I O U R N A L OF

ELSEVIER Journal of Non-Crystalline Solids 172-174 (1994) 1408-1412

'Window' effect in the analysis of frequency dependence

of ionic conductivity
H. Jain*, C.H. Hsieh
Department of Materials Science and Engineering, Lehigh University, 5 E. Packer Avenue, Bethlehem, PA 18015-3195, USA

Abstract

Usually the frequency dependence of ionic conductivity of solids is analyzed in the form of a power law or as the
deviation of imaginary part of electric modulus from ideal Debye peak. The power law formalism is shown to be sensitive
to the choice of frequency window employed in the analysis. The results demonstrate the inadequacies of either formalism
and a method is suggested of combining the two formalisms for parameterizing non-ideal electric response in the vicinity
of the electrical conductivity relaxation time.

1. Introduction unity. Here A' is another fitting parameter. They

Various ionic conductors have similar dispersion
of electrical conductivity, tr, as a function of fre-
quency. Often this has been analyzed in the form of
a power law [1]
t r = t r d c + A O 9 ~, 0 < S < 1.
trdc is the dc conductivity, ~o = 2rcf is the angu-
lar frequency and A and s are fitting parameters.
The exponent s has been found to be material-
dependent [1]. Very recently Lim and co-workers [2]
have extended the range of temperature, T, and
suggested
(7 ~--- O'd¢"Jl-A e f ° + A'(o 1"°, 0 < So < 1,
based on the observation that the exponent, s, in
Eq. (1) has a transition with increasing temperature
from s = 1 to a constant s = So which is less than
* Corresponding author. Tel: + 1-6107584220. Telefax: + 1-
610 758 4244.
concluded that the transition of s is actually
a superposition of two distinct and separate pro-
cesses with different exponents, namely, So and 1.0.
Here the last term becomes important only at rela-
tively low temperatures or high frequencies, i.e.,
Eq. (2) reduces to Eq. (1) at moderate T and (o.
(1)
Alternatively, the conductivity dispersion is ana-
lyzed in the complex electric modulus M*
( = M' + iM") formalism [3],
M*(~o) = e~l [1 - dtexp( - io)t)( - d~b/dt)],
o
(3a)
(2) with the field decay given by Kohlrausch function
[4]
q~(t) = exp - (t/r) ~, 0 < B < 1, (3b)
where e~ is the high frequency dielectric constant
and r is the electrical conductivity relaxation time.
B is also a material constant [5], and has been

