Solid State Ionies 8 (1983) 159-164

North-Holland PublishingCompany

THE DETERMINATION OF HOPPING RATES AND CARRIER CONCENTRATIONS

IN IONIC CONDUCTORS BY A NEW ANALYSIS OF ac CONDUCTIVITY

D.P. ALMOND
School of Materials Science, University of Bath, Claverton Down, Bath BA2 7,4 Y, UK

and
G.K. DUNCAN, A.R. WEST
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB9 2UE, Scotland, UK

Received 7 October 1982

ABSTRACT
The a.c. conductivity o(m) of ionic materials takes the form, o(m) = o(o) + Amn. The c a r r i e r
hopping rate, Up, is obtained from the new expression o(o) = Aconn and the c a r r i e r concentration is
estimated from o(o). The contribution of creation and migratio~ terms to the activation energy for
conduction may be determined from the thermal activation of o(o) and ~D and the corresponding entropy
terms quantified. D a t a have been analyzed for four widely d i f f e r e n t ibnic materials: single crystal
Na B-alumina, p o l y c r y s t a l l i n e Li4SiO~, AgTl~AsO~ glass and Ca(NO3)2/KN03 glass and melt. For each,
the c a r r i e r concentration and hopping rates have been obtained.

The conductivity of an ionic conductor is constant, T is absolute temperature and Up is

determined by both the concentration of the the hopping rate of the ions. The hopping
mobile ions and the rate at which they are able rate is thermally activated and is given by:
to hop from site to site in the material.
Experimentally, the separation of these two Up = moeXp(-AGa/kT)
terms has been found, in general, to be
= moexp(ASa/k)exp(-Ea/kT)
difficult. Methodswhich have been used with
some success include: the Hall effect [ l ] , the
doping of ionic crystals with aliovalent = meexp(-Ea/kT) (2)
impurities [2] and the electrochemical measure- where &Ga, Ea and ASa are the free energy,
ment of a c t i v i t i e s in glasses [ 3 ] . None of activation energy and entropy of the hopping
these methods appear, however, to be readily process, mQ is the vibrational frequency of
applicable to a l l ionic conductors. In this
ions in t h e l r l a t t i c e sites and me is an e f f e c t -
paper we demonstrate that c a r r i e r concentrations ive attempt frequency which includes the entropy
and hopping rates can be separated by a new term. The concentration c of mobile ions may
treatment of a.c. conductivity. The potential
or may not be temperature dependent. In the
scope of the method is i l l u s t r a t e d by the
former case,
analysis of four very d i f f e r e n t materials: a
single crystal superionic conductor (Na
B-alumina), a p o l y c r y s t a l l i n e i o n i c conductor c = CoeXp(-AGc/kT)
( L i . S i O , ) , a vitreous e l e c t r o l y t e (AgTI.AsO.
glass) and a poorly conducting n i t r a t e glass = CoeXp(ASc/k)exp(-Ec/kT)
(40 mol % Ca(NOa)2 - 60 mol % KN03) both above
and below the glass transformation temperature. = CeeXp(-Ec/kT) (3)
The d.c. c o n d u c t i v i t y of a c r y s t a l l i n e i o n i c
conductor is determined by the expression where AGc, Ec and ASc are the free energy,
activation energy and entropy for the creation
obtained from the theory of random walk [ 4 ] :
of mobile carriers and ce is the effective
a(o) = Kmp = (Ne2aZ/kT) yc(l -C)mp (l) i n f i n i t e temperature c a r r i e r concentration.
Measurements of d.c. conductivity, over a
where y is a geometrical factor that may include
range of temperatures, provide numerical values
a correlation factor, c is the concentration of
for the net activation energy and pre-exponent-
mobile ions on N equivalent l a t t i c e sites per
ial factor for the overall conduction process.
unit volume, a is the hopping distance, e is
The d i f f i c u l t i e s which often arise in c o r r e l a t -
the electronic charge, k is Boltzmann's

