor composition
Matsuoka12 ,13 has measured the nonlinear electrical
behavior of ZnO-based varistors containing varying
amounts of metal oxide additives. He finds an essen-
tially linear behavior (Ohmic) for an additive content of
less than 0.2 mole%. Above this "threshold" value,
varistor (nonlinear) behavior is initiated. We can thus
interpret an additive content of about 0.2 mole% as the
minimum amount necessary to coat the ZnO grains.
Increasing the additive content above this value leads
presumably to the formation of agglomerates of "inter-
granular material" at the grain corners. Neglecting the
dissolution of some ZnO by the additives (and vice
versa), and once again idealizing the ZnO grains as
cubes of side d surrounded by an intergranular layer of
thickness t, we have from
Volume(additives) '" 3t '" 0 002 (8)
Volume (total) d .
that t"'200 A for d=25 /1.
C. Transmission electron microscopy
A portion of a GE-MOV™ varistor was polished
mechanically to a thickness of about 100 /1 and then
further thinned by ion milling. The specimen was
mounted upon a liquid-nitrogen-cooled cold finger and
studied by transmission electron microscopy. Typical
micrographs are given in Figs. 8 and 9. The inter-
granular barrier between two ZnO grains is clearly
visible in Fig. 8 (t'" 600 A) and with somewhat more
difficulty in Fig. 9 (t'" 200 A).

1336 J. Appl. Phys., Vol. 46, No.3, March 1975 L.M. Levinson and H.R. Philipp 1336

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 -INTER GRANULAR
MATERIAL

ZnO GRAIN

FIG. 9. Electron transmission micrograph

of a thinned section of a GE-MOvT M vari s-
tor. The intergranular material is
indicated.

o
5000 A
f----l

In Fig. 10 we give an electron diffraction pattern ob-

tained upon passing the beam through a thin web of
intergranular material lying at the triangular shaped
region formed by the junction of three ZnO grains (see
Figs. 8 and 9). An extremely diffuse ring pattern is ob-
tained. Although only one line is easily visible in the
positive reproduced in Fig. 10, careful analysis of the
negative plate using a densitometer gives "d spacings"
of 3.00, 1.77, and 1 .21 1 for the centers of three dis-
cernible broad rings. By measuring the half-breadth of
the 3. ~O-A reflection (visible in Fig. 10) and using the
standard relation between line broadening and crystal-
line size, we obtain a mean "crystallite" size of 20 1
for this material. However a truly amorphous material
could also give a diffraction pattern of this breadth. It
is difficult to distinguish between a material composed
of 20-1 crystalline particles and one that is amorphous
on this basis. We shall consider the intergranular layer
in GE-MOyTM to be amorphous.
To summarize the results of Sec. IYA-Iye, we con-
clude that GE-MOyTM varistors have an amorphous
intergranular layer lying between the high-conductivity
ZnO grains with thickness t around 100-200 A. The
uncertainty in t is at least a factor of 2.
We can now estimate fa' the actual field in the inter-
granular boundary at breakdown. Since the ZnO grains
are conducting and do not support an applied field (in
the current range we are considering, 1. e., below
"upturn") we have from Fig. 7
FIG. 10 Electron diffraction pattern of the intergranular
fa = Fa d/ t . (9) material in a GE-MOvT M varistor. The pattern was ob-
tained by passing the electron beam through the triangular-
Using Fa ,.,10 3 Y/cm from Fig. 5, and d"'25 /1, t",200 A, shaped region lying at the junction of three ZnO grains (see
we obtain Figs. 8 and 9).

