International Journal of Engineering Sciences, 2(7) July 2013, Pages: 302-309

TI Journals

International Journal of Engineering Sciences

ISSN
2306-6474

www.tijournals.com

Dielectric and AC Conductivity Studies in

Alkali Doped Vanadophosphate Glasses
T. Sujatha 1, G.B. Devidas 2, T. Sankarappa *3, S.M. Hanagodimath 4
1,3,4
2

Department of Physics, Gulbarga University, Gulbarga , Karnataka, India.

Government First grade College, Aurad, Bidar (DT), Karnatka, India.

AR TIC LE INF O

AB STR AC T

Keywords:

Two series of vanadophosphate glasses doped with single and mixed alkali ions have been
investigated for dielectric properties and ac conductivity over a wide temperature range and in the
frequency range 10Hz to 1kHz. Conductivity increased with temperature and alkali content (second
alkali content in mixed alkali glasses) and, decreased with increase in frequency. High temperature
activation energy for ac conduction of all the glasses has been determined by employing Motts
small polaron hopping model. Frequency exponent values for ac conductivity have been
determined for both the series of glasses. Dielectric constant and dielectric loss were decreased
with increase of frequency and increased with increase of temperature. The variations of
conductivity and dielectric properties with temperature, frequency and composition are discussed.
It is for the first time that the mixed conducting glasses studied here have been investigated for
dielectric properties and conductivity.

Glasses
Transition metal ions Dielectric constant
AC conductivity
PACS:
61.43.Fs; 72.60.+g; 84.37.+g

2013 Int. j. eng. sci. All rights reserved for TI Journals.

1.

Introduction

Glasses containing transition metal ions (TMI), such as V, Mo, W, etc., are known to be electronically semiconducting [1-4]. Conduction in
these glasses is explained by the phonon assisted hopping of electrons (small polaron hopping) between the low and high valence states of
TMI for example, between V 4+ and V5+states in vanadium glasses and Fe2+ and Fe3+ in iron based glasses [5]. Electron hopping in
vanadophophate glasses depends on the distance between the V 4+ ions and V5+ ions and their concentration. Phosphate glasses have got
many applications in optics and other areas and they are easy to prepare because of their low melting and glass transition temperatures [67]. Phosphate glasses are being used as host materials for lasers, optical filters, and reference electrodes and also to store nuclear wastes.
Pure phosphate glasses are highly hygroscopic and as a result very limited studies are conducted on them. However, alkali oxide modified
phosphate glasses are quite stable and durable. In phospomolbdate and phosphotungstate glasses [8] activation energies for dc conduction
were found to be dependent on temperature and it has lead to a conclusion that conductivity is thermally activated process and variablerange hopping mechanisms were operated in different temperature regimes. Electrical conductivity was found to increase with iron content
in iron phosphate glasses [2]. The cesium iron phosphate glasses have been examined for dc conductivity and observed that conductivity
was due to electronic motion between the iron ions and ionic conduction was immeasurably small [9]. The dc conductivity of mixed alkali
iron phosphate glasses has been observed to be independent of Na/K ratio [10] up to a total of 20% alkali content. This means that no ionic
contribution to total conductivity was detected in these glasses. Ternary vanadium phosphate glasses of the type, (V 2O5)0.3-(P2O5)0.6(MO) 0.1, where MO=TeO2, GeO2 and B2O3 were investigated for ac conductivity and dielectric properties [11]. It was mentioned that at low
temperatures the conductivity follows variable range hopping mechanism and at high temperature Motts model of polaronic hopping
theory is obeyed. The conductivity of glasses in (V2O 5)0.5-(P2O5)0.5-x-(A2O)x where A=Li, Na, K, Rb have been investigated [12] as a
function of frequency at a fixed temperature, over the range x=0.1 to 0.4. In zinc vanadophosphate glasses [13], electrical conductivity was
observed to be remarkably dependent on the concentration of zinc concentration. Structural investigations on binary alkaline earth vanadate
glasses [14] revealed that the increase in alkaline earth content reduces the total V-O coordination number and V-V distance significantly.
In general, in single alkali transition metal phosphate glasses, different processes contribute to the electrical conduction at different
temperatures. For example, ionic conduction is because of the motion of alkali ion and as a consequence, the electrical conductivity is
expected to increase proportional to the concentration of alkali ions. The electronic conduction is due to small polaron hopping between
transition metal ions. When the second alkali was introduced into glasses they have exhibited remarkably lower conductivities and the
conductivity passed through deep minimum. This is called mixed alkali effect (MAE). The MAE in different physical properties are
observed in silicate, borate, germanate and telluride glasses [15]. To our knowledge, it appears that there have been not many efforts made
to investigate single and mixed alkali effects on ac conductivity of vanadophosphate glasses. However, elsewhere [16] we have reported dc
conductivity studies for these glasses. Since in alkali doped vanadophosphate glasses electrical conduction can be due to both ions and
electrons, it is interesting to investigate single and mixed alkali effects on conductivity of these glass systems.

