IONIC CONDUCTIVITY MEASUREMENTS OF

HEAVILY DOPED AgCl : Cd CRYSTALS

K. Zierold, M. Wentz, F. Granzer

To cite this version:

K. Zierold, M. Wentz, F. Granzer. IONIC CONDUCTIVITY MEASUREMENTS OF HEAVILY DOPED AgCl : Cd CRYSTALS. Journal de Physique Colloques, 1973, 34 (C9), pp.C9415-C9-420. <10.1051/jphyscol:1973969>. <jpa-00215445>

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JOURNAL DE PHYSIQUE

Colloque C9, supplimetlt au t1 1 1- 12, Tot~c.34, Novembre-Dkcembre 1973, page C9-415

IONIC CONDUCTIVITY MEASUREMENTS

OF HEAVILY DOPED AgCl : Cd CRYSTALS
K. ZIEROLD, M. WENTZ and F. G R A N Z E R
Tnstitut fiir angewandte Physik, D 6 Frankfurt a m Main,
Robert-Mayer-Strasse 2-4, B R D

Resume. - Nous avons mesure la conductivite ionique de AgCI, fortement dopC par Cdz+
(0 a 5 000 ppm). Dans le domaine de temperature 250-400 K, nous avons Ctudie la solubilite de
Cd++ dans AgCI. Pour la discussion des resultats obtenus en mesurant la conductivite ionique
au-dessous de 240 K et pour expliqucr les energies d'Arrhenius tres Clevees dans ce domaine de
temperature, nous avons propose les deux modeles suivants : 1) Association des dipdles aux
agregats plus grands. 2) Precipitations d'une superstructure : CdCI2, 6 AgCI.
Abstract. - Ionic conductivity measurements in heavily doped AgCI : Cd crystals (from 0
to 5 000 ppni) were carried out. A solubility curve of Cd? in AgCl for the temperature range
250 K to 400 K is presented. Very high Arrhenius energies were measured below 240 K. A dipole
association model and a superstructure model are discussed to explain the obtained conductivity
data. I t is shown that the experimental results can appropriately be described by the assumption
of the precipitation of this superstructure (CdC12.6 AgCI).

I . Introduction. - Ionic conductivity measurements

in AgCl doped with divalent metal ions have been
performed by many authors [ l ] to [ 5 ] . Mainly crystals
with small impurity concentrations were used, which
have been investigated extensively over the whole
temperature range. Examinations of heavily doped
samples were usually limited t o temperatures between
room temperature and melting point. Therefore a
lack of information exists, concerning all properties
related to transport phenomena in heavily doped
ionic crystals below room temperature. It is the aim
of this contribution to present some preliminary
results obtained by ionic conductivity measurements
of AgCl Crystals containing between 0 and 5 000 ppm
cadmium.

evaporated Ag-electrodes

1. p l a t e l e t s

/I

quarzglas
2 . Bridgman crystals

,evaporated

Ag-electrodes

2. Experimental. - 2 . 1 CRYSTALPREPARATION.
T w o different shapes of crystals were used in the
experiments (Fig. 1) :
a) Plate-like crystals about 200 11 thick, individually
doped u p to 5 000 ppm C d Z + and grown by the
sandwich method. This method was introduced by
Clark and Mitchell [6] and improved by Zorgiebel
and Wendnagel [S].
b) Discs of about 3 nim thickness cut from a cylindrical crystal of 15 mni in diameter grown by the
Bridgman method.
The second were used for comparison and to
exclude surface ell'ects. The impurity concentration
of the Bridgmnn-samples was determined by the
distribution coefficient [9].
T o achieve smooth surfaces, all samples were polished
with KCN
01- NaZS,O, - solutions. T o avoid
-

FIG.1 . - Measuring arrangement.

polarization effects silver electrodes were evaporated

on [lo].
2 . 2 MEASUREMENTS.
- The
of the samples was measured
(Knick company), which has
up to 10" 52 and an accuracy ol
on sensitivity range.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1973969

electrical resistance
with an ohmmeter
an input resistance
3 to 10 '%, dependent

K . ZIEROLD, M . WENTZ A N D F. GRANZER

C9-416

First the samples were cooled down in a cryostat

to a temperature of about 170 K and kept thus at
least for 2 h. During the measuring procedure the
samples were warmed up with a heating rate of
0.5 K/min. The electrical resistance was measured at
intervals of 2 to 10 K. We have checked a t different
temperatures, that a storage time up to one hour did
not affect the results.

3. Theory. - The theoretical backround is well

established [l I], 1121. It follows a short repetition of
the final equations. The conductivity a is given by :

; L1 = mobility ; q = ion charge).

