Chemical Physics Letters 424 (2006) 295–299

www.elsevier.com/locate/cplett

Relaxation of silver ions in superionic borate glasses

S. Bhattacharya, A. Ghosh *

Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, West Bengal, India

Received 11 April 2006; in final form 20 April 2006

Available online 29 April 2006

Abstract

We have investigated the conductivity spectra at different temperatures for the AgI doped silver borate superionic glasses and esti-
mated the concentration of mobile Ag+ ions as a function of temperature and composition. It is observed that the concentration of
mobile Ag+ ions is independent of temperature and only a fraction of the total Ag+ ions in these glasses participate in the diffusion pro-
cess. The increase in conductivity due to the insertion of AgI can be attributed to the increase in hopping rate of Ag+ ions which is sup-
ported by FT-IR results.
Ó 2006 Elsevier B.V. All rights reserved.

1. Introduction
The understanding of ion diffusion process in superionic
glasses is of both practical and academic interest [1–4].
These materials are currently under investigation for tech-
nical application as solid electrolytes in electrochemical
devices such as batteries, sensors, electrochromic displays,
etc. due to their high ionic conductivity, high stability
and large available composition ranges. It is also interest-
ing in the academic level to understand the nature of ion
diffusion in these materials.
A particularly interesting class of fast-ion conductors is
the AgI-doped silver borate glasses which can accommo-
date a high content of AgI in a disordered phase without
any evidence of crystallization [1,2]. The best conducting
glasses may reach conductivity up to 102 S/cm at room
temperature [2]. The role of Ag2O seems to be quite differ-
ent from other modifying cations, because the local coordi-
nation is characterized by an unusually low coordination
number and a short distance, as shown by EXAFS mea-
surements [5]. Much attention has been focused on how
AgI is introduced into the glassy borate network. Mainly
two models have been proposed: first suggests that AgI is
coordinated with the BO4 units and thus is homogenously
*
Corresponding author. Fax: +91 33 2473 2805.
E-mail address: sspag@iacs.res.in (A. Ghosh).
dispersed in the host Ag2O–2B2O3 network [6] and the sec-
ond proposes that AgI forms small clusters or microdo-
mains of an ‘amorphous-like’ AgI with tetrahedral
coordination to that of crystalline superionic a-AgI [7].
Raman spectroscopy result [8] suggests existence of such
a-AgI domains, especially at higher AgI concentrations
although (EXAFS) [9], 109Ag NMR [10] and X-ray diffrac-
tion [11] support absence of an ordered AgI phase resem-
bling a-AgI. In the microdomain model, the Ag+ cations
exist in two coordination environments, one related to
the iodide anion and the other with oxygen ions (bridging
or non-bridging oxygens) [6]. In the latter model, the Ag+
cations share a common coordination with iodide anions
and oxygen atoms [5]. Recently X-ray and neutron-diffrac-
tion data of silver borate glasses have been used [12] for
structural modelling for fast ion conducting glass systems
using the reverse Monte Carlo method [13] which predicts
that most of the Ag+ ions are coordinated to both I ions
and BO4 units in the network [12]. It is concluded that,
while the short-range order of the borate network is unaf-
fected by AgI doping, by increasing the amount of AgI
content improves the medium-range order of the glass by
inducing ordering between the neighboring boron–oxygen
chain segments. It is therefore proposed that the improve-
ment of medium-range order in glass can be connected with
the network expansion and the creation of new pathways
for ion transport [13].

0009-2614/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2006.04.077
296 S. Bhattacharya, A. Ghosh / Chemical Physics Letters 424 (2006) 295–299

