Electrode effects in positive temperature coefficient and negative temperature

coefficient devices measured by complex-plane impedance analysis

D. P. Cann and C. A. Randall

Citation: 80, (1996); doi: 10.1063/1.362961

View online: http://dx.doi.org/10.1063/1.362961
View Table of Contents: http://aip.scitation.org/toc/jap/80/3
Published by the American Institute of Physics
Electrode effects in positive temperature coefficient and negative
temperature coefficient devices measured by complex-plane
impedance analysis
D. P. Canna) and C. A. Randall
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802
~Received 23 February 1996; accepted for publication 24 April 1996!
Impedance spectroscopy in conjunction with capacitance measurements were utilized to study the
electrical contact behavior of commercial positive temperature coefficient and negative temperature
coefficient ceramics. The impedance spectroscopy data, measured at frequencies ranging from 100
Hz to 40 MHz, exhibited a double semi-circle shape characteristic of systems which have both
barrier and bulk contributions to the impedance of the device. From the impedance data, equivalent
capacitive-resistive circuits were assigned to grain, grain boundary, and barrier elements. These
barrier capacitances and resistances were measured for Au, Ag, Pt, and In-Ga electrodes. The trends
in the magnitude of the barrier resistance are discussed with relevance to the thermodynamic work
of adhesion and the effect of metal-oxygen and metal-metal interactions at the interface. © 1996
American Institute of Physics. @S0021-8979~96!03815-7#

I. INTRODUCTION trodes are analyzed using ac capacitance measurements and

Semiconducting oxides have found many applications in
recent years.1 Barium titanate-based positive temperature co-
efficient ~PTC! resistors are used as current surge protectors,
thermal sensors, television degaussers, and self-regulating
heaters to name a few. Semiconducting n-doped barium ti-
tanate exhibits an increase in resistance of over three orders
of magnitude in the vicinity of the Curie temperature. This
phenomena was explained by Heywang as a consequence of
the double Schottky barriers formed at the grain boundaries
and the strong temperature dependence of the permittivity of
barium titanate.2
Negative temperature coefficient ~NTC! resistor devices
have found many applications including circuit temperature
compensation, temperature sensors, and telecom-
munications.3 NTC’s are most often composed of either
complex transition metal spinels such as ~Ni,Mn,Co!3O4 or
Li-doped transition metal oxides such as ~Mn,Ni,Co!O.
Nickel manganate spinels NiMn2O4 are of special interest
due to their low resistivity at room temperature ~r 25 °C
; 103 V cm!. The negative temperature coefficient is the re-
sult of thermal population of states in the conduction band.
Electrode contacts to these semiconducting oxides are
required to have a high conductivity and to form an Ohmic
contact to the semiconductor.4 With continued trends in min-
iaturization, there exists a need to further understand the area
of electroding of electroceramic materials. The electrical
contact behavior of Ni, Pt, Bi, Au, Sn, Ag, In, Ga, Pb, Cu
metals on semiconducting BaTiO3 has been studied for a
variety of different processing schemes.5–11 The results vary
widely depending on surface and processing conditions.
From the work of Kurtin et al.,12 the electrode-
semiconductor interfacial characteristics can be related to the
relative strengths of chemical bonds at the interface. In this
research, the contact properties of sputtered noble metal elec-
a!
Electronic mail: dpc2@psu.edu
complex impedance analysis.13 From the measurement of the
complex impedance (Z5R1iX), the elements in the repre-
sentative circuit shown in Fig. 1 can be calculated where R gr
is the grain resistance, R gb and C gb are the grain boundary
resistance and capacitance, respectively, and R b and C b are
the barrier resistance and capacitance, respectively.14 The
trends in the barrier resistance, R b , will be related to the
chemical interaction potential of the interface.
II. EXPERIMENT
Commercial PTC and NTC ceramics were obtained from
Keystone Thermometrics. The PTC material was BaTiO3
based and in the form of dense disks with a diameter of
approximately 10 mm and a thickness of approximately 1
mm. The NTC material was based on NiMn2O4 spinel and
came in the form of dense disks with a diameter of 2.5 mm
and a thickness of 1.7 mm. The intrinsic resistivities of the
PTC and NTC materials were near 100 V cm and 1 kV cm,
respectively. Before application of the electrode, the surfaces
of the samples were washed in acetone and dried at 120 °C.
Electrodes of Au, Ag, and Pt were applied by sputtering.
In-Ga alloy electrodes were applied by a paintbrush.
The impedance and capacitance measurements were
conducted at room temperature using a Hewlett–Packard
4194A Impedance Analyzer. The frequency range was from
FIG. 1. Equivalent circuit for semiconducting PTC and NTC material with
a barrier resistance and capacitance.

