Solid State Ionics 70/71 ( 1994) 505-5 10

SOLID
North-Holland STATE
IOWICS

Determination of the free ionic carrier concentration:

A discussion of different methods
H. J. Schiitt
Fachbereich Physik, Vniversitiit Restock, Vniversitiitsplatz 3, D-18051 Restock, Germany

A model of space-charge relaxation is derived and used for the determination of free ionic carrier concentration from experi-
mental data of admittance spectroscopy of glasses. Transient current and Hall-voltage measurements give comparable concentra-
tions due to analogous electrodynamic description. Concentrations given by the homovalent-doping method do not have the same
significance.

1. Introduction kali borosilicate glasses with batch compositions in

mol% given by ( 16 + x) L&O-4Na,O- 1OSiOz-
The determination of the magnitude of charge car- ( 70-x)Bz03, with x=0, 10, 20, 30. These glasses
rier density and mobility is a fundamental problem are of special interest, because for the same glasses
of ionic conductivity in solids. Information on con- a determination of the carrier concentration is known
centration and mobility of ionic charge carriers in from the application of the homovalent doping
glasses have been estimated from the methods of method by Ingram et al. [ 2-41. Disks of 25 mm dia-
homovalent doping [ I-41, field assisted diffusion meter and approximately 2 mm thick were used for
(Chemla method) [ 561, the isothermal transient admittance measurements. After grinding the sur-
ionic current (ITIC) [ 7- 10 ] and Hall effect (HE) face of the specimen have a roughness of the O.Ol-
[ 11,12 1. The published data differ by several orders 1 urn range [ 141. The vacuum evaporated alumi-
of magnitude due to fundamental differences in the num electrodes are blocking for alkali ions and do
underlying conceptions of the transport mechanism. not diffuse into the specimen. The sample holder with
Sometimes conductivity and mobility are even used guarding electrodes [ 15 ] reduces thermal gradients
as synonymous terms supposing that ali mobile ions and thermoelectric voltage.
participate in the charge transport [ 13 1. In this pa- The determination of admittances in the range
per it is compiled how the frequency dependence of 293-7 13 K at constant temperature ( 4 0.25 K) and
the effective dielectric constant in the frequency range at frequencies of lo-‘-lo6 Hz is accomplished by
of the drift- and diffusion-determined space charge different measuring methods. In the frequency range
(DDSC) relaxation has been used to determine a free of lo’-1 O6 Hz, depending on the value of the con-
carrier concentration, no. The comparison of our re- ductivity, a General Radio bridge 162 1 or above 10m4
sults with literature data was carried out on the basis S a commercial admittance bridge SWM 3-2 were
of the corresponding assumptions of the models used used. The accuracy of this measurements was -t 2%.
in the different methods. Below 100 Hz the admittances were evaluated with
an accuracy of + 5% from the phase difference be-
tween the stimulating voltage and the response cur-
2. Experimental rent determined with a laboratory equipment. The
fundamentals of the method are given in [ 161; our
In the experimental part of this work the admit- equipment was modified for measuring voltages be-
tance has been measured on fast ion-conducting al- low 0.1 v.

0167-2738/94/S 07.00 0 1994 Elsevier Science B.V. All rights reserved.