However, despite many experimental and theoretical
efforts [1–3,12,13] the mechanism of Ag+ ion dynamics in
AgI doped borate glasses is partly understood yet due to
the difficulty in separating the contribution of the ion con-
centration and the mobility from the measured conductiv-
ity. There is no general agreement about the fraction of
Ag+ ions participating in the dynamic process, which is
one of the most critical parameters to explore the transport
mechanism of the presently studied system.
Conductivity spectroscopy is a well established method
for characterizing the hopping dynamics of the ions. A
variety of different materials have been studied using this
technique. It is well documented in the literature [14,15]
that in the usual experimental frequency window and tem-
perature range, the overall frequency response of the real
part of the conductivity can be described by
n
r0 ðxÞ ¼ rdc ½1 þ ðx=xc Þ ; 06n<1
which is the sum of a constant dc conductivity, rdc and a
fractional power law dependence with an exponent n. xc
is a characteristic crossover frequency from dc to dispersive
conductivity. Both the dc conductivity and the crossover
frequency, above which r 0 (x) µ xn, are thermally acti-
vated. However, there is another contribution to the dis-
persive conductivity, which consists of a nearly frequency
independent dielectric loss and corresponds to an almost
linear frequency dependent term of the form r 0 (x) = Ax
for the real part of the complex conductivity. At sufficiently
(Magna IR-750, Series II) at 25 °C and at relative humidity
of 50–60%. For FT-IR measurements, pellets of thickness
1 mm and diameter 13 mm were obtained by pressing a
mixture of 1 part of glass and 60 parts of KBr at a pressure
of 200 kg/cm2. The electrical measurements such as capac-
itance and conductance of the samples were carried out on
gold coated samples of diameter 1 cm in the frequency
range 10 Hz to 2 MHz using a RLC meter (QuadTech,
model 7600)and in the temperature range 93–393 K.
3. Results and discussion
The frequency dependence of the conductivity at differ-
ent temperatures for a typical glass composition is shown
in Fig. 1a. At low frequencies the conductivity is indepen-
dent of the frequency corresponding to the dc conductivity.
ð1Þ The frequency dispersion starts at a higher frequency as the
temperature is increased. The dispersive portion is first
analyzed by subtracting the dc conductivity from the mea-
sured conductivity as shown in Fig. 1b. It is noted that in
-5
1x10
-6
10
σ' (ω) (Ω-1 cm-1)

low temperatures or high frequencies, the Ax term domi- 10

-7
T=153K
nates over the power law dependence of the conductivity T=158K
T=163K
given by Eq. (1) [16]. T=173K
T=183K
In this Letter, we have investigated the conductivity 10
-8
T=193K
T=203K
spectra for AgI doped silver diborate glasses at different T=213K
temperatures and estimated Ag+ ions participating in the T=223K

-9 (a)
transport process. We have shown that the increase in the 10
conductivity due to the AgI doping is not due to the 3
10 10
5 7
10
increase in the number of mobile Ag+ ions, but is due to ω [rad s-1]
the increase in the mobility of Ag+ ions. The results are
clarified also by the analysis of the FT-IR absorption spec-
tra of the glasses.
-6
10
(σ' (ω)-σdc) (Ω-1 cm-1)

2. Experimental

Glass samples of compositions xAgI  (1  x)(Ag2O– -7

10 T=153K
2B2O3), where x = 0–0.5 were prepared in two steps. First, T=158K
T=163K
Ag2O–2B2O3 base glass was obtained by melting AgNO3 T=173K
T=183K
and H3BO3 at 750 °C for 6 h in a platinum crucible and -8 T=193K
10 T=203K
then quenching the melt in an aluminum mould. In the sec- T=213K
T=223K
ond step, appropriate amounts of AgI and the base glass
(b)
were mixed, melted in platinum crucible at 750 °C for -9
10
30 min and poured in an aluminum mould to get final glass 4
10
5
10 10
6
10
7

samples. Glass samples of thickness 0.1 cm were obtained ω [rad s ]

-1

for x = 0–0.5. Glass formation was confirmed from X-ray

diffraction. The density of the samples was measured using
Archimedes’ principle with acetone as an immersion liquid.
The FT-IR spectra of the bulk glass samples in absorption
mode were recorded in a Nicolet FT-IR spectrophotometer
Fig. 1. (a) Conductivity spectra for the 0.2AgI  0.8(Ag2O–2B2O3) glass
composition at different temperatures shown in the inset. The solid lines
are best fits to Eq. (1). (b) Variation of the dispersive conductivity
(r 0 (x)  rdc) with frequency for the same glass composition and temper-
atures as in (a).
 S. Bhattacharya, A. Ghosh / Chemical Physics Letters 424 (2006) 295–299 297

the frequency window the slopes give power law exponent x = 0.0
(0.65) which is much less than unity and independent of 7 x = 0.1
temperature. Thus, the nearly constant loss region is absent x = 0.2
x = 0.3
in the investigated frequency window and the temperature 6 x = 0.4

log10 [ωh (rads-1)]