0 167-2738/83/0000-0000/$ 03.00 © 1983 North-Holland

160 D.P. A l m o n d et al. / Hopping rates and carrier concentrations in ionic conductors
ing such values w i t h the t h e o r e t i c a l expressions,
( I ) , ( 2 ) , ( 3 ) , are :
a) i t is not possible t o determine,
unambiguously, whether or not the c a r r i e r
c o n c e n t r a t i o n is t h e r m a l l y a c t i v a t e d , i . e .
whether the measured a c t i v a t i o n energy of o ( o )
is (E a + Ec) or Ea alone.
b) i t is not p o s s i b l e t o determine the
magnitudes of me and c e since t h e y are present
as a product in the p r e - e x p o n e n t i a l f a c t o r .
Up to now the main reasons f o r using a . c .
techniques to measure i o n i c c o n d u c t i v i t y have
been t o avoid the n e c e s s i t y of non-blocking
e l e c t r o d e s and t o f a c i l i t a t e the s e p a r a t i o n of
g r a i n boundary and bulk phenomena in p o l y -
crystalline materials. I d e a l l y , a frequency
independent c o n d u c t i v i t y , equal to the d.c.
c o n d u c t i v i t y , should be obtained a t h i g h e r
frequencies where e l e c t r o d e and grain boundary
phenomena are i n s i g n i f i c a n t . In p r a c t i c e , such
a frequency independent p l a t e a u is observed,
often over several decades of frequency, but is
l i m i t e d at higher frequencies by an a d d i t i o n a l
bulk phenomenon. This takes the form of a
power law increase in c o n d u c t i v i t y w i t h
frequency. The a . c . c o n d u c t i v i t y a(m) is
found t o v a r y w i t h angular frequency co as
~(co) = o(o) + A~n (4)
where a(o) is the d.c. c o n d u c t i v i t y , A is a
temperature dependent parameter and n is found
to take values between 0 and I . Jonsche~ [ 5 ]
has suggested t h a t t h i s power law is a
' u n i v e r s a l ' p r o p e r t y of m a t e r i a l s t h a t is
r e l a t e d t o the dynamics of hopping conduction.
R e c e n t l y , we have shown [ 6 ] t h a t t h e r e is a
simple r e l a t i o n s h i p between a(o) and A. The
c o n d u c t i v i t y o(co) can then be expressed as
, l-n n This r a i s e s the question o f the magnitude o f
• o(co) = K~p + ~CJp co (5)
where K was defined in equation (1). By
combining equations (4) and (5) the hopping
rate cop is given by
co = ( ~ ( o ) / A ) I / n (6)
P
This provides a p a r t i c u l a r l y sir.lple way of
quantifying m . The t h e o r e t i c a l temperature
dependences of p o(o) and A may be obtained by
s u b s t i t u t i n g f o r K and cod from ( I ) , (2) and (3)
in ( 5 ) . For m a t e r i a l s 'in which the c a r r i e r
c o n c e n t r a t i o n is independent of temperature,
o n l y mo is t h e r m a l l y a c t i v a t e d and the
a c t i v a t i o n energies of a(o) and A are Ea and
(I - n ) E a, r e s p e c t i v e l y . For m a t e r i a l s in which
the c a r r l e r c o n c e n t r a t i o n is a l s o t h e r m a l l y
a c t i v a t e d , K is t h e r m a l l y a c t i v a t e d and
consequently, the a c t i v a t i o n energies of ~(o)
and A become Ec + Ea and E + (I - n ) E a,
respectively, c glass.
The above r e l a t i o n s h i p s have been used to
analyse a.c. c o n d u c t i v i t y data from f o u r
d i f f e r e n t i o n i c conductors. The f i r s t three :
s i n g l e c r y s t a l Na B-alumina, p o l y c r y s t a l l i n e
L i , S i 0 4 and AgTI,AsO, g l a s s , appear t o have
temperature independent c a r r i e r c o n c e n t r a t i o n s
whereas the f o u r t h , K/Ca n i t r a t e g l a s s , appears
to have a temperature dependent c a r r i e r
c o n c e n t r a t i o n above the glass t r a n s f o r m a t i o n
temperature, Tg.
C o n d u c t i v i t y data at several temperatures
f o r the f i r s t t h r e e m a t e r i a l s are shown in
Fig. I . The s o l i d l i n e s through the data are
f i t s to equation (4). The values of o(o) and
A used f o r these f i t s are shown p l o t t e d in
conventional Arrhenius format as Fig. 2. In
each case, the a c t i v a t i o n energies of a(o) and
A are in the r a t i o 1 : (I - n ) as p r e d i c t e d .
The hopping rates up c a l c u l a t e d from
the same data using equation (6) are shown in
Arrhenius format as Fig. 3. The data were
f i t t e d by the s t r a i g h t l i n e s shown using l i n e a r
regression and values of the a c t i v a t i o n energies
and e f f e c t i v e attempt frequencies were obtained
from the slopes and i n f i n i t e temperature
intercepts, respectively. The a c t i v a t i o n
energies f o r each are w i t h i n experimental e r r o r
the same as those found f o r a(o) in Fig. 2.
This i n d i c a t e s t h a t the thermal a c t i v a t i o n s
of these c o n d u c t i v i t i e s are caused by the
thermal a c t i v a t i o n s of the hopping rates alone.
The e f f e c t i v e attempt frequency me of B-alumina
obtained from Fig. 3 is v e r y s i m i l a r to the
value 2 x 1012 Hz associated with the v i b r a t i o n -
al frequency mo obtained d i r e c t l y from i n f r a -
red a b s o r p t i o n measurements [ I 0 ] . This shows
t h a t the e n t r o p y term ASa in equation (2) is
small in t h i s p a r t i c u l a r m a t e r i a l . Several
authors [4, I I ] have iTnd,~ed suggested t h a t
these e n t r o p y terms should be small in f a s t ion
conductors such as B-alumina.
For L i , S i O , and the Ag+ g l a s s , the e f f e c t -
ive attempt f r e q u e n c i e s , I0 zsHz Fig. 3, are
c o n s i d e r a b l y higher than l i k e l y values of
corresponding v i b r a t i o n a l f r e q u e n c i e s , ~1013Hz.
the e n t r o p y of a c t i v a t i o n ASa in these, and
o t h e r , i o n i c conductors. Some i n s i g h t may be
obtained by using the formula f o r ~Sa which
was d e r i v e d by Wert and Zener [12] in t h e i r
t h e o r y of i n t e r s t i t i a l d i f f u s i o n in m e t a l s :
AS - BEa (7)
a T
m
where Tm is the m e l t i n g temperature and B is
a dimensionless number, ~ 0 . 4 , which is r e l a t e d
to the temperature dependence of the shear
modulus of the m a t e r i a l . Estimates of the
magnitude of the term exp(ASa/k) in me,
obtained using equation (7) are 40, I I and 1.3
f o r the Ag+ g l a s s , Li4SiO, and B-alumina
respectively. These e n t r o p y values match,
to w i t h i n a f a c t o r of f i v e or b e t t e r , those
determined using equation (2) and Fig. 3 and
assuming wo ~ 1013 Hz f o r L i , S i 0 4 and the Ag+
In view of the e r r o r s in e s t i m a t i n g me,
8 and mo ( e s p e c i a l l y f o r Li4Si04 and the Ag+
glass) t h i s is a l l t h a t can be expected at
t h i s stage.
A f t e r the hopping rates have been
determined, i t is p o s s i b l e to estimate the
carrier concentrations. For B-alumina, however
 D.P. A l m o n d et al. / Hopping rates and carrier concentrations in ionic conductors 161

