Volume 9, number 4 MATERIALS LETTERS February 1990

ac ELECTRICAL PROPERTIES OF HIGH-CURIE-POINT BARIUM-LEAD TITANATE

PTCR CERAMICS

T.Y. TSENG and S.H. WANG

Institute of Electronics, College of Engineering, National Chiao-Tung University, Hsinchu, Taiwan, China

Received 7 August 1989; in final form 2 1 December 1989

Hip-~~e-~int ~miconducting baas-lead titanate PTCR ceramics of imposition B~.s~,Pb~.~~~,~~TiO~ were prepared.
The electrical properties of grain and grain boundary of the sample were studied by a combination of complex-plane impedance
analysis and impedance spectra methods. The PTC originated only in the grain boundary material.

The positive temperature coefficient (PTC) of re-
sistance observed in semicondu~ting BaTi03 ce-
ramics is well explained qualitatively by Heywang’s
barrier model [ 11. The grain boundary potential
barriers have been observed by means of a decora-
tion technique [ 2 1, emission electron microscopy
[ 3 1, voltage contrast imaging [ 41, and at room tem-
perature via cathodoluminescence [ 5 ], and the two-
probe method using a micromanipulator and fine Al
wire [ 6 1. However, there is still a lack of experi-
mental evidence of the nature of the grain boundary
potential barrier.
Several authors have indicated the usefulness of
the complex-plane impedance diagram to differen-
tiate between bulk, grain boundary, and electrode in-
terface resistances for semiconducting barium titan-
ate [ 7-91. Recently, Tseng and Lu [ lo] have
reported that the grain boundary resistance in-
creased with increasing tempe~ture abruptly and that
the bulk resistance only slightly changed with in-
creasing temperature by using complex-plane
impedance analysis. Unfortunately, with this method
it is impossible to obtain the resistivity of the grain
boundary when the low-frequency intercept is large
and beyond the capability of the measurement in-
strument. This problem can be overcome by using
the concept of impedance spectra [ 111. The purpose
of the present work is to examine how the temper-
ature affects the electrical property of the grain
boundaries of (Bao.89,Pbct.,dlao.oo3)Ti03ceramics by
a combination of complex-plane analysis and
impedance spectra methods.
Commercial barium titanate, BaTiOx was used as
starting material. PbO was used to shift the Curie
point. La203 as semiconducting dopant was pre-
pared from La(N03)*6H,0. TiOz was used to con-
trol stoichiometry. The mixtures of the raw materials
were mechanically b~l-milled for about 24 h in
deionized water with plastic coated iron ball media
in a plastic jar. The milled slurry was dried by an IR
lamp and calcined at 950°C for 2 h. The calcined
powders were then ball milled, dried as previously
described and sieved through 140 mesh screen to
produce starting semiconducting powders with a
composition of ( Bao.897Pb0.10Lao.oo3)Ti03. The pow-
ders were pressed into samples of 10 mm in diameter
and 2 mm thick. The pellets were stacked inside an
A1203 crucible packed with PbTiOll powder, and
covered with a tightly fitted lid to prevent volatili-
zation of PbO during firing. Sintering was performed
at a temperature of 1250°C for 30 min in a pro-
grammable furnace. A cooling rate of lOO”C/h was
used.
The average weight gain of the sample after sin-
tering is about 3.7 wt”h. It is expected that Pb from
the PbTi03 packing powder diffused into the pellet
during sintering resulting in a considerable weight
gain. The X-ray diffraction patterns of fired speci-
mens all belong to BaTiO, single phase. A two-probe
method with dc bias in the ohmic region was used to
measure the resistivity-temperature characteristics

164 0167-577x/90/$03.50 0 Elsevier Science Publishers B.V. (North-Holland)

Volume 9. number 4 MATERIALS LETTERS February I990

of the sample. An indium-gallium alloy was rubbed
on both surfaces to produce good ohmic contact for
testing. Prior to the resistivity measurement both the
electrode surfaces of a sample were covered with thin
steel sheets pressed on to prevent the electrode ma-
terial from vaporizing during heating. The measure-
ments were executed on heating at a rate of S”C/min
in a programmable furnace. The temperature of the
samples was determined by the attachment of a ther-
mocouple to the sample surface. The complex-plane
impedance of the sample was measured at different
temperatures up to 600°C with an HP 4192 imped-
ance analyter. Based on the equivalent circuit for the
PTC resistance shown in ref. [ 12 1, the resistivity of
the grain can be decided from the highest-frequency
real-axis intercept of the Cole-Cole plot and the grain
boundary resistance from the low-frequency inter-
t RGB iA)
CGB
cept. The resistivity of the grain can always be ob-
tained from the Cole-Cole plot. Nevertheless, at
higher temperature, it is difficult to extract the re-
sistivity of the grain boundary from the complex-
plane impedance due to the spread of the Cole-Cole
plot at the grain boundary resistance of PTC ce-
ramics at higher temperatures. As shown in fig. IB,
the impedance spectrum, i.e. a plot of Z” (imagina~
part of the impedance) versus log w (u is the an-
gular frequency) appears as a symmetric (Debye)
peak which is proportional to RGB as shown by the
equation
2” =
RGB~(RGBccm
)
1+ (WRGBCGB)~ ’
Tim = R&2 . (2)
Therefore, the grain boundary resistance ( RGB)can
be obtained.
The typical resistivity-temperature characteristic
of the present sample is shown in fig. 2; this sample
108c