1337 J. Appl. Phys., Vol. 46, No.3, March 1975 L.M. Levinson and H. R. Philipp 1337

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 10'3[- ,- -r--,--'-~-j TTl trapping states of various kinds and densities. For the
C~"O~T n~1 purposes of this paper we will therefore confine our
attention to the prebreakdown and breakdown regions of
; , the characteristic, the qualitative features of which are
',:::1 BREAKDOWN -2 preserved for a wide variety of varistor compositions
!
REGION x
and processing variables. Thus the theory for conduc-
10'61 :"
0
tion in the non-Ohmic region must relate to gross es·
x
sentially intrinsic electronic features which exist in
I /0

10-7 )()(x 0 such intergranular materials or interfaces.

1 Iisoe
XX

0 " We cannot at this time explicitly specify the electron

CJ)
a... 10'81 states which "feed" the conduction processes nor can
::E
« PREBREAKDOWN 0 we establish whether they are associated with the bulk
0
REGI9N
IOl
0

0
0o " intergranular material or with the ZnO-intergranular-
0
0
" material interface. In the latter case the states might
."
0
10'10 I
0 0
be identified with levels in the ZnO or with states lying
24°C "
.. possibly in the transition region (interface) between the
0
o<l'
10-1I~ .0

ZnO and the intergranular material. The barrier to

-32°e •• conduction would be associated with the interface. AL-
10-12~ ternatively, the barriers to conduction may be entirely
within the intergranular layer _ The electrons could then
10-13l L.L.LL~_-----'-----l-----'------'-.L.L.L..1._-----l-----.L .L.L.LL.U..l
arise from valence band states which for these amor·
I 10 100 1000
VOLTS
phous materials might be highly localized (tail states).
FIG. 11. Current-voltage characteristics of a GE-MOyTM In Fig. 12 we give model energy-level diagrams for
varistor (type V130LA20) at various temperatures.

ZERO FIELD APPLIED FIELD

fB ~ 10 V/cm.6 (10)
This high value of the breakdown field is consistent with
,

I (i)
-" pF I/ 2
I L
field-assisted tunneling. 22 We utilize this information in
Sec. V.
" 1 . tiTi
"~--"', ,
I! ,
FERMI----·. -. --:
LEVEL •
v. CONDUCTION MECHANISM INTERGRANULAR
ZnO LAYER ZnO
In Fig. 11 we give the dc current-voltage character- INTERGRANULAR
istic of a GE-MOV™ varistor (Type 130LA20) at various LAYER
temperatures. The data are restricted to current
values low enough for measurement with negligible (a)
joule heating. The series resistance of the ZnO grains
is not a factor at these current values.
ZERO FIELD APPLIED FIELD
A number of salient features in these curves should
be pointed out: (i) In the "breakdown region" the points
appear to be on a straight line [cr. Eqs. (1) and (2)].
Upon closer examination, however (not evident on the
scale of this figure), we find a definite curvature to the T
E'
data when displayed on a log-log plot. That is, the ex-
ponent a in Eq. (1) is not a constant. In addition the
varistor characteristic in this region is relatively in-
i
sensitive to temperature. At constant current, LOCALIZED LEVEL IN INTERGRANULAR LAYER
(1/V)(dV/ dT) ~ - 2 X 10"'" OK-I. (ii) In the "prebreakdown
region", the current-voltage characteristics exhibit an (b)
obvious temperature dependence best described in terms FIG. 12. (a) Schematic depiction of the escape of an electron
of an activation energy. In the voltage range plotted from the ZnO conduction band into the conduction band of the
(down to ~io of the breakdown voltage) the curves are intergranular material. Process (0 is Schottky emission.
non-Ohmic. Process (il) is Fowler-Nordheim tunneling. (b) Diagramatic
representation of the processes for electron escape from a
At even lower voltages (not shown) the varistor ex- Coulombic center in the intergranular materiaL Process (i)
hibits an essentially Ohmic behavior. However in this corresponds to Poole-Frenkel emission. Process (ii) is a
range "steady-state currents" may not be achieved until Fowler-Nordheim-type tunneling. Process (i) in both (a) and
considerable time has elapsed after setting the voltage. (b) occurs at intermediate temperatures and moderate fields
(prebreakdown region). Here electron escape proceeds by
This is especially obvious at low temperatures where thermal activation over a field-lowered barrier. At high fields
the currents are quite small. Presumably these effects [case (ii)) quantum-mechanical tunneling occurs as shown.
are associated with polarization currents ariSing from This is the mechanism giving rise to varistor action.