506 H.J. Schiitt /Free ionic carrier concentratcon
3. Results
From the measured admittances the effective di-
electric constant, F’, and the effective electrical con-
ductivity, 5, are evaluated and summarized as mas-
ter curves shown in fig. 1 for one glass composition.
The term “effective” is used since in the low fre-
quency range the data do not represent volume prop-
erties. The master curve of the conductivity is based
on measurements at medium temperature where the
frequency-independent conductivity is a, z 2.4
X 1O-5 Sm-‘. The apparent wide frequency range is
obtained by reduction of the measuring series from
different temperatures to the bulk relaxation time,
7D, of the electrical modulus M*(W). Therefore, the
high frequency parts of the master curve, represent-
ing the bulk relaxation, stem from measurements at
lower temperatures. The low frequency parts are fit-
ted to the curves at medium temperature from mea-
surements just below Tc The high and low frequency
parts of the conductivity curves are shifted along the
axis of conductivity to lit the middle part at
0,=2.4x IO-‘Sm-‘.Uncertaintyassociatedwiththe
effective conductivity and dielectric constant is & 3%
for data from measurements above 1 Hz and * 6%
below 100 Hz. In the range lg(wrD) = -2...+2 the
bulk polarization appears. The frequency depen-
dence of the admittance on concentration and tem-
I I
Fig. 1. Experimental master curves of the frequency dependence
of the effective dielectric constant, F’, and the effective electrical
conductivity, 8, of an alkali borosilicate glass in comparison with
theoretical curves evaluated for the space charge relaxation model
(eq. (10)). rD is explained in the text.
perature in this region was discussed earlier [ 17 ] for
potassium borosilicate glasses. The dispersion in the
frequency range lg( wzu) = - %..- 2 is caused by the
drift and diffusion-determined space-charge polar-
ization at blocking electrodes. A theoretical descrip-
tion of the DDSC-relaxation is given in the next
section.
4. Theory
The aim of the theoretical analysis is at first the
construction of a model for small-signal space-charge
relaxation which gives a good approximation to the
experimental data. On the basis of this relation we
will then determine the free carrier concentration
from the frequency dependence of the admittance.
A one-dimensional model is evaluated on the fol-
lowing assumptions which take into account the spe-
cific properties of the ion-conducting oxide glasses:
(a) One sort of mobile ions moves in an isotropic
material with absolute permittivity E= toe: (to is the
permittivity of the vacuum, EL is a real term of the
relative permittivity in the low-frequency bulk re-
laxation process) between blocking electrodes at
x= -d and x= +d.
(b) A compact double layer exists near the elec-
trodes. Since its capacity is approximately a hundred-
fold higher than the capacity built up by space-charge
relaxation, the compact double layers correspond to
a capacitive short circuit which can be neglected in
this case. There is no static space-charge apart from
the compact double layer.
(c) The electrode interface is assumed to be per-
fectly flat. The influence of roughness shown by Bates
et al. [ 141 is discussed.
(d) In the beginning of the space charge relaxation
the bulk polarization can be regarded as stationary
(tk =const.).
(e) The system is linearized by using small signals
(L’cO.1 V).
(f) The changes in the migrating (free) charge
carrier concentration, )n 1, produced by the periodic
electric field during space-charge relaxation are small
in comparison with the equilibrium concentration
without external fields ( 1II 1<< no).
(g) The diffusion coefficient, D, and mobility, ,LL,
are assumed to be constant in space and time.
 H.J. Schiitt /Free ionic carrier concentration 507

If a small external electric field

6
(
w7s2
EoF*2.E 1+ (10)
E,(t)=E,exp(iot) (1) l+(07fI)2 -l l+(w7s)* >.
is applied to the ionicly conducting sample, drift and A more detailed discussion of the model is given in
diffusion cause small spatial and temporal devia- [181.
tions from the carrier concentration in the zero field Due to the limited frequency range ( 10 -‘- 1O6Hz)
case, n,: a curve fitting of eq. ( 10) was not conducted. The
low frequency increase in conductivity or the low
n(x, t)=nO+n(x) exp(iot) . (2)
frequency plateau of the effective dielectric constant
Analogous relations describe the electrical potential are unsuited for estimations, because in this fre-
and field strength inside the sample quency range curves can be modified by discharge
processes. Therefore, the high-frequency part of E”’
@(x, 0 =@(x) exp(iwt) , (3)
immediately below the frequency range of bulk po-
E(x, t) =E(x) exp(iot) , (4) larization is used for analysis. The effective dielec-
tric constant in the DDSC-relaxation range is de-
where n(x), d(x), and E(x) are complex terms. For
rived from eq. ( 10)
the ionic current density a drift and a diffusion term
is considered 6