* Corresponding author.
Email address: sankarappa@rediffmail.com

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Internat ional Jour nal of Engineeri ng Science s, 2(7) July 2013

In this communication, we report ac conductivity studies on Series (i): (V2O5) 0.3 (P2O5)0.7-x (Na2O)x ; (x=0.1, 0.125, 0.15, 0.2) labeled as
SA1, SA2, SA3 and SA5. Series (ii): (V2O5)0.3 (P2O 5)0.5 (Na2O)0.2-x (K2O)x; (x = 0.04, 0.12) labeled as MA1 and MA3. These systems have
not been investigated previously for ac conductivity and dielectric properties.

2.

Methodology

Appropriate amounts of analytical grade vanadium pentoxide (V 2O5), ammonium dihydrogen orthophosphate (NH4H2PO4), sodium
carbonate (Na2CO3) and potassium carbonate (K2CO 3) were thoroughly mixed in a porcelain crucible and heated up to melting in a muffle
furnace. The melt was then quickly quenched to room temperature. To remove strains present in samples, if any, they were annealed for an
hour at 400 0C. Powder X-ray diffraction studies were performed and the spectra did not show any sharp peaks indicating that the samples
were non-crystalline in nature.
The frequency dependence of capacitance, C, and the dissipation factor, tan, were measured at five different frequencies; 10Hz, 50Hz,
100Hz, 500Hz and 1kHz in a computer controlled HP Impedance Analyzer (4192A LF) in the temperature range 300K to 500K.
Using the measured values of C, tan and dimensions of the samples the dielectric constant,
conductivity,

dielectric loss factor,

ac , were determined as per the following expressions:

Cd
0 A

(1)

tan

(2)

ac 0

(3)

where,

and ac

0 is the permitivity of free space, d is the thickness of the sample, A is cross sectional area of the sample and 2 f

with f

being applied frequency.

3.

Results and discussion

3.1. Conductivity
3.2 Series (i)
The ac conductivity of these glasses was found to be in the range of 10-6 to 10-8 ohm-1m-1. The data was looked at closely and found that ac
conductivity at all the studied frequencies increased with increase in temperature and Na 2O content. The former indicate the conduction
process to be thermally activated and of semiconductor type. From the later observation, it can be inferred that the total conductivity at all
the frequencies is due to both polarons and Na+ ions and, the conductivity increases proportionately with alkali ions. The conductivity (at
450K and 500Hz) versus mole fraction of Na2O is shown in Fig.1. From the figure, it can be seen that conductivity increases with Na2O
content indicating that there is ionic contribution to the total conductivity in addition to electronic.
Since the variation of conductivity was observed to be thermally activated process and is due to the hopping of polarons [17], the
temperature dependence of conductivity has been considered in the light of Motts small polaron hopping mode. Based on diffusion model,
Mott [18] has discussed the conduction process in terms of hopping electrons between localized states and proposed an expression for the
electrical conductivity in semiconducting glasses:

0 e2C (1 C )
exp(2 R) exp(W / k BT )
k BTR

where,

(4)

0 is the characteristic phonon frequency, is the rate of wave function decay, C is the ration of ion concentration in low valence

state to total concentration of transition metal ions, R is the average hopping distance, W is the activation energy, e is the electronic charge,
kB is the Boltzmann constant and T is the absolute temperature.