0022-3093/94/$07.00 © 1994 Elsevier Science B.V. All rights reserved

SSDI 0 0 2 2 - 3 0 9 3 ( 9 4 ) 0 0 0 1 5 - F
 H. Jain, C.H. Hsieh / Journal of Non-Crystalline Solids 172 174 (1994) 1408-1412
correlated to the activation energy of ionic conduc-
tion [5] and the average distance between conduct-
ing ions [6]. One may predict that /3 ~ 1 - s
because mathematically Eq. (3) would give
a oc to I # in the high frequency limit. However,
deviations are often observed in this formalism; for
example, the experimental M" data are higher than
the values given by Eq. (3) for frequencies much
larger than the M" peak frequency. It has been
suggested [7,8] that this discrepancy can be
explained by considering the contribution of asym-
metric double well potential (ADWP) configura-
tions to the total conductivity.
Experimentally one has a limited range fre-
quency window available for determining the elec-
trical parameters. If the fitting parameters in
Eqs. (1)-(3) were to represent a true physical phe-
nomenon, the choice of frequency window should
not determine s, fl or the transition of s. The pur-
pose of this paper is to examine the question: does
the choice of frequency window affect s (or fl) or the
transition of s?
2. Data analysis and discussion
We have analyzed the electrical conductivity
data of several solids: a sodium aluminosilicate
(Na20-0.4A1203-2.2SiO2) glass, a quartz crystal
and a lithium triborate glass. The method of sample
preparation is described in Ref. [9] for sodium
aluminosilicate glass, in Ref. [10] for quartz crystal
and in Ref. [11] for lithium triborate glass. All
results reported here are based on data obtained
using precision capacitance bridge assembly (GR
1616) at 10-105Hz. Details of conductivity
measurements are presented in Ref. [12].
Conductivity data are analyzed according to the
power law expression, Eq. (1), using the non-linear
regression procedure (NLIN) in SAS program [13].
Experimental values of conductivity and corres-
ponding frequency are input as values of the vari-
ables a andf. The mathematical model defining the
relationship between a and f is: a = ad¢ + A * f s
where A* and s are the fitting parameters and A* is
related to A in Eq. (1) by A* = A 2 n ~. A weighting
factor w = a-2 is used for each data set when evalu-
ating the error sum of squares in the least squares
1409
1 0 -a
N a20-0.4AI203-2,2SIO = glass
A k
E
o
1 0 -r
0~
C /'/ ~i
. ~G~
104
1 01 10 = 10s 1¢ 0s
f (Hz)
Fig. 1. The effect of frequency window width on s. The open
circles represent experimental data.
procedure. For analysis of lithium borate and
sodium aluminosilicate glasses above room tem-
perature, dc conductivity values are taken from
complex impedance plots. For the data analysis of
the latter glass below the room temperature, trdc is
determined by extrapolating high temperature con-
ductivity using the Arrhenius equation. Only those
a values are used which are not affected by the
electrode effects (as determined from complex im-
pedance plots or the frequency dependence of
capacitance). Nearly the same values of the fitting
parameters are obtained when we use log(a)
and log(f) as input data, and log(a)=
log(ado + A*10 s log(:)) as the model expression to fit
the data without any weighting factors.
Three frequency windows are chosen to examine
the effect of window width on exponent s of Eq. (1).
The result is shown in Fig. 1, as an example, for ac
conductivity data of sodium aluminosilicate glass
at 59.8°C. In this case the power law region with
s = 1 is at a much higher frequency than the experi-
mental range available so that Eq. (2) becomes
practically equivalent to Eq. (1). The important
observation we find from the analysis is that, as the
frequency window increases from the low frequency
side encompassing higher and higher frequency re-
gion, s decreases. Further, we note that s is most
sensitive to the window width in the frequency
region where conductivity just begins to deviate
from the dc plateau. Away from this 'bend' in log(a)
1410 H. ,lain, C.H. Hsieh / Journal of Non-Crystalline Solids 172-174 (1994) 1408-1412
1,2
1.1
N a20-0.4AI203-2.2SIO 2 glass
1.0 0 This shift should result in a higher s, as observed.
0.9
m 0.8
H
0.7
o o
o
0.6
o 50 - 5k Hz
[] 500- 50k Hz
0.5
0.4 i i i i i i
0 50 100 150 200 250 300
T (K)
Fig. 2. Variation of s with temperature, T, for two frequency
windows of the same width.
vs. log(f) plot, s becomes less and less sensitive to
the choice of frequency window. These observa-
tions imply that Eq. (1) does not describe the data
completely, particularly in the region of the bend. It
is noteworthy that this failure of Eq. (1) for describ-
ing the data is outside the uncertainty arising from
errors in the measurements or the choice of dc
conductivity.
Next, following Lim and co-workers [2], ac con-
ductivity data of sodium aluminosilicate glass over
the temperature range of 4.3-350K is analyzed
using power law to examine the transition of s. Two
frequency windows of the same width are chosen:
50 Hz-5 kHz and 500 Hz-50 kHz. The result is
shown in Fig. 2. Up to ~ 100 K we obtain s - 1.02
irrespective of the window position. This region is
discussed by Lu et al. [14] in these proceedings.
Above ~ 100 K, s shows a transition from s - 1.02
to s < 1, but the transition is dependent on the
choice of frequency window. A lower frequency
window reduces the transition temperature. Fur-
ther, from ~ 300 to ,,~ 350 K, s increases again
rather than remaining constant (s = So) as reported
by Lim and co-workers [2] and shown by the
broken line in Fig. 2. This increase can be under-
stood as follows. We noted above from Fig. 1 that,
when the frequency window width decreases by
excluding higher frequency data, s increases. When
the temperature increases, the dc plateau covers
a greater part of the experimentally available
window, which means that, effectively, the
frequency window moves to lower frequencies.
Since we have carefully chosen the a data that
is unaffected by electrode effects, this phenomenon
O
should not be caused by errors from electrode
E~
effects. Apparently Nowick et al. found a plateau,
s = So, around room temperature because they
confined the analysis to those frequencies for which
ff ~> 2adc [2b].
By shifting log(a) and log(to) axes with a scaling
i
350 400 factor determined by the dc conductivity and elec-
trical conductivity relaxation time, Kahnt [15] ob-
tained one 'master' curve of a(to) for several glasses.
So he concluded that all the materials have funda-
mentally the same frequency dispersion. In order to
examine this suggestion, we plot a(to) and M"(to)
together for two different solids in Fig. 3. One is
sodium aluminosilicate glass which has high Na
ion concentration ( ~ 28mo1% Na20) and the
other is a quartz crystal with total mobile ion
concentration of several hundred ppm. For the
high mobile ion concentration glass which is typi-
cal of the glasses used by Kahnt, the M"(to) peak
frequency occurs where a(to) begins to increase rap-
idly (Fig. 3(a)). For quartz crystal, the peak in
M"(to) occurs, however, where a(to) is very slowly
varying, i.e., much before the bend in the a(to) plot
(Fig. 3(b)). From a comparison of these two plots,
we suggest that the relative position of the bend in
a(to) with respect to the conductivity relaxation
time (as given by the frequency where M" is max-
imum) could be a sensitive function of ion concen-
tration and possibly some other material property.
This effect is apparently obscured if comparison is
made among different solids with relatively high
mobile ion concentration. Fig. 3(b) shows that for
quartz there is a slowly varying afro) which contrib-
utes to the non-Debye characteristics in the M"
peak. Apparently, in high mobile ion concentration
solids investigated by us, the s < 1 and s = 1 re-
gions are not so clearly resolved and we see a con-
tinuous variation from dc-like to s = 1 behavior.
Thus, in general, there is a material-dependent
component in the a(to) plot. This component is
most easily observed in the frequency range deter-
mined by the conductivity relaxation time, or the
 H. Jain, C.H. Hsieh ,' Journal o[ Non-Crystalline Solids 172- 174 (1994) 1408 1412 1411