(x =
The summation runs over all possible kinds of charge
carriers i. The mobility is given by :

p =T eipj-

$1

Arrhenius energies as a function of activation energies

in the region I to IV.
(HF = Frenkel enthalpy, Uo, UD resp. migratiorz
energy for interstitials resp. vacalicies ;
U, = activation energy for association of impurityvacancy-dipoles ;
U p = activation energy for oacancies in the cr precipitation region )).
Region
Region
Region
Region

I : intrinsic region
I1 : vacancy region
111 : dipole association region
1V : (( precipitation region ))

El = H F / -I-~ UO
EII = Un
EIII = Un
UA/~
Erv = UiIi
Ul,

+
+

Regions 111 alld IV are liere of special interest, especially because region I V is assumed to be a rather
unknown (( precipitation region D.
4. Results. - 4 . 1 DESCRIPTION
OF THE CONDUCPLOTS.- Figure 3 and figure 4 show the Arrhenius plots of the two types of crystals with various
impurity concentrations. Let us first consider the
curves of the (( pure )) crystals i n both graphs. We can
distinguish the regions I, 11 and 111. It is well known
from theory e. g. [ I 11, [I21 that the transition temperature between region I and I1 depends on the
impurity concentration, namely the lower the transition temperature the lower the impurity concentration. Consequently the undoped Bridgman crystals
are (( purer )) than the platelets. In the other curves
TIVITY

( U = activation energy ; T = Kelvin temperature ;

k = Boltzmann's constant ; B = constant).
Whence follows the final equation :
o~

- (
exp

(3)

E being a sum of different activation energies depending

on the temperature range.
Figure 2 shows the typical Arrhenius-curve obtained
from the conductivity of an ionic crystal doped with
divalent metals.

region

1.. Ag CI "pure"

1 1

2.0

FIG.2. - Typical Arrhenius plot of ionic conductivity.

4 CI 50ppm Cd
+

3.0 Ag C l * 500ppm C d
L.fiAgCI

Generally 4 well defined slopes will be observed

with different corresponding Arrhenius energies E.
Table I shows the functions between the Arrhenius
energies and the different activation energies, i. e.
the dominating conductivity process in these regions.

'5.4

5.0

4.6

4.2

5 0 0 0 ppm Cd

3.8

3.4

3.0

2.6

2.2

1000

c-

FIG.3. - Ionic conductivity of AgCI : Cd (platelets).

IONIC CONDUCTIVITY MEASUREMENTS O F HEAVILY DOPED AgCI : Cd CRYSTALS

C9-4 1 7

a hint can be taken to a precipitated superstructure

of CdC1, . 6 AgCl which will be discussed later on.
In some other crystals a slightly larger Arrhenius
energy was observed which can be interpreted as
many small indistinguishable solution processes.
4 . 2 ACTIVATION
ENERGIES. -The activation energies
for the intrinsic region E,, the vacancy migration U,
and the association to dipoles UAare calculated from
the Arrhenius energies with the formulae of table I.
In table I1 these results are compared with those of

Values for defects paran~etersin AgCl : Cd

Miiller
(1965)

Abbink
and
Martin
(1966)

Corish
and
Jacobs
(1972)

Present
work

0.785
0.35
0.27

0.725
0.27
0.47

0.74
0.29
0.29

0.78
0.30
0.30

El (eV)
U , (eV)
U , (eV)

FIG.4.

onic condi~ctivity of AgCI : Cd (Bridgman).

different slopes of region 111 and IV type as well as

their transition regions are well discernible. The
measured curves could be satisfactorily reproduced
with one and the same sample. Different samples
with the same impurity concentration showed good
agreement in Arrhenius energies of region I, 11 and I11
(AE = 1 5
On the other hand the transition temperature between
region IT1 and IV and the Arrhenius energies of
region 1V showed great differences. There was no
relation to be found between the impurity concentration and the slope of region 1V.
The differences in slope of region IV between the
two types of crystals may be due to an enhanced
surface conductivity originating from the measuring
arrangement of the platelets. The transition region
occurs in 3 difl'erent types.

other authors. Our value for the intrinsic region is

in good accordance with that found by Miiller (31,
the values for the vacancy migration and the association agree well with those of Corish and Jacobs (51.
4.3 SOLUBILITY
LIMIT.
- Isotherrnes of the conductivity versus the Cadmium-ion concentration are
plotted in figure 5.

x).

1) A slow nlonotonous transition.

2) A n abrupt change.
3) A vague step-like change (Fig. 3, curve 3).

It is remarkable that sometimes a n effect occurs

in region 111 which is eminent for the interpretation
of region IV, illustrated i n figure 4, curve 4. The slopes
of the longer parts correspond to the usual slopes of
region 111, that is [he Arrhenius energy of the dipole
association region. The edges in the curve :ire interpreted to be spontaneous increments of the silver
vacancy concentration, which may be due to a sudden
solution process of a precipitated phase in the crystals
caused by heating. From t h i \ very I;lst running process

FIG.5. - lonlc conductivity isothermes of AgCl : Cd (platelets)

Alg ( u T )

' 0.15.