1628 J. Appl. Phys. 80 (3), 1 August 1996 0021-8979/96/80(3)/1628/5/$10.00 © 1996 American Institute of Physics
 FIG. 2. Current-voltage data for Ohmic In-Ga electroded PTC BaTiO3 ~left!, and non-Ohmic Au, Ag, and Pt electrodes ~right!.
100 Hz to 40 MHz. The oscillating voltage used in the mea-
surements was 10 mV for the PTC’s and 100 mV for the
NTC’s.
III. RESULTS
A. PTC materials
The In-Ga electrode on PTC BaTiO3 formed an Ohmic
contact as shown in the linear current-voltage data in Fig. 2.
The Au, Ag, and Pt electrodes on PTC BaTiO3 all formed
non-Ohmic contacts as is evidenced by the departure from
linearity ~Fig. 2!.
Complex impedance plots for the PTC samples are
shown in Fig. 3. The data for the In-Ga electroded sample
showed one semicircle centered slightly off of the real axis.
For the ohmic In-Ga sample, this represents a relaxation of
the internal space charge regions located at the grain bound-
aries which are peculiar to PTC BaTiO3 .15 The series resis-
tance indicated in the impedance spectra is a measure of the
resistance of the interiors of the grains. This relaxation is
FIG. 3. Impedance data for In-Ga, Au, Ag, and Pt electrodes on PTC BaTiO3 .
J. Appl. Phys., Vol. 80, No. 3, 1 August 1996
consistent with the Debye relaxation model,14 where the fre-
quency dependence of the impedance is given by
Rs
Z ~ v ! 5R ` 1 .
11i v t 0
The impedance data were fit to circular equations and the
circuit parameters, R g , R gb, and C gb were calculated as
shown in Table I. The displacement of the semicircle from
the real axis indicates a departure from ideal Debye behavior
that can be accounted for by introducing a term a into the
Debye equations:13
Rs
Z ~ v ! 5R ` 1 ,
11 ~ i v t p ! 12 a
where a5u/~p/2! and u is the depression angle. For the case
of In-Ga electrodes a was measured to be 0.1.
For the non-Ohmic electrodes on PTC BaTiO3 , the im-
pedance data was similar to that for the In-Ga results with
the addition of a second semicircle at low frequencies. This
second semicircle is indicative of a Schottky barrier present
D. P. Cann and C. A. Randall 1629
 TABLE I. Equivalent circuit parameters for the circuit pictured in Fig. 1 derived from the impedance data on
PTC BaTiO3 .

Rg R gb C gb Rb Cb

Electrode ~V! ~V! ~nF! a1 ~V! ~mF! a2

In-Ga 19.2 37.3 4.9 0.10 ••• ••• •••

Au 18.8 45.1 3.7 0.11 182 2.7 0.04
Ag 17.2 55.3 3.6 0.15 419 2.6 0.05
Pt 19.2 43.2 4.9 0.13 4200 1.4 0.04

at the electrode/PTC interface which is comprised of both
capacitive and resistive elements.15 The derived parameters
for these data are also shown in Table I .
The magnitude of the barrier resistance is dependent
upon the electrode type as seen in Table I. Pt yielded the
largest barrier resistance ~4.2 kV! followed by Ag ~419 V!
and Au ~182 V!. Conversely, Pt had the lowest barrier ca-
pacitance ~1.4 mF! as would be expected from the equation
for the capacitance of a Schottky barrier assuming that the
barrier resistance is related to the Schottky barrier height:17
C5A A~ K 8 e 0 qN D ! /2F B .
As seen in Table I, the a parameter for both the intrinsic
and barrier elements ranged from 0.04 to 0.15. This broad-
ening of the relaxation is probably due to a number of ef-
fects. The polycrystalline nature of the PTC ceramic will
inherently cause the space charge layer to be heterogeneous.
Also, the complex grain boundary chemistry of the PTC ma-
terial will certainly introduce a range of interface states at the
boundary.
The capacitance versus frequency plot in Fig. 4 shows a
large space charge capacitance on the order of 1 mF at low
frequencies which is due to the presence of a Schottky bar-
rier at the metal-semiconductor interface. At higher frequen-
cies ~;100 kHz! the space-charge capacitance relaxes out
and eventually at 1 MHz the capacitance drops three orders
of magnitude to 1 nF. In conjunction with this relaxation,
there exists a peak in the dielectric loss at approximately 40
kHz.
This capacitance data suggest that the Maxwell–Wagner
model for heterogeneous systems is relevant to these
samples. If we consider the equivalent circuit of Fig. 1 and
also that the Schottky barrier is insulating in comparison to
the bulk of the PTC sample, we can express the complex
dielectric permittivity of the material as16
K s8 K 8̀ is
K * ~ v ! 5K 8̀ 1 1 .
11i v̄ t v̄
If it is assumed that the bulk thickness is much greater than
the barrier thickness and that the relative dielectric permit-
tivity of both the barrier and the bulk are equivalent, the real
part of the permittivity can be written as18
K ~ t 1 1t 2 !
K s5
t1
and
K ` 5K,
where K ` and K s are the high- and low-frequency permit-
tivities, t 1 and t 2 are the thicknesses of the barrier and bulk,
respectively, and t is the relaxation time. Using the capaci-
tance data of Fig. 4 for Pt electrodes, the barrier thickness t 1
was calculated to be 2.5 mm. This compares surprisingly
well with the depletion layer width expected for an ideal
Schottky barrier, 1.3 mm, as calculated from the equation:19
W5 A~ 2K s e 0 V 0 ! /qN D ,
assuming a built-in voltage of 1.25 eV and a donor density of
1017 cm23.20,21
Also from the Maxwell–Wagner model, the bulk resis-
tivity of the material can be expressed as
t
r 25 At / ~ t 1t ! ,
Ke0 1 1 2
where t is the relaxation time. From the relaxation frequency
measured in Fig. 4 and the geometric parameters t 1 and t 2
calculated above, the resistivity of the barrier was calculated
to be 3.5 V m. This correlates well with the measured resis-
tivity of 2.1 V m from current-voltage measurements.

FIG. 4. Capacitance data for PTC BaTiO3 with non-Ohmic Pt electrodes.
B. NTC materials
The complex impedance data for the NTC materials is
shown in Fig. 5. None of the electrode materials yielded
purely Ohmic contacts as evidenced by the presence of the
secondary semicircle in all of the data. The high-frequency
semicircle was virtually constant for all electrode configura-
tions and must represent an intrinsic element to the NTC
material. All of the samples showed nearly perfect Debye
behavior as seen in the low a coefficients ~a,0.02!.

1630 J. Appl. Phys., Vol. 80, No. 3, 1 August 1996 D. P. Cann and C. A. Randall
 FIG. 5. Impedance data for In-Ga, Au, Ag, and Pt electrodes on NTC.

The magnitude of the barrier resistance was dependent
upon electrode composition ~Table II!. The lowest barrier
resistance of 103 V was measured for the In-Ga contact.
Since all of the samples had one side electroded with In-Ga,
all barrier resistances and capacitances were normalized to
factor out the effect of having one In-Ga barrier. The Pt
electrode, which had the largest barrier resistance for the
PTC’s had a barrier resistance similar in magnitude to the
In-Ga electrode on the NTC material.
IV. DISCUSSION
The variation in Schottky barrier height with electrode
metal has been studied extensively by Kurtin et al.12 and
Brillson.19 Assuming that the barrier resistance is a function
of the Schottky barrier height, from the arguments of Brill-
son, the barrier resistance should be dependent on the oxida-
tion potential of the electrode metal. From the data in this
research, it is apparent that metal-oxygen ionic interactions
alone cannot explain the trends in barrier resistance.
The model presented by Kurtin et al. and Brillson can be
expanded by representing the relative strength of the chemi-
cal interactions at the interface by the thermodynamic work
of adhesion, W ad . Recently, an empirical model for the work
of adhesion was developed by Chatain et al.:22
W ad52
a
V S `
DH O~me!
1 `
1 DH Me~me!
n
. D
The coefficient a is a constant, V is the interfacial molar
area, and n is the ratio of anions to cations in the oxide. The
principal terms describing W ad are the partial enthalpies of
`
mixing at infinite dilution of oxygen (DH O~me! ) and the
`
semiconductor cation ~Me! (DH Me~me!! into the electrode
`
metal ~me!. As experimental values for DH O~me! and
`
DH Me~me! are sparse, approximate values can be obtained
from the model by Miedema et al.23,24
`
A comparison of the magnitudes of DH Me~me! for the
electrode metals in this study can explain some of the trends
in the barrier resistance measurements. For the PTC BaTiO3
sample, while Ag has a more stable oxide compared to Au,
significantly lower barrier resistances were measured for the
Au electrode. This can be explained by the fact that the metal
cation-electrode metal interactions are significantly stronger
in the case of Au as described by the partial enthalpies of
mixing:
` `
DH Ti~Au!~ 2210 kJ/mol! ,DH Ti~Ag!~ 255 kJ/mol! ,
` `
DH Ba~Au!~ 2276 kJ/mol! ,DH Ba~Ag!~ 2155 kJ/mol! .
This can also explain the relatively low barrier resistance of
Pt on NTC NiMn2O4 as compared to Au and Ag:
` `
DH Mn~Pt!~ 2101 kJ/mol! ,DH Mn~Au!~ 240 kJ/mol!
`
,DH Mn~Ag!~ 137 kJ/mol! .

TABLE II. Equivalent circuit parameters for the circuit pictured in Fig. 1 derived from the impedance data on
NTC.

Rg R gb C gb Rb Cb

Electrode ~kV! ~kV! ~pF! a1 ~V! ~nF! a2

In-Ga 2.1 8.8 1.2 0.00 103 36.4 0.01

Au 1.8 6.3 1.6 0.02 455 6.2 0.14
Ag 2.0 6.4 1.6 0.01 442 20.0 0.19
Pt 2.1 6.7 1.5 0.00 191 17.5 0.11

J. Appl. Phys., Vol. 80, No. 3, 1 August 1996 D. P. Cann and C. A. Randall 1631
 Thus, the variation of the barrier resistance with elec- 1
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trode type is qualitatively consistent with what is expected
2
W. Heywang, J. Mater. Sci. 6, 1214 ~1971!.
3
R. C. Buchanon, Ceramic Materials for Electronics ~Marcel Dekker, New
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York, 1986!.
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5
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V. CONCLUSIONS 8
S. H. Wemple, D. Kahng, C. N. Berglund, and L. G. Van Uitert, J. Appl.
The electrode-ceramic interfacial characteristics of PTC Phys. 38, 799 ~1967!.
9
S. H. Wemple, in Ohmic Contact to Semiconductors, edited by B.
and NTC devices were measured using complex-plane im- Schwartz ~The Electrochemical Society, New York, 1969!, p. 128.
pedance analysis. Equivalent circuits for PTC and NTC 10
J. W. Fleming and H. M. O’Bryan, Am. Ceram. Soc. Bull. 55, 715 ~1976!.
samples electroded with Ag, Au, Pt, and In-Ga were ob- 11
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12
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~1969!.
barrier resistance, which is related to the Schottky barrier 13
A. K. Johnscher, Dielectric Relaxation in Solids ~Chelsea Dielectrics,
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A. R. Von Hippel, Dielectrics and Waves ~Wiley, New York, 1954!.
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H. S. Basu and R. N. Maiti, Mater. Res. Bull. 21, 1107 ~1986!.
16
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17
E. H. Rhoderick and R. H. Williams, Metal-Semiconductor Contacts
ACKNOWLEDGMENTS ~Clarendon, Oxford, 1988!.
The authors would like to thank the Center for Dielectric
18
L. M. Levinson and H. R. Philipp, J. Appl. Phys. 49, 6142 ~1978!.
19
L. J. Brillson, Surf. Sci. Rep. 2, 123 ~1982!.
Studies and the ISHM Educational Foundation for funding 20
D. P. Cann and C. A. Randall ~unpublished results!.
this research. Thanks also to J. Stauffer, D. Horsey, and D. 21
D. Y. Wang, J. Am. Ceram. Soc. 77, 897 ~1994!.
22
Sorge of Keystone Thermometrics for insightful discussions D. Chatain, L. Coudurier, and N. Eustathopolous, Rev. Phys. Appl. 23,
regarding PTCR and NTC ceramics. Thanks go to our col- 1055 ~1988!.
23
A. R. Miedema, F. R. de Boer, R. Boom, and J. W. F. Dorleijn,
leagues at MRL for many useful discussions including J. P. CALPHAD 1, 353 ~1977!.
Dougherty, T. R. Shrout, L. E. Cross, R. E. Newnham, L. C. 24
F. R. de Boer, R. Boom, W. C. M. Mattens, A. R. Miedema, and A. K.
Burton, N. M. Rodriguez, and R. T. K. Baker. Niessen, Cohesion in Metals ~North Holland, New York, 1988!.

1632 J. Appl. Phys., Vol. 80, No. 3, 1 August 1996 D. P. Cann and C. A. Randall