1 0 "6 0.04 1 0 "e 0.08

(a) N a20-0.4AI203-2.2SIO 2 glass (b} Quartz
M" (223°C)
M" (79.80C) 298.8°C

I 0 "7 0.03 0.06

1 0 "e 2230C

U) b l0-, 0.02 ~.- 161.4°C 0.04

1 0 "10 120"C

1 0 "9 0.01 0,02

/
1 0 "1° 0 1 0 "1= ................. ' ....................... 0
101 102 103 104 10 s l0 s 101 1 02 1 03 1 04 1 0s 1 0~

f (Hz) f (Hz)

Fig. 3. Location of M" (to) peak with respect to conductivity dispersion in (a) glass and (b) high purity quartz crystal. Curves are to guide
the eye.

M" plot. For a discussion of various processes 0.05

lO'e,
observed from the frequency and temper- A: I~:0.53 Lithium Trlborate (#28)
B: s=o.6g
ature dependence of a, the reader is referred to C: s=0.75 ." . ' 0.04
1 0 .7 ~" ~ , C a formalism
Ref. [ 16]. ,~ 20 - 5k Hz . ' ~ /
¢ "~ \..j.
We emphasize that often we are forced to choose .'<o 0.03
a frequency window by the equipment. This is the 1 0 -e a
/ ' '--~
~..O ~
"~ ~B
a formallam
window of a(to). M"(og) formalism often selects 0.02