range, and the data can be described by the power law x = 0.5
model (Eq. (1)). The conductivity spectra for all composi- 5
tions were then fitted to Eq. (1). We have replaced rdc in
Eq. (1) by the following expression for rdc given by the 4
Nernst–Einstein relation
rdc ¼ q2 d 2 nc xh =12pkT ; ð2Þ 3

where nc and d is the mobile ion concentration and the 2

jump distance, respectively. It has been pointed out [17] (a)
that short range displacements of the ions at higher fre- 3 4 5 6 7 8 9
quencies are thought to be coupled to the ionic environ- -1
1000 / T (K )
ment. Interionic interactions become important, and the
short range hopping is often viewed as the highly correlated
motion in which the ions perform several reiterated for- 10
ward–backward hops before completing any successful for-
ward displacement [17,18]. The power law dispersion (Eq. 9
(1)) is thus a consequence of this reiterated hopping and oc-

log10 [ωh (rads-1)]

curs down to the crossover frequency xc below which suc-
cessful hops can be completed [17]. Thus in the present
approach it can be tacitly assumed [17–19] that the cross-
over frequency, xc in Eq. (1) is close to the hopping fre-
quency of the mobile Ag+ ions, presented as xh in Eq.
(2). Recent NMR and conductivity experiments of some
crystals and AgI-doped fast ion conducting glasses [20–
22] have indicated that xc is slightly longer than xh, which
does not change the values of nc drastically, justifying our
assumption for the present AgI-doped glasses. Three
parameters nc, xh and n were obtained at different temper-
atures for all glass compositions. We have taken the jump
distance as the nearest Ag–Ag distance for these glasses ob-
tained from structural studies [12].
We note that the values of power law exponent n are
almost independent to AgI content within experimental
errors. The temperature dependency of xh is shown in
Fig. 2a. Fig. 2b shows the variation of the hopping rate
xh of mobile Ag+ ions at room temperature as function
AgI content. It is observed that the hopping rate increases
linearly with the increase of AgI content in the host glass
network. From Fig. 2a it is noteworthy that xh shows
Arrhenius behavior with activation energy (Eh) very close
to the activation energy (Er) for the dc conductivity rdc
(Fig. 3). The Arrhenius temperature dependence of nc is
shown in Fig. 4a, which indicates that nc is almost indepen-
dent of temperature. The variation of the estimated mobile
ion concentration nc with AgI content in the compositions
is shown in Fig. 4b. The variation of the total Ag+ ion con-
centration is also shown in the same figure. It is clear in the
figure that the mobile Ag+ ion concentration obtained
from the analysis is much less than the total Ag+ ion con-
centration. Thus, a fraction of the Ag+ ions are mobile and
are weakly dependent on composition.
It is worthy to mention here that the NMR experiments
of AgI doped borate glasses [23] have also demonstrated
8
7
6
(b)
5
0.0 0.1 0.2 0.3 0.4 0.5
x
Fig. 2. (a) Arrhenius plots of the hopping frequency of xAgI  (1  x)-
(Ag2O–2B2O3) glasses, obtained from the best fits of conductivity spectra,
for different values of x, to Eq. (1). The solid lines are the least-square
straight line fits of the data. (b) Compositional variation of the hopping
frequency of mobile ions xh at room temperature (298 K).
that a fraction of Ag+ ions participate in the dynamic pro-
cess. In Fig. 4b, we have also included the mobile ion con-
centration obtained from NMR experiments [23]. We note
that the fraction of mobile ions obtained from the present
analysis are comparable with those reported from NMR
experiments [23].
The FT-IR absorbance spectra of AgI doped and
undoped silver diborate glasses is shown in Fig. 5a in the
frequency range 500–1550 cm1. Strong band envelopes
centered at 1350 and 1000 cm1 are observed in all glass
compositions. These features are attributed to the asymmet-
ric stretching of B–O bonds in borate triangles BO3 and
BO2O (1350 cm1) and in tetrahedral units, BO 4
(1000 cm1), respectively [24,25]. The remaining band enve-
lopes centered at 700 cm1 arise from the deformation
modes of borate network structures [7]. All the spectra in
Fig. 5a present quite similar band shapes, indicating that
AgI addition does not cause the formation of new structural
units in the borate network, although the AgI content are
varied in a rather broad range, 0 6 x 6 0.5. However, it is
298 S. Bhattacharya, A. Ghosh / Chemical Physics Letters 424 (2006) 295–299

x=0.0
0 x=0.1
x=0.2
log10 [σdc T (Ω-1 cm-1 K)]

x=0.3 x=0.5
x=0.4
-2 x=0.5

arb. units
x=0.4

x=0.3
-4
x=0.2

x=0.1

-6 x=0.0
(a)

600 900 1200 1500

-8 Wavenumbers (cm ) -1
2 3 4 5 6 7 8 9
-1
1000 / T (K )
Fig. 3. Arrhenius plots of dc conductivity obtained from complex
impedance plots of xAgI  (1  x)(Ag2O–2B2O3) glasses, for different 1.2
values of x. The solid lines are the least-square straight line fits of the
data.