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-14.0

-14.2

-14.4

ln()(ohm m)

-1

-14.6

-14.8

-15.0

-15.2

-15.4

-15.6

-15.8
0.10

0.12

0.14

0.16

0.18

0.20

Mole fraction of Na2O

Figure 1. A plot of ln() versus mole fraction of Na2O at temperature,

450K and frequency of 500Hz for series (iii) glasses.

Eq.(4) describes a non-adiabatic regime of small polaron hopping and is usually used to analyze the electrical conductivity of glasses
coantaining transition metal ions. The non-adiabatic term 0exp(-2R) describes the probability of an electron tunneling from the potential
well. Eq.(4) can also be written in the Arrhenius form:

( T ) 0 exp( Eac / k BT )

(5)

or

ln( T ) ln( 0 ) ( Eac / k BT )

(6)

where, 0 is the pre-exponential factor in Eq.(4) and Eac is the activation energy.
The plots of ln(T) versus (1/T) were made for these glasses as Motts expression for small polaron conduction (Eq.6) and shown in Fig. 2.
The least square linear fits were performed on high temperature data and the slopes of these lines gave activation energies in the range
0.45eV to 0.90eV. The activation energies were found to be deceased with frequency and increased with Na2O content, which is in
agreement with the reported results on similar systems [19-21]. Activation energy as a function of Na2O content at a frequency of 500Hz is
plotted in Fig.3.
The increase of activation energy with increase of alkali content is expected because the high temperature activation energies represent
predominantly the polaron conduction and increases with alkali content as, addition of alkali ions to the glass net work add to more
scattering of polarons. Further, it is possible that addition of alkali content increases the average hopping distance between the two
localized hopping sites of vanadium, V4+ and V5+ and thereby the electronic contribution to the total conductivity decreases. Similar results
were obtained in case of dc conductivity studies of the same systems [16].
Further, it is observed that the total conductivity decreased with increase in frequency. This may be due to the fact that as the frequency is
increased ionic movements will come down and thereby the total conductivity, which is the sum of electronic and ionic conductivities, will
decrease. Also, the decrease in Eac with increase in frequency hints at the process of polaronic conduction increasingly getting activated
with frequency though the conduction due to alkali ions can be expected to behave oppositely. The nature of variation of Eac with frequency
agrees with [22,16].

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Internat ional Jour nal of Engineeri ng Science s, 2(7) July 2013

10Hz
50Hz
500Hz

10Hz
SA1
-12

SA2

50Hz
100Hz

-12

500Hz
1kHz

100Hz

-1

-1

ln(T)(ohm m )

-1

-1

ln(T)(ohm m )

1kHz

-15

-14

-18
-16
1.8

2.1

2.4
-1

10Hz

2.7

2.1

-3

2.2

2.3
-1

(1/T)(K )x10

(1/T) (K )x10

-3

2.4

2.5

50Hz
-12

SA3
-14

SA5

10Hz

500Hz

-1

-1

-1

ln(T)(ohm m )

-16

-1

ln(T)(ohm m )

100Hz

500Hz
-18

50Hz
100Hz
-15

1kHz

-18
-20

2.0

2.2

2.4

2.6

2.8
-1

3.0
3

(1/T)(K )x10

3.2

3.4

2.2

2.4

2.6
-1

-3

(1/T)(K )x10

Figure 2. The plots of ln(T) versus (1/T) for series (iii) glasses. Solid lines are the least square linear fits to the high temperature data.