K. ZIEROLD, M . WENTZ A N D F. GRANZER

C9-418

It can be seen that the conductivity reaches a

saturation at relatively low concentrations. From
these saturation values the concentrations of the
free Silver vacancies xu depending on temperature
can be computed by eq. (1) to (3). The concentrations
of free vacancies and free Cd-ions must be equal
for electroneutrality. The total number of nonprecipitated Cd2+-ions ys is given by :

where a denotes the degree of association :

( x , = concentration of dipoles), K A ( T ) is tlie equilibrium constant of the reaction for the association
of dipoles :

(U, = activation energy for the association), y equals

the activity coefficient of the Debye-Hiickel-Theory
for long range ionic interaction [ l l ] :
Iny =

- z2 e2 X
2 &kT(1 + XR)

Using eq. (4) to (8) the solubility limit of Cd2'-ions

in AgCl as a function of temperature is shown in
figure 6. A solubility limit of 200 ppm was found at
room temperature, which is in good accordance
with observations of the turbidity limit in doped
AgCl : Cd crystals.
5. Discussion. - 5.1 PRELIMINARY
REMARKS.
The most striking effect of the conductivity measurements is the existence of tlie region IV below 240 K,
the tt p~.c'cil~itation
r ~ g i o nD. In this region the conductivity mechanism is assumed to be determined by
vacancies too. Therefore the changed slope in region 1V
can be explained in two different ways :

I ) Enhanced binding energy for vacancies by dipole

agglomeration.
2) A new mechanism dominates for the generation
of vacancies, because the ili~purity-vacancy-pairs
have disappeared by precipitation.
Independently of the detailed mechanism both
processes are controlled by diffusion. On the other
hand it is well known from diffusiori data in AgCl [I 81,
[I91 that the diffusion coefficients D of Cadmium-ions
and Silver vacancies are small at temperatures below
cm2/s, DCd2+ = 10-'a cm2/s.
240 K : Da =
The mean diffusion length 1 may be approximated by :

where X, the Debye-Hiickel screening constant, is

given in the case of AgCl by :
For T = 240 K and a diffusion time
resp. diffusion lengths are :
( E = dielectric constant, R = closest distance of interacting ions, V = volume per ion pair).

I,

<5

x lo4 cm,

100 s the

lCd2+ < 2 x 10-'cm

The diffusion length being extremely small, the precipitation from a homogeneous distribution of Cd2+-ions
turns out to be very improbable. These inhomogenities
may be due to
1) locally enhanced concentration of two or more
dipoles which then will form dimers or trimers ;
2) dipoles localized near the surface of precipitations.
In both cases only short diffusion lengths are needed,
and each of the two ways mentioned above may be
used to interprete tlie slope in region IV.
5 . 2 DIPOLEASSOCIATION MODEL.- The dipole
association mechanism is illustrated in figure 7 [13],
[14]. The association energies U D for dimers and U ,
for trimers were roughly calculated by a simple Coulomb interaction taking into account the dielectric
constant of AgCI.

260

2i0

300

3$0

340

3k0

3b0

400

FIG. 6. - Solubility curve of Cd2+ in AgCl ; calculated from

the measured saturation values.
Errnftit~l: On the top of the figure please read : Y S = X n -1- XA
instead of Y = X u
XA.

(zi =
I for Cd-ions ; zi = - 1 for vacancies ;
r i j = distance between charges i, j ; E = 12.5).

For an impurity-vacancy-dipole results the binding

energy U , = - 0.29 eV, for a dimer U D = - 0.75 eV

IONIC CONDUCTIVITY MEASUREMENTS OF HEAVILY DOPED AgCI : Cd CRYSTALS

(100)

impurity

C9-419

of AUD and AU, are very small. Therefore the measured high Arrhenius energies of region 1V cannot
be explained by the dipole association model.

5 . 3 SUPERSTRUCTURE
MODEL. - It is reasonable to
discuss a superstructure CdCl, . 6 AgCl with twice
the lattice constant of the host lattice (Fig. 8).

(100)

- vacancy - dipole

dimer

trimer

FIG.8.

FIG.7. - Dipole association model ; impurity-vacancy= impurity ion, n = vacancy,

dipole, dimer, trimer [13], [14]
= Ag-ion, - - CI-ion.

+-

and for trimer UT = - 1.18 eV. The effective binding

energies AUD or AUT respectively are the differences
between the energies U D or UT resp. and the sum of
the energies of the isolated dipoles.
AUD = U D - 2 UA = - 0.17 eV
AUT = UT - 3 U , = - 0.31 eV

Superstructure model of C d C l ~ p . 6AgCI, model

after Suzuki [15].