1338 J. Appl. Phys., Vol. 46, No.3, March 1975 L.M. Levinson and H.R. Philipp 1338

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 ; -,--.---,~ r T--':-::
BREAKDOWN ::~
.. ..
10- 4 REGION ••• ,g
~ ~
-~
10-5 _PRE BREAKDOWN •••• • •• 'r,8
REGION •••• :/h
ISSoC ••
FIG. 13. Metal oxide varistor characteristic in the prebreak-
down region. The straight line behavior corresponds to field-
assisted thermal emission. At higher fields the transition to
the breakdown region is evident.
one specific case each involving (a) an interfacial and
(b) an intergranular (localized) barrier as described
above. These diagrams are schematic and are not in-
tended to depict particular materials. Process (i) in
Fig. 12(a) corresponds to thermionic emission over a
field-lowered barrier, called Schottky emission. Pro-
cess (ii) in Fig. 12(a) proceeds by quantum-mechanical
tunneling of the electron through the field-lowered bar-
rier and is denoted Fowler-Nordheim tunneling. We
wish to emphasize that processes (0 and (ii) are in fact
two solutions, each valid 23 for different values of field
and temperature and applicable to the single physical
process of electron emission under the action of an
intense applied field. A third limiting case (Ohmic
conduction) exists at low fields and is not considered
here.
Figure 12(b) gives the equivalent mechanisms for the
escape of an electron in the intergranular barrier from
a Coulombic well. The ionizable center lies at a depth
E/ below the quasiconduction band of the amorphous
intergranular material. Process (i) corresponds to the
thermal escape of an electron at moderate temperatures
and fields over the field-lowered barrier. This effect is
denoted Poole-Frenkel emission, and differs from the
Schottky case insofar as we are dealing with localized
electrons emitted over a Coulombic barrier. The theory
applicable to this mechanism in insulators is given by
Hill24 who also derives the equations relevant to the
high-field case (ii). The latter process proceeds by
quantum-mechanical tunneling of the electron through
the field-lowered barrier and is similar to the Fowler-
Nordheim tunneling of Fig. 12(a).
Before proceeding to an analysis of the varistor con-
duction in terms of the mechanisms discussed above,
1339 J. Appl. Phys., Vol. 46, No.3, March 1975
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we wish to point out that we have at present no means of
distinguishing between the models represented by Figs.
12(a) and 12(b). Except for some differences in detail,
both models are described by a similar2 3- 27 functional
dependence of current denSity upon electric field.
Moreover, in the complex ceramic system comprising
the metal oxide varistor we do not have the liberty to
vary either the electrode material or the barrier thick-
ness in any known way. The freedom to vary these
parameters is usually essential in distinguishing be-
tween interface-limited [Fig. 12 (a)] and bulk-limited
[Fig. 12 (b)] conduction mechanisms.
In view of these limitations, and also of our lack of
detailed knowledge of the composition or thickness of
the intergranular layer we will not pursue this point
further. Fortunately, as noted by Chynoweth22 and
Jonscher,25 both in the case of field-assisted tunneling
and field-assisted thermal emission, the current-den-
sity-field relations are largely model independent. The
observation that the general features of varistor action
are preserved for a wide variety of ZnO plus insulating
oxide mixes is probably closely related to the insensi-
tivity of the conduction processes to the actual details
of the model.
A. Schottky (Poole-Frenkel) emission
This process is dominant in the prebreakdown region
(Fig. 11). It corresponds to thermionic emission over
the field-lowered potential barrier. The applicable re-
lation23 - 27 between the current denSity J and field F is
(11)
where {:l=(e3/47TEoE1Dt)1/2 and we have taken J 1 to be ap-
prOXimately constant.
Some comments are in order with regard to J 1 and {:l.
Various derivations23-27 lead to somewhat differing
forms for J 1 and {:l. The former parameter is in fact a
function of F and T but we shall ignore this variation in
comparison with the strong field and temperature depen-
dence of the exponential. With regard to {:l, the assump-
tions made in some derivations give {:l a numerical value
T (OK)
500 400 300 250
-6
-7
-8
-9
~
lIE
...
c.:>
lIE
-10
c -II
::;;
0 -12
<F
0
...J
-13
-14
-15
1 2 3
lIT (OK-I)
FIG. 14. Plot of logloJ (extrapolated to F APPL = 0 using Fig. 13)
against inverse temperature.
L.M. Levinson and H.R. Philipp 1339
 T (OK) B. Fowler-Nordheim tunneling
500400 300 250
0.10 We have previously noted that the magnitude of the
.,..- field f B present in the intergranular layer at breakdown
~ 0.09
:E is consistent with Fowler-Nordheim tunneling. 22 This
0
0.08 process is dominant when the field F (Fig. 12) is so
~
(/')
0.07 high that electrons can tunnel through the narrowed
~
0 0 potential hill into the conduction band. A simplified
> 0.06 0
0