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0.90

SA series

0.85

Eac(eV)

0.80

0.75

0.70

0.65

0.60

0.10

0.12

0.14

0.16

0.18

0.20

Mole fraction of Na2O

Figure 3. Activation energy, Eac versus mole fraction of Na2 O for

series (i) glasses at frequency of 500Hz.

The frequency exponent, s, values were determined by plotting ln() versus ln() for all the systems. The s values thus obtained were
0.2090.03, 0.1010.01, 0.4770.05 and 0.2620.03 for SA1, SA2, SA3 and SA5 respectively. A typical plot of ln() versus ln() for SA1
s

is shown in Fig.4. It can be noted from the figure that the relation ( ) A is very much valid for these systems even in the limited
frequency range considered. The slope of the fit linear line is negative. This should not be taken to read the frequency exponent to be
negative. More over, the negative slope of the line indicates that the ac conductivity decreases with increase of frequency. From the s values
obtained for these series of glasses, it is clear that no definite relation between the s value and composition can be established. Similar plots
were obtained for the remaining samples in this series
-14.6

SA1 at 450K

-14.8

-15.0

ln()

-15.2

-15.4

-15.6

-15.8

ln()

Figure 4. A plot of ln() versus ln() for SA1. Solid line is a least square
fit linear line through the data.

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3.3 Series (ii)

The ac conductivity of series (iv) glasses was found to be in the range of 10 -6 to 10-7 ohm-1m-1. The plots of ln(T) versus (1/T) are shown
in Fig.5. From the figure, it can be seen that conductivity (i) increases with temperature, (ii) decreases with frequency and (iii) increases
with second alkali content. The activation energies estimated from the slopes of the linear fits to the high temperature data were in the range
of 0.4eV to 0.6eV for the frequency range considered.
The increase in conductivity and decrease in activation energy with second alkali content, K 2O indicate that the composition of the present
glasses falls beyond the composition corresponding to conductivity minimum, if the mixed alkali effect (MAE) is a property of these
systems [16,23]. The decrease in conductivity with increase in frequency can be attributed to decrease in the ionic contribution for higher
frequencies. The values of frequency exponent, s at 450K obtained were 0.860.11 and 0.640.09 for MA1 and MA3 respectively.

100Hz
50Hz
10Hz

-10

MA3

-12

100Hz
500Hz

-12

MA1
10Hz

-14

-1

-1

-1

ln(T)(ohm m )

50Hz

-1

ln(T)(ohm m )

-14

-16

-18

-16

-18

500Hz
1kHz

1kHz
-20

-20

2.0

2.2

2.4

2.6

2.8

3.0

3.2

3.4

2.0

2.2

-1

2.4

2.6

2.8

3.0

3.2

3.4

-1

(1/T)(K )

(1/T)(K )

Figure 5. The plots of ln(T) versus (1/T) for series (ii) series of glasses. The solid lines
Are the least square linear fits to the high temperature data..

3.4 Dielectric properties

The study of dielectric properties of semiconducting glasses acquired enormous importance due to rapid expansion of solid-state
electronics. Of all, dielectric constant, , and dielectric loss factor, tan, are the most important properties which decides the applications
of the glasses [24]. The dielectric constant and dielectric loss factor were determined at the frequencies operated in the present experiments.
The values were found to be in the range of, 102 to 103 and 101 to 103 for series (i) and (ii) respectively. The values were found to
be in the range of 107 to 108 and 106 to 107 for series (i) and (ii) glasses respectively. The following are the remarkable observations made
in the variations of and with the variables used in the experiments such as frequency, temperature and composition.
(i).

and

(ii).

and

(iii).
(iv).

have been decreased with the increase of frequency.

have been increased with the increase of temperature.

and were negligibly small below the temperature 400K.

and become negligibly small for frequencies above 500Hz in both

the series of glasses.