This superstructure was first found by Suzuki [I51

in NaC1 : Cd and also reported by Lilley and Newkirk [I61 for LiF : Mg. Preliminary interpretations
of small angle X-ray measurements confirm the
assumption to have such a superstructure in AgCI.
For the reason of simplicity the basis of the superstructure is considered to be composed of 4 Cd-ions
and 4 vacancies. The binding energy Us of this basis
is calculated by eq. (lo), furnishing :

(1 1)

Then the following equation system was used to

calculate x n ( T ) :

A vacancy dissociating from this basis leads to a

positively charged configuration with the binding
energy :
US-3

X* = K D ( T )=
xD

( x , , xT
Thence

exp -

$1

0.90 eV .

The difference energy U s - n - Us is the energy for

separating one vacancy from the superstructure :
(14)

concentration of dimers and trimers resp.).

The dissociation of a second vacancy once more

lowers the binding energy US-2D of the remaining
configuration and for the activation energy U 2 of
this vacancy follows :

In analogy dissolving a third and fourth vacancy

resp., the activation energies are given by :
The values of x n ( T ) obtained by this equation were
used to calculate the Arrhenius energy E I Vby eq. (1)
to (3). Using the following reasonable seeming parameters UIIl= 0.30 eV, U , = 0.29 eV, AU, = 0.17 eV.
AUT = 0.31 eV as a typical energy value is obtained :
E,,

0.52 e\'

It is seen by a variation of these paranletel-s that E,,,

is mainly determined by U , . while the contributions

By this simple consideration it is seen that the activation energies for taking off free vacancies from a
superstructure particle depends on the size and the
remaining charge of the precipitated state. By means
of this model i n comparison witti the dipole association model the measured high and different Arrhenius
2R

C9-420

K. ZIEROLD, M. WENTZ AND F. GRANZER

energies of region IV can be explained most favourably :

1) The high Arrhenius energies can be understood
as functions of averaged activation energies for
vacancies from the superstructure lattice.
2) The scattering range of the measured energies
from 0.61 eV to 1.8 eV may be due to superstructure
particles of different size and (( ionizatiorz degree D.

6. Conclusion. - Ionic conductivity measurements

in heavily doped AgCl : Cd crystals within a temperature range from 170 K to 470 K were carried out.
The solubility curve (Fig. 6) and the existence of
the region IV below 240 K indicate the presence of

precipitation. It was shown that the dipole association

model cannot explain the high Arrhenius energies
measured in region IV. But the superstructure model
of CdCl,. 6 AgCl satisfactorily describes all measured
results. An exact prove however for this kind of
precipitation cannot be obtained by ionic conductivity
itself; other measuring methods [I71 like ITC-measurements, X-ray experiments, and electron microscope investigations will be used for getting more
detailed information about the precipitation mechanism observed in AgCl : Cd.
Acknowledgement. - This work has been supported
by the Deutsche Forschungsgemeinschaft.

References
[I] KOCH, E. and WAGNER,
C., Z . P11ys. Cller?~ieB 38 (1937)
295.
121 EBERT,I. and TELTOW,J., A I I I I ~der
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P.,, P I I ~ sSrar.
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Sol. 12 (1965) 775.
[3] M ~ L L E R
[4] ABBINK,H. C. and MARTIN,
D. S., J. Phys. & Cl~c,r,~.
Solids
27 (1966) 205.
P. W. M., J . P11y.s. & Chern. Solids
[5] CORISH,J. and JACOBS,
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J. W., J. Photogr.
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Sci. 4 (1956) 1.
F. et al., Z. Angew. Plzys. 30 (1970) 316.
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[8] GRANZER,F., HENIG, G., SCHOTT,U., DARDAT,K.,
WENDNAGEL,
Th., HAASE.G., Z ~ ~ R G I E BF.,
E L , in :
(( 8th Int. Conference on Nuclear Photography and
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[lo] MATEJEC,R., Z. Phys. 148 (1957) 454.

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DISCUSSION

A. KESSLER.
- If your crystals were not in perfect
equilibrium, one could expect some hysteresis in the
data goinp up and down with temperature. Have
you observed something of this kind ?
K. ZIEROLD.
-Yes. By cooling from room temperature or any other temperature in region I11 the
conductivity is lower than by heating. The contrary
effect is observed by cooling (or quenching) from the
intrinsic region.

R. CAPELLETTI.
- Which is the heating rate during
the ionic conductivity measurements ?
If it is high you are actually measuring non-thermodynamical equilibrium situation and the activation
energy in region IV experimentally obtained is expected to be higher than the real one.
Generally the accomplishment of thermodynamical
equilibrium between simple defects and precipitated
phase requires long time, for instance in alkali halides
doped with divalent cation impurities.