w form of the relation appropriate to this region is given

0-
0
0.05 by
...J
(/')
0.04 (12)
x
~ 0.03 where image effects and the field dependence of the pre-
0.02 exponential barrier have been neglected. Here
0.01 Y== 4(2m)I/2/3ne== 6. 8 x 107E~/2,
°0~--~--~2~--~3----~4-x~163 if E f is in eV and F is in V/cm.
The breakdown characteristics of a GE-MOVTM varis-
tor are plotted in Fig. 16. Note that the curves have
FIG. 15. Slope of logl~ versus Fl/2 (Fig. 13) plotted against
inverse temperature. been displaced for clarity. {The actual temperature de-
pendence of the current-density-vs-field curves in
this region is very small [(1/ F)(dF/ dT) = - 2 X 104 °C- 1 ]
and presumably arises from the temperature depen-
twice as large as that given in Eq. (11). We note, how- dence of E j . } We also note that the abscissa in Fig. 16
ever, that the field F in Eq. (11) is the field in the in- is 1/F APPL and not 1/ F. Since we have no accurate value
tergranular layer, and since we have no accurate value for t an absolute determination of y from the slope of the
for the layer thickness t, there exists a corresponding curves is not possible. Taking, however, d/t=10 3 , we
uncertainty in F. We have therefore somewhat arbi- obtain y=7x10 7 V/cm, which in view of the uncertainty
trarily chosen {3 as given above. in d/ t, is in good agreement with the expected y = 5
x10 7 V/cm (we have used EI =0.8 as determined above).
In Fig. 13 we plot 10gJ vs F}/ipL' If Eq. (11) holds It is of interest at this point to compare Eqs. (2) and
for the prebreakdown region, we expect a series of (12). The empirical relation is known to give a rea-
straight lines as is in fact the case. The zero-field cur- sonable approximation to the varistor characteristic,
rents may be obtained by extrapolating the curves of
Fig. 13 to FA PPL == O. If these values are now plotted on
a log scale vs 1/ T, the slope should give the activation 10- 3
energy E j • From Fig. 14 we find E j ==0.82 eV. It is
apparent that the - 32 °C point deviates from the straight o ~ 'REAKDOWN REGION
line, and we find this deviation is accentuated at even /~
lower temperatures. We have no well-established ex-
\, ~_ X.jiO
planation of this effect at present but it should be noted v-
that prebreakdown currents involved at low tempera- '" PREBREAKDOWN
tures are small « 10-13 A). It is in fact probable that ~ REGION
the observed currents are not indicative of the true dc
10- 6 "'j.......
equilibrium values, but are greatly increased by the ""::IE
u 1/
64°C
L> .......
simultaneous presence of slowly decaying polarization .....
a.. Xi{i .......
currents. The decay of these polarization currents over ::IE
<[ 10- 7
'"
a period of days has been observed at low temperatures,
and will be the subj ect of a forthcoming report. '" 24°C
'0....
.......
~
It is also possible to evaluate {3 in Eq. (11) by plotting
the slope of the 10gJ vs FIjiPL curves against l/T. A
straight line passing through the origin is expected, and
this is demonstrated to be the case in Fig. 15. The
lowest-temperature data point does not follow the ex- I 0 -IO~'----L-..J-----.J--'-1--'-1----'-----.l----'----l X 10-4
pected relation, as was the case in Fig. 14 above. 6.8 7.2 7.6 8.0 8.4 8.8 9.2
A precise calculation of {3 requires an accurate know- I/FAPPL. CM/VOLT
ledge of t. However using d/t=10 3 (i.e., t"'200 A, d
== 25 IJ.) we find a value of f3 corresponding to €lnt =30 FIG. 16. Fowler-Nordheim plot of the varistor characteris-
tic. The dashed lines correspond to the transition to the pre-
[cf. Eq. (11)]. Considering the uncertainty in t and the breakdown region (Fig. 13). The field F in the intergranular
approximations involved in our derivation, this number material is a factor d/t (R< 1(3) greater than the applied field
is in reasonably good agreement with our experimental- F APPL' Note that the curves have been displaced for reasons
ly determined €lnt = 15. of clarity.