c
106 c

Fig. 1. (A) Proposed equivalent circuit of PTCR ceramics with

good ohmic contact (negligible contact resistance) and its asso-
ciated Cole-Cole plot at low (solid line) and high (dashed line)
temperatures. R, is the grain resistance, ROB the grain boundary
resistance, Co, the grain boundary capacitance. (B) Proposed Temperature ( “Cl)
impedance spectra for PTCR ceramic with good ohmic contact. Fig. 2. Resistivity-temperature characteristics of the sample.

165
Volume 9. number 4 MATERIALS LETTERS February 1990

with the Curie point around 2 10’ C exhibits a PTCR

effect of more than 3.5 orders of magnitude. The
composition with 10 mol% PbTi03 should have a
Curie point of 180’ C, but the present sample’s Curie
point around 2 10’ C is expected to be due to the dif-
fusion of Pb into the pellet during sintering. The
sample with the Curie point of 2 10” C is reprodu-
cible under the same processing procedure. The
scanning electron micrograph of the fracture surface
of the sample as shown in fig. 3 revealed a wide dis-
tribution of grain sizes with pores at the grain
boundaries and grain junctions. From electron probe
microanalysis, it is found that the sample was non-
uniform, with a higher Pb content near the surface
than exists in the interior, as shown in fig. 4. Fig. IA
shows that the uncompleted circle observed at higher
temperature results from the overscale of the instru-
ment used. Therefore, the resistivity of the grain
boundary cannot be obtained from Cole-Cole plots.
The impedance spectra were used to decide the re-
sistance of the grain boundary. As shown in figs. 5A,
5B and 5C, the Z” Debye peaks were shifted slightly
to higher frequency values when the temperature was
below 143’ C; when temperatures were increased over
143°C the Z” Debye peak heights increased dras-
tically and were shifted to lower frequency values
until 483’ C. The Debye peak heights decreased and
were shifted to higher frequency values again at tem-

Fig. 4. Electron probe microanalysis of the sample: (A) Pb X-ray

mapping of the surface and (B) Pb X-ray mapping of the frac-
ture surface of the sample.

peratures higher than 483°C. There is only one De-

bye peak for each temperature.
Based on the Debye peak values shown in imped-
ance spectra plots, the grain boundary resistance can
be calculated by using eq. (2) for each different
temperature.
Grain resistances were extracted from Cole-Cole
plots. The available grain resistance and grain
boundary resistance data are plotted in fig. 6 as a
function of temperature. It is obvious that even be-
Fig. 3. Scanning electron micrograph of the fracture surface of low the Curie temperature the grain boundary resis-
the sample. tance is dominant, the PTC effect is attributed to in-

166
Volume 9. number 4 MATERIALS LETTERS February 1990

106
- IJ grain boundaries
- 0 grain

105-

10-2:
100 102 lo4 106 106

f (Hzb---
106b I

lolo 0

Temperature (‘C)

Fig. 6. Resistance-temperature characteristics of the grain and

grain boundaries of the sample.

100 102 104 106 106 ter-grain boundary layers. The result is in good
agreement with that obtained by Nemoto and Oda
f (Hz)-
[ 61, who directly examined the electrical properties
1 of single grain boundaries by the two-probe method
using a micromanipulator and fine Al wire, but stul-
tifies the result reported by Sinclair and West [ 13 1,
who indicated that both the grain boundary and the
bulk resistance exhibit the PTC effect.
With the use of a combination of complex-plane
impedance analysis (Cole-Cole plot) and imped-
ance spectra methods, the resistance of bulk grains
and grain boundary in high-Curie-point PTCR ce-
ramics were revealed. Based on the result obtained

4 Fig. 5. Impedance spectra of the sample at different tempera-

tures: (A) 43-143°C; (B) 163-483°C; (C) 503-603°C.

167
Volume 9, number 4 MATERIALS LETTERS
by these methods, the PTC obviously originates only
in the grain boundary. However, whether the PTC
mechanism should be related to a change of the po-
tential barrier height at the grain boundary or to a
change of the electron mobility in the grain bound-
ary has still to be clarified.
References
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[Z] P. Gerthsen and K.H. Haerdtl, Z. Naturforsch. I8a ( 1963)
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[ 3 ] H. Rehme, Phys. Stat. Sol. 26 ( 1968) Kl.
[4] H.B. Hannstra and H. Ihrig, Phys. Stat. Sol. 39 (1977) K7.
[ 51H. Ihrig and M. Klerk, Appl. Phys. Letters 35 (1979) 307.
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February 1990
[6] H. Nemoto and I. Oda, 3. Am. Ceram. Sot. 63 (1980) 398.
[ 71 N.E. Cipollini, J.M. Sowa, C.E. Forbest and J.F. Lynch, in:
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