a smaller frequency window around ~ = 1. a(~o) A

1 0 -o
data are likely to be more accurate than M"(co) data 0.01

(when electrode effects are not dominant) because M" formalism - ~_

the error in M" includes error from conductivity as 1 0 "I° 0
101 102 10 s 104 105 10 e
well as capacitance measurements. So in order to
f (Hz)
determine the material response in the vicinity of
conductivity relaxation time, it appears logical to Fig. 4. Appropriate selection of frequency window
choose the window width from M"(to) plot and (20 Hz-5 kHz) for analyzing the data by the power law using
then use this window for analyzing a(~o) via Eq. (1). M"(to) formalism as the basis.
With this view, we have analyzed the conductivity
data of lithium triborate glass. The fl-value has
been determined earlier to be 0.53 [7] by using the
M"(~o) formalism. As shown in Fig. 4 and observed 20 Hz to 5 kHz, which is the range in which M"(~o)
by many others (for example, Ref. [3]), there is formalism shows a good fit to the experiment data.
a significant deviation of experimental M" data It gives s = 0.75. In either case, note that fl :~ l-s,
from the fitted curve at high frequencies. Two fre- which indicates that the often used approximation
quency windows are chosen to analyze the data in fl--- l-s should be used with caution. To confirm
a(~) formalism by using Eq. (1). One is from 20 Hz its validity, one must exclude contributions to
to 100 kHz, which is the same as the total window conductivity from sources like A D W P configura-
of datapoints. It gives s = 0.66. The other is from tions.
1412 11. ,lain, C.H. Hsieh / Journal of Non-Crystalline Solids 172-174 (1994) 1408-1412

3. Conclusions J.M. Tarascon and M. Armand (materials Research

Society, Pittsburgh, PA, 1993) p. 219.
From above analysis, we conclude the following. (b) A.S. Nowick, B.S. Lim and A.V. Vaysleyb, these Pro-
ceedings, p. 1243.
(1) The presence of window effect illustrates that [3] C.T. Moynihan, L.P. Boesch and N.L. Laberge, Phys.
conductivity power law (Eq. (1)) is only an approxi- Chem. Glasses 14 (1973) 122.
mate description of the actual frequency depend- [4] G. Williams, D.C. Watts, S.B. Dev and A.M. North, Trans.
ence of ionic conductivity. Faraday Soc. 67 (1971) 1323.
[5] K.L. Ngai, J.N. Mundy, H. Jain, O. Kanert and G. Balzer-
(2) The transition from s = 1 to s < 1 region
J611enbeck, Phys. Rev. B39 (1989) 6169.
with increasing temperature is sensitive to the [6] H.K. Patel and S.W. Martin, Phys. Rev. B45 (1992)
choice of frequency window. 10292.
(3) The frequency response in the vicinity of con- [7] K.L. Ngai, R.W. Rendell and H. Jain, Phys. Rev. B30
ductivity relaxation time is a material property, i.e., (1984) 2133.
it is not the same for all the ionic conductors. [8] K.L. Ngai and R.W. Rendell, in: Handbook of Conducting
Polymer, Vol. 2, ed. T.A. Skotheim (Dekker, New York,
(4) A more accurate description of material re- 1986) p. 967.
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[11] H.L. Downing, N.L. Peterson and H. Jain, J. Non-Cryst.
Solids 50 (1982) 203.
The authors wish to thank X. Lu for sharing his [12] H. Jain, in: Experimental Techniques of Glass Science, ed.
low temperature electrical data. This work is sup- C.J. Simmons and O.H. E1-Bayoumi (American Ceramic
ported by National Science Foundation. Society, Westerville, OH, 1993) p. 433.
[13] SAS/STAT User's Guide, ver. 6, 4th Ed., Vol. 2, 1989, SAS
Institute Inc., Cary, NC 27512, USA.
[14] X. Lu, H. Jain and O. Kanert, J. Non-Cryst. Solids, these
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[15] H. Kahnt, Ber. Bunsenges. Phys. Chem. 95 (1991) 1021.
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