1340 J. Appl. Phys., Vol. 46, No.3, March 1975 L.M. Levinson and H.R. Philipp 1340

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 and must therefore be compatible in some sense with
the theoretical result Eq. (12). From Eq. (2) we have
For a reasonable range of current and for varistors of
high 0' (high nonlinearity) F/ Fl is close to unity. Thus
log(J2 /Jl),"0'(I-F/F 2 ),
where we have kept the first two terms in the expansion
of log(F2 /F1 ).
Alternatively, from Eq. (12),
log(J/ J 1 ) = - y(~ - ~)
F2 Fl
=1:.. 11 _ F1 ).
F1 " F2
Equations (14) and (15) are equivalent upon making the
identification 0' = Y/ Fl' The error involved in using the
empirical result, Eq. (2), is -Hl- F/F2)2, the first
neglected term in the expansion for log(F/ F 1 ). In addi-
tion we can use this identification to estimate 0'. Since
Fl '"106 V/cm and y::::5xl07 V/cm, we obtain 0' '"50.
The experimental values of the exponent 0' for metal
oxide varistors are indeed in the range 30-50.
Note added in proof: Recent photoconductivity mea-
surements have conclusively established that the elec-
tron states controlling the nonlinear varistor behavior
are associated with the ZnO-intergranular material in-
terface, i.e., Fig. 12(a) is applicable. These results
will be presented in a forthcoming paper.
ACKNOWLEDGMENTS
The authors are indebted to M. Garfinkel, G.D.
Mahan, G.A. Slack, and J. Wong for helpful discus-
sions. J. E. May and R. S. Schlotterbeck supplied a
variety of samples used in this study. Data provided by
F .D. Martzloff are gratefully acknowledged. The com-
petent technical assistance of R.G. Yelle facilitated
many of the measurements reported here.
1341 J. Appl. Phys., Vol. 46, No.3, March 1975
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15The binary ZnO-based varistors have considerably lower
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component varistors such as GE-MOyTM.
16J. Wong, Bull. Am. Ceram. Soc. 53, 320 (1974).
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1BL. M. Levinson and H. R. Philipp (unpublished).
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22 A. G. Chynoweth, in Ref. 19, p. 95.
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27J. G. Simmons, J. Phys. D 4, 613 (1971).
LM. Levinson and H.R. Philipp 1341