A4/A3
0.9

(b)
0.6
10
22 0.0 0.1 0.2 0.3 0.4 0.5
x
nc (cm -3)

x = 0.0
Fig. 5. (a) FT-IR absorption spectra for xAgI  (1  x)(Ag2O–2B2O3)
21 x = 0.1 glasses for different values of x. (b) Relative absorption A4/A3 as a
10 x = 0.2 function of AgI content in xAgI  (1  x)(Ag2O–2B2O3).
x = 0.3
x = 0.4
x = 0.5
(a)
observed that AgI addition induces a change in the relative
20
10
3 4 5 6 7 8 intensities of the envelopes at 1350 and 1000 cm1. The nar-
-1
1000/T ( K ) rowing of the 1350 cm1 envelope indicates the occurrence
of AgI-induced structural rearrangements in these glasses.
The integrated absorption of the characteristic band
envelopes between 780 and 1180 cm1 (A4) and between
1180 and 1570 cm1 (A3) was calculated to probe the rela-
10
22
tive population of borate tetrahedra (BO 4 ) and triangles
[Ag ] (cm- 3)

(BO3 and B2O), respectively, in the glasses. The A4/A3

ratio presented in Fig. 5b demonstrates a strong depen-
+

dence on the AgI doping into the host network. It is note-

worthy from Fig. 2b that hopping rate xh also varies in the
same manner with AgI content. Since addition of AgI to
(b) Ag2O–2B2O3 glass is not expected to change the total for-
21
10 mal negative charge on the borate network, the dependence
0.0 0.2 0.4 0.6 0.8 1.0
of the A4/A3 ratio on AgI content can be understood in
x term of changes in the population of borate species. This
Fig. 4. (a) Arrhenius plots of the mobile Ag+ ion concentration obtained can be expressed by the following chemical equilibrium
from the analysis of the conductivity spectra of xAgI  (1  x)(Ag2O– [26] that takes place in the melt and involves the isomeric
2B2O3) glasses, for different values of x. (b) Variation of Ag+ ion B2O and BO 4 species
concentration with composition for xAgI  (1  x)(Ag2O–2B2O3) glasses:
(h) total Ag+ ion concentration obtained from the composition and BO
4  B2 O

ð3Þ
density; (e) mobile Ag+ ion concentration nc obtained from the analysis
of the conductivity spectra; ($) mobile Ag+ ion concentration obtained The data presented in Fig. 5b indicate that when the AgI
from NMR experiments [23]. content is increased the above equilibrium shifts progres-
 S. Bhattacharya, A. Ghosh / Chemical Physics Letters 424 (2006) 295–299
sively to the left. Thus the Ag+ ions coordinate with both
I ion and BO 4 units with the insertion of AgI into the
host glass network. The host glass network expands consid-
erably to accumulate the dopant ions [12,13] and changes
of the intermediate structure are indicated. This expansion
enhances the hopping rate of mobile Ag+ ions as shown in
Fig. 2b and hence increases the ionic conductivity.
4. Conclusions
We have studied the dynamics of Ag+ ions in superionic
silver borate glasses by conductivity spectroscopy and esti-
mated the mobile Ag+ ions participating in the transport
process. We have observed that the mobile Ag+ ion con-
centration is less than the total Ag+ ions estimated from
glass compositions and density and is independent of AgI
doping. Thus AgI insertion into the host network primarily
enhances the mobility, i.e. the hopping rate of mobile Ag+
ions by the improvement of the medium-range order of the
glass as observed from the analysis of FT-IR absorption
spectra.
Acknowledgements
The work is supported partly by the Department of Sci-
ence and Technology (via Grant No. SP/S2/M43/99) and
partly by Department of Atomic Energy (via Grant No.
2002/37/32/BRNS), Government of India.
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