Li&SiO4 n : 0.68 AgTILAs~ n :0.68

Z
E
f184K
u

..(Z
0

b
~ 4 8 0 K ~ 1 4 0 K ~

2 3 A 5 6 2 3 4 5 6 2 3 4 5 6 7
log f(Hz)

FIG. 1
Conductivity data for single crystal Na 6-alumina (ref. 6,7), polycrystalline Li,SiO, (ref. 8)
and Ag~l,AsO4 glass (ref. 9) at a selection of temperatures. Solid curves are f i t s of equation (4)
to the experimental data. Errors in n are estimated as ±0.03. The experimental data for
6-alumina and AgTI,AsO, at the highest temperatures and low frequencies show a conductivity dispersion
associated with electrode polarisation effects.

4t Na /B-alumina Li/.Si 04

n:O-60 n :0.68

1 o-(olT
log o'(o)T 0 -~Eo = 17± 2 kJ moL-1
or - ~ 80±2
1
log AT }

26±2 tl
§
0, 2 4 6 8 10 0 2 Z. 0 4 6 8 10
1000IT (K '1)

FIG. 2
Arrhenius plots of o(o)T and AT.
16 2 D.P. Almond et al. /Hopping rates and carrier concentrations in ionic conductors
161
i Na /~-alumine
15 i
14
13
li
Iog~(secP)1(119~ =15-+2kJrnO[-1
7 •
1000/T ( K4 )
Arrhenius plots of ion hopping rates, Up.
equation ( I ) may be used only semiquantitatively
because of uncertainties in y, a and N : the
mechanism of conduction is an interst~t~alcy one
involving several Na+ ions and two types of
l a t t i c e s i t e , the Beevers-Ross and mid-oxygen,
are involved in the conduction. Further +
d i f f i c u l t i e s arise with Li,SiO, and the Ag
glass because the conduction mechanisms are not
known and in the Ag+ glass, the structure is
completely unknown. We estimate the net c a r r i e r
concentration c' using the approximation:
c' = c ( l - c ) N (8)
and substituting into equation (I) wish assumed
average values for a and y of 3 A and
0.33 respectively. The net a l k a l i ion c a r r i e r
concentrations, c ' , are then calculated to be
22%~(Na B-alumina) 0.5% (Li,SiO,) and I . I %
(Ag" glass).
The composition of the Na B-alumina crystal
was ~ 1.2 Na20.IIA~203 and the high conductivity
of B-alumina has been attributed to the 0.2
excess soda content. Our estimate of the
c a r r i e r concentration of ~22% is in f a i r agree-
ment with t h i s . The room temperature conduct-
i v i t y of the Ag÷ glass is comparable to that of
Na B-alumina despite i t s lower c e r r i e r concent-
I
T Liz.Si04 " Ag71 z.A sO4
/ 78-*4 I \ 25±2
FIG. 3
ratio~. However, in the Ag+ glass, the density
of Ag- ions is about 4 times greater than the
density of Na+ ions in B-alumina and therefore,
the ionic c a r r i e r density difference between the
two materials is only a factor of ~5. This
difference is offset by the higher (~7 fold)
hopping rate in the Ag+ glass at room temperat-
ure as shown in Fig. 3. This enhanced hopping
rate can be a t t r i b u t e d , almost e n t i r e l y , to the
large entropy of activation of the Ag+ glass.
The estimated room temperature conductivity of
Li,SiO, is some I0 decades less than that of
the other two materials. This is largely due
to the much reduced hopping rate in Li,Si04,
Fig. 3, which in turn is a consequence of i t s
much higher activation energy.
Conductivity data for the fourth material
the K/Ca n i t r a t e glass, are shown in Fig. 4a.
The data f a l l into two groups, above and below
the glass t r a n s i t i o n temperature, Tg, ~60°C.
These data were analysed in the same way and i t
is evident that the q u a l i t y of some of the f i t s ,
solid lines Fig. 4a, is not so good as that for
the other three materials, Fig. I. The reasons
for this are not understood. Nevertheless,
reasonable estimates of o(o) and A were obtained
from the low and high frequency l i m i t i n g regions
 D.P. A l m o n d et al. / Hopping rates and carrier concentrations in ionic conductors 163