-pne%
r’=E;
(
1+
1+(07s)2 >.
(11)

ax-De*
j(x,t)=
ax’ The concentration of free charge carriers results from
this relation if we determine the frequency oIo6,
where p is the mobility of the free charge carriers, D,
where E”‘(wlos) = lot:, using the Nemst-Einstein re-
the diffusion coefficient.
lation, D= pkT/e:
Introducing the equation for the conservation of
charge
(12)
&re
-- aj
at --ax (6)
Further details of this derivation are given in [ 19 1.
it follows that

an
-= 5. Discussion
at (7)

If the last term in eq. (7) is substituted by the Pois- Complex admittances of ionicly conducting glasses
son equation determined at frequencies of 10-2-106 Hz have
shown that the DDSC-relaxation begins at lower re-
a*n
--__ en duced frequencies (Ig (wzp) = - 2... - 8 ) after the
ax* - E
(8)
volume polarization with the relaxation time 7,, has
from the resulting deviation of the equilibrium free reached its low frequency stationary state, E;. There-
carrier concentration, n(x), the macroscopic space- fore we can directly use relations of the model of
charge polarization is given by DDSC-relaxation established above for the estima-
+d tion of the free carrier concentration, no, from the
frequency dependence of the effective dielectric con-
P(0) = Cdj xn(x)dx. (9)
stant, g’. The errors due to high field discharge and
-d
surface roughness remain relatively low, since for the
For specimens of conducting glasses with d= 1 mm, estimation the frequency wloc is determined in the
it is commonly found that d/L,=6> 1 (LD=@, frequency range of the beginning of the DDSC po-
the Debye length, 7=~~~~/0~). Then the effective larization where 5’= 10~:. The no-values of the in-
permittivity is given approximately by vestigated alkali borosilicate glasses are located in the
508 H.J. Schiitt /Free ionic carrier concentration
range of 10z2- 1O24 mm3 corresponding to ppm por-
tions relating to the composition. Concentration, n,,,
and mobility, ,LL,of free carriers evaluated according
to
0, =noey
are summarized in fig. 2 for one glass composition.
The statistical error of the no-values estimated from
experimental conditions is ? 50%.
In a test for the frequency ~~~~ at the characteristic
depth of 3 x 1O-* m from the electrodes 1n(x) 1 was
determined to be 2x 102’ rnm3. Since no was found
to be 6x 1O22me3 at this temperature, the required
relation no> I n(x) 1 confirmed the model assump-
tion at this frequency.
In this layer, near the electrodes, the electric field
strength was found to be 4 X 1O4V m- ’ which is typ-
ical of linear behaviour in bulk relaxation. This jus-
tifies the use of linear equations in the theory. How-
ever, in the frequency range of the low-frequency
?-plateau (o<l/rS), In(x)] was found to be
7 x 1O23 m-3, and the field strength at the charac-
T that all existing alkali-ions are mobile. Since this
E
9 estimated mobility represents a mean value for all
F
2L
23
Fig. 2. Temperature dependence of the free ionic carrier concen-
tration, no, and the corresponding mobility, p, of an alkali boro-
silicate glass determined by eqs. ( 12 ) and ( 13 ) , respectively. The
probable error of k 50% is given by the bar. The lines are guides
to the eye.
teristic depth was 2X lo6 V m-i. This value is be-
yond the linear range in bulk measurements.
It is seen that the model predicts, for the para-
meters expected for ion-conducting glasses in the
middle frequency range of DDSC-relaxation, a
(13) C’-0 -’ dependence, whereas the experimental val-
ues are proportional to w-‘.‘~‘---‘. According to the
results of Bates et al. [ 141 we have to give up the
assumption of a plane interface and to consider the
type of roughness and pores, respectively, which de-
termines the exponent of the constant phase angle
(CPA)-element &.,=A (io) -“, for the metal-elec-
trolyte interface. Using n=0.9 the theoretical curve
gives a good approximation to the experimental data
of the glass composition shown in fig. 1.
If in the Nernst-Einstein relation the Haven ratio
HR= D*/D, is introduced (D’ is the self diffusion
coefficient for tracer ions; D,=akT/( n,,e*), where
ylst is the concentration of carrier ions according to
the composition), one ought to consider the factor
H,=O.2...0.45 [ 61. The systematic errors caused by
roughness and the Haven ratio compensate each