The typical plots of

and

versus temperature at different frequencies, for one sample from each series of the glasses investigated are

shown in Fig. 6. Similar variations of

observed.

and

with temperature and frequency in the case of other samples in each series were

At temperatures above 400K, in both the series of glasses, both and show strong temperature dependence and frequency
dispersion. This kind of temperature dependence is typical of polar dielectrics in which the orientation dipoles are facilitated with increase
of temperature, which results in the increase of dielectric constant. At low temperature, the contributions of electronic and ionic

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Inter nat ional Journal of Engineer ing Sci ences, 2(7) July 2013

components are small while the orientational component can be neglected. With increase in temperature, both electronic and ionic
contributions increase in addition to dipolar polarizability [25].

3000

1.6x10

10Hz

10Hz

SA1

SA1

1.4x10

2500
4

1.2x10
2000

Dielectric loss, "

Dielectric constant, '

1.0x10

1500

1000

8.0x10

6.0x10

4.0x10

50Hz

500
3

2.0x10
50Hz
100Hz
500Hz

350

400

450

500

500Hz
1kGz

0.0

1kHz
300

100Hz

550

300

350

T(K)

400

450

500

550

T(K)

2500

10000

10Hz

8000

1500

6000

1000

50Hz

4000

50Hz
2000

500

100Hz
500Hz 0
1kHz

300

Dielectric loss, "

'

Dielectric constant,

MA1

10Hz

MA1
2000

350

400

450

T(K)

Figure 6. Plots of dielectric constant,

and dielectric loss factor,

500

300

100Hz
500Hz
1kHz
350

400

450

500

T(K)

as a function of temperature for different frequencies for SA1 and MA1 glasses.

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Internat ional Jour nal of Engineeri ng Science s, 2(7) July 2013

It can be specially noted that the increase in and with temperature above 350K is rapid, which may not be completely due to
electronic, ionic and dipolar polarizabilities but could be partly due to enhanced electrode polarization as the temperature raised. Similar
observations were made and conclusions were arrived in other glasses [26,27].
Dielectric constant, increases with decrease of frequency or it decreases with increase of frequency and this may be explained as follows.
When the frequency is increased the dipoles (or ions) are no longer able to rotate sufficiently rapidly so that their oscillations begin to lag
behind those of the field and hence the observed decrease in dielectric constant with increase of frequency. As the frequency becomes
higher and higher, the ionic and orientation polarizations will decrease continuously and finally disappears because of the inertia of the
molecules or ions. Dielectric loss at high frequency is much lower than that occurring at low frequencies. This kind of frequency
dependence of dielectric loss is always attributed to be associated with losses by conduction. The frequency dependence of dielectric loss is
very similar to that of dielectric constant but differs in values and agrees with observations made in [16,21,22].

4.

Conclusion

Two series of single and mixed alkali doped vanadophosphate glases were prepared by melt quenching method and their non-crystallinity
has been confirmed by XRD studies.
The dielectric properties and ac conductivity were investigated over wide range of temperature and at five different frequencies below
1kHz. Conductivity increased with temperature and alkali content (second alkali content in mixed alkali glasses) and, decreased with
increase in frequency. High temperature activation energy for ac conduction of all the glasses has been determined by employing Motts
small polaron hopping model. Frequency exponent values for ac conductivity have been determined for both the series of glasses. Dielectric
constant and dielectric loss were decreased with frequency and increased with increase of temperature. The variations conductivity and
dielectric properties with temperature, frequency and composition have been thoroughly discussed in terms of polaron hopping distance and
polarization components such as electronic and ionic.
It is for the first time that the mixed conducting glasses studied here have been investigated for dielectric properties and conductivity.

Acknowledgements
One of the authors, T.Sankarappa acknowledges the rigorous research training that he received from Professor Mike Springford and
Dr.P.J.Meeson at H. H. Wills Physics Laboratory, University of Bristol, UK.

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