0 4Ca{NO3}2 0.6KNO3 Tg~ 3 ~ 0 6 3 of these data. Results are shown plotted in

Arrhenius format in Fig. 4b. In the low
353.3K~ : :~ ~ _ . w ~ 0'63 temperature region, below Ta, the activation
energies of o(o) and A are Tn the r a t i o l :
(l - n ) as with the other three materials, Fig. 2.
Above Tg, however, this relationship does not
"T hold. The activation energies are in the r a t i o
E
of I:0.5 whereas a r a t i o I:0.37 might be
expected since in this region n ~ 0.63. The
b --
o', 11
hopping rates, uD, calculated using equation
o (6) and the values of ~(o) and A shown in
Fig. 4b, are plotted in Arrhenius format as
&3 (a} Fig. 4c. In the low temperature region,
T~_ below Ta, the activation energy for ~n is very
0 1 2 3 L 5 6 s i m i l a r ~ t o t h a t of o ( o ) , Fig. 4b. Ab6ve Tn,
log f IHz) however, the a c t i v a t i o n energy of ~(o) is
s i g n i f i c a n t l y higher than t h a t of Up. This is
i n t e r p r e t e d as being due to a temperature
dependent c a r r i e r concentration above TO. The
(b)
temperature dependence of o ( o ) , equati6ns ( I ) ,

~
( 2 ) , ( 3 ) , is in g e n e r a l , caused by the thermal
a c t i v a t i o n of both the c a r r i e r c o n c e n t r a t i o n , c,
328_t 17 kJ mo[ 4 and the hopping rate u D. Thus the a c t i v a t i o n
energy f o r o ( o ) , Fig. ~b, above TQ is taken to
log o-(o)T be Ea + Ec whereas t h a t of Up is ~ Ea alone,
or cr(o)T i.e. Ea = 257 kJ mol "I and Ec = 71 kJ mol " I ,
In the presence of a t h e r m a l l y a c t i v a t e d
IogAT c a r r i e r concentration i t was shown e a r l i e r t h a t
o(o) and A should have a c t i v a t i o n energies in
the r a t i o (E c + Ea) _~c(EC + ( I - n ) E ~ ) . _ Using
i5 the above values OT and Ea with = 0.63 t h i s
r a t i o becomes 1:0.5 which i.s e s s e n t i a l l y the
, ;g , 36_.5, same as the observed r a t i u , Fig. 4b. The
T~ c a r r i e r concentration in the n i t r a t e glass was
2.8 3-0 3.2 3.4 estimated in the same way as f o r the other three
systems. Assuming that only K+ ions c o n t r i b u t e
1000IT (K -1) to the c o n d u c t i v i t y , the concentration of mobile
K+ tons is ~ 0.1% below Tg.
7 Using the new method of analysis proposed
(c) here we are able to u t i l i s e the dynamical
c h a r a c t e r i s t i c s of a.c. c o n d u c t i v i t y to separate
6 the c o n t r i b u t i o n s made by the m o b i l i t y and
concentration of ions to d.c. c o n d u c t i v i t y . The
5 57_.1/., kJ mot -1 method has been used successfully on four
log 0 m a t e r i a l s of widely d i f f e r i n g s t r u c t u r e s and
P4 conductivities and each with a d i f f e r e n t
(sec -1) mobile c a t i o n : Li +, Na+, K+ and Ag+: In the
3 evaluation of ion hopping r a t e s , the c o n t r i b u t -
ion of the associated entropy term has become
e v i d e n t . The q u a n t i f i c a t i o n of t h i s term raises
2 i n t e r e s t i n g questions as to i t s physical o r i g i n
in i o n i c conductors. The a b i l i t y to separate
1 Tg the c o n t r i b u t i o n s of c a r r i e r c o n c e n t r a t i o n , with
! i t s possible temperature dependence, and hopping
0 i i i~ i i i i
rates providesa powerful new way of studying
2.8 3.0 3.2 3-4 ionic transport.
10001T (K ~ ) ACKNOWLEDGEMENT
We thank Dr. M.D. Ingram f o r providing
FIG. 4 (a, b, c) o r i g i n a l c o n d u c t i v i t y data f o r the Ag+ glass.
Conductivity data f o r K/Ca n i t r a t e glass and
supercooled melt a) c o n d u c t i v i t y data ( r e f . 13)
and f i t t e d curves, b) Arrhenius p l o t s of o(o) T
and AT, c) Arrhenius p l o t of Up.
164 D.P. Almond e# al. /Hopping rates and carrier concentrations in ionic conductors

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