other approximately and are not considered in this
estimate.
The Chemla method makes the assumption that
diffusion as well as mobility is determined by self-
diffusion of tracer ions in an electric field [ 5,6] and
method sums up the effects of all charge carriers, the
charge carriers.
The homovalent-doping method of Bruce et al. [ 1 ]
gives in the work of Ingram, Mtiller and Torge [2-
4] for the same borosilicate glasses as in this work
concentrations of mobile charge carriers in the range
1026-1027 m-3. The significance of these concentra-
tions depends upon the model which is constructed
by the application of the weak electrolyte theory to
ion conducting solids [ 201. The ionization process
was described as [ 2 1,221
M+h*=M*+h; [M*] < [Ml, (14)
(M, M* are the cations in normal and interstitial sites;
h, h* are the vacant normal and interstitial sites).
Mobile ions appear as pairs of alkali ions where one
alkali ion is bound to a non-bridging oxygen ion and
the other mobile ion is considered as an interstitial
ion (mobile defect) contributing to the concentra-
 H.J. Schiitt/Free ionic carrier concentration
tion of mobile interstitials, [M*]. This model was
extended to systems with two different alkali ions
(mixed-mobile-ion effect) assuming that the foreign
cations ( I6 mol%) form fixed immobile cation
pairs. Thus a free carrier concentration is, by this
method, not determined, however, a total concen-
tration of the interstitial ions which, according to the
underlying law of mass action for the ionization pro-
cess, exist in the system and are able to participate
in the charge transport.
The isothermal transient ionic current of lithium
ions in amorphous polymers was studied by Watan-
abe et al. [ 731. They created a space-charge near
the electrodes with a dc voltage and determined the
drift mobility from the maximum in the time-de-
pendent depolarization current which is connected
with the ion time of flight. Chandra [ 91 emphasized
the ability to identify different sorts of carriers as an
advantage of this method. Abdel-Gawad and Bhat
[ lo] used an improved theoretical model of the ITIC
process. The mobility of 1.6~ 10m9 m2 V- ’ s- ’ eval-
uated by this method is in the same range as in the
present study. However, the statement of the initial
conditions and their nonreproducibility make the
ITIC method problematic.
Clement et al. [ 111 investigated the Hall effect of
Ag+ ion conducting (1 -x)AgPO,-xAgI(O<x<O,
5) glasses. Because electrode reactions must be
avoided they used a symmetric square wave current
( l-5 x IO3 Hz; 0. I- 100 PA), which allowed sam-
pling of the response signal in the stationary ohmic
range at a suitable frequency. The investigations give
nearly constant Hall mobilities ,LL~ = (6 * 2) x 1O-*
m2 V-’ s-’ and carrier concentrations
n~4.2~ 102’-4x lO25 m-3. Denoyelle et al. [ 121
used the same apparatus on Ag,O-P,05 glasses and
determined pLH= lx IO-* m2 V-’
n=2.Ox lO22 me3 which are comparablesw:th “,“,“,
data. I point out that the Hall method is used near
its limit of resolution and that a theory of the Hall
effect for ion-conducting solids considering diffu-
sion and drift as in our theory does not exist.
6. Conclusions
The ITIC and the HE as well as the DDSC-relax-
ation method require for the determination of the
509
carrier concentration no transport mechanism as-
sumptions. The results of ITIC and HE method are
comparable with the free ionic carrier concentration
from DDSC-relaxation, which are caused by the
comparable current voltage relations during the
measurements and the analogous “time windows”.
This means that, in the time domain of the ITIC and
HE method, as well as in the frequency varying
DDSC relaxation method the time- and frequency-
independent conduction, respectively, is investi-
gated by different methods of stimulation. The ad-
vantages of the DDSC relaxation method consist in
a careful analysis of the transport processes and the
measuring data and in the higher precision generally
obtained by the application of sinusoidal ac meth-
ods. In the future we have to investigate the influ-
ence of roughness in more detail. A test of the dif-
ferent methods on the same specimen would be very
desirable.
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