Electrical Conductivity and Dielectric Properties of Some Vanadium-Strontium-Iron Unconventional Oxide Glasses
Electrical Conductivity and Dielectric Properties of Some Vanadium-Strontium-Iron Unconventional Oxide Glasses
Electrical Conductivity and Dielectric Properties of Some Vanadium-Strontium-Iron Unconventional Oxide Glasses
Review
Received 4 February 2006; received in revised form 2 July 2006; accepted 23 July 2006
Abstract
An unconventional oxide glass system of the composition (80 − x)%V2 O5 ·x%SrO·20%FeO (0 ≤ x ≤ 40) was prepared by the press-quenching
technique. The electrical conductivity (σ dc and σ ac ) was measured in the temperature range from 308 to 588 K. σ dc was found to follow a mixed
conduction of both small polaron hopping (SPH) and variable range hopping (VRH) mechanisms up to 418 K. Above this temperature σ dc follows
SPH conduction mechanism only. σ ac was determined at four frequencies (102 , 103 , 104 , 105 Hz). It was found that the correlated barrier hopping
(CBH) was the applicable mechanism, and the exponent factor (s) varied from 0.1 to 0.83. The theoretical fitting between the proposed models
and the experimental data showed good agreement. σ dc and σ ac were found to decrease with the increase of SrO content, and both the dielectric
constant ε and loss ε were found to increase with temperature and decrease with the frequency.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Unconventional oxide glasses; Iron–vanadate glasses; Electrical and dielectric properties
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Experimental details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Electrical conductivity measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1. dc Conductivity and activation energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.2. Relation between the activation energy and the mean V-ion spacing (R) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Oxygen anions density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.4. ac Conductivity and dielectric properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1. Introduction their important application [1–6]. Such glasses exhibit also many
interesting physical properties such as switching phenomenon,
Oxide glasses containing transition metal ions (TMI) are of electrochromic properties, etc. [7–12].
special interest because of their semiconducting behavior and In glasses containing vanadium both V4+ and V5+ ions are
presented, and the electrical conduction results by the hopping
of the unpaired 3d1 electron between V4+ and V5+ states [5,6].
∗ Corresponding author. Tel.: +20 57 403980; fax: +20 57 403868.
The unpaired electrons induce polarization around vanadium
E-mail addresses: elagwany75@mans.edu.eg, ions and hence, form polarons. Also in iron containing glass
elagwany75@yahoo.com (E.M. Ahmed). both Fe+2 and Fe+3 ions are present and the electrical conduction
0921-5107/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.07.025
2 F. Abdel-Wahab et al. / Materials Science and Engineering B 134 (2006) 1–8
occurs due to the hopping of the unpaired 3d5 electron between frequencies [102 , 103 , 104 , 105 Hz], and all measurements were
Fe2+ and Fe3+ sites forming another polaron. performed in the temperature range from 308 to 588 K.
The dominant charge carrier in such glasses may be elec-
trons, ions, polarons and/or protons [13,14]. All these types 3. Results and discussion
produce the same behavior when dc conductivity measurement
is considered. In addition, the effect of pilling-up of ions by 3.1. dc Conductivity and activation energy
electrodes (polarization) makes it impossible to differentiate
between various charge carriers [15,16]. Therefore, ac conduc- Fig. 1 shows the relation between σ dc and [103 /T] for all
tivity measurements are usually used to determine the type of samples. It appeared that these glasses have dc conductivities
the dominant carriers and to avoid the effect of electrode polar- in the range from 10−10 to 10−3 S cm−1 . The general behav-
ization. ior of the conductivity is the presence of two regions in [σ dc
It is suggested that electrical transport in TM doped oxide versus 103 /T] relation, one at relatively low temperature, while
glasses may occur by small polaron hopping between two differ- the other appears at high temperature. The change in these two
ent valency states of the TM ions [1,17,18], or by multiphonon regions is linear and these two straight lines intersected at def-
hopping of localized electrons with a weak electron–phonon inite temperature (Tx ) differ from one sample to another. It is
interaction [19]. There exists also a controversy over the nature supposed that at such definite temperature there may be a change
of hopping mechanism in different temperatures and composi- in the role played by strontium. According to Hirashima,
tion regions [20,21]. In addition some iron vanadium strontium
Tx = θD /2,
oxide glasses exhibit an interesting switching properties [22],
and hence additional work in this field have to be done. where (θ D ) is the characteristic Debye temperature that defined
However, this article aims to investigate the electrical con- by [23],
ductivity (dc and ac) and the dielectric relaxation properties of
V2 O5 ·SrO·FeO glass system as well as to clarify the type of hυ0 = kθD
charge carriers and the dominant conduction mechanism. where h is Planck’s constant, υ0 the optical phonon frequency
and k is Boltzmann constant. The obtained θ D and υ0 values
2. Experimental details are listed in Table 1. The characteristic Debye temperature of
the Sr-free sample was about 667.6 K. The introduction of only
2.1. Sample preparation 5 mol% SrO increases such temperature to 689.7 K. As SrO was
gradually increased from 5 up to 15 mol%, Debye temperature
A glass system of the composition: (80 − x) V2 O5 ·(x) SrO·20
show some fluctuations between the value 671.3 for sample
FeO, was prepared on the bases of the percentage molecular
weights, within the glass formation limits 0 ≤ x ≤ 40. Aldrich
and BDH companies supply all the used chemicals with purity
not less than 99.98%. Vanadium pentoxide and strontium oxide
were added as such while iron oxide was added as anhydrous
ferrous oxalate in order to achieve chemically reducing medium.
The finely mixed batches were melted in porcelain crucibles in
an electric muffle furnace for 90 min, at temperatures ranging
between 850 and 950 ◦ C depending on the batch composition.
The melts were stirred several times during melting, and they
were then poured between two pre-cooled stainless steel plates
in air. The obtained solid samples were directly transferred to the
annealing furnace at 200 ◦ C, which was then left to cooled very
slowly with a decreasing temperature rate of about 0.35 K/min
in order to obtain strain free samples.
containing 10 mol% SrO, and the value 676.5 K for the sample
3.190614
3.291952
3.383693
3.468815
3.574794
3.706739
3.854209
4.008922
4.203523
Density
(g/cm3 )
that contains 15 mol% SrO. Finally, Debye temperature show
a gradual decrease as the SrO content was increased up to the
sample that contains 40 mol% SrO. The high difference in θ D
(1022 cm−3 )
between the Sr free sample and those containing SrO may be due
4.601148
NTM-ions
4.76069
4.69955
4.71331
4.61678
4.55404
4.56427
to the opening of the glass network structure produced by the
4.5352
4.6609
large Sr2+ volume, which increases the thermal vibration of the
network. This in turn act directly to increase the optical phonon
frequency and the vibrational amplitude of the glass network.
(1022 cm−3 )
This was also noticed obviously as Sr2+ cations were just intro-
1.69033
1.62275
1.57794
1.49314
1.41674
1.35009
1.22865
1.13808
1.3193
NO-ions
at 503 K
E
σ(T ) = σ0 exp − (1)
4.25
3.76
3.33
3.17
2.83
2.63
2.29
2.43
2.08
kT
where σ 0 is a pre-exponential value, E is the activation
energy and T is the absolute temperature. This case cannot
εp × 10−12
kT
0.157
0.159
0.161
0.164
0.167
0.169
0.171
0.175
0.179
where,
υ0 NC(1 − C)e2 R2
σ0 =
(1013 s−1 )
exp(−2αR)
k
1.39
1.44
1.40
1.41
1.35
1.32
1.29
1.28
1.26
and
υ0 NC(1 − C)e2 R2
σ0 =
θ D (K)
667.6
689.7
671.3
676.5
648.2
632.8
620.1
613.4
604.9
k
[in adiabatic region that is exp(−2aR) = 1]
where N is the transition metal ion density, C the fraction
FeO
0
5
10
15
20
25
30
35
40
equation [5,15]:
80
75
70
65
60
55
50
45
40
S1
S2
S3
S4
S5
S6
S7
S8
S9
E = EH + ED /2 for T > Tx
E = EH for T < Tx /2
The obtained values for the activation energy E in the two
temperature regions (low (II) and high (I) temperatures) are pre-
sented in Fig. 2, as a function of SrO content. It can be seen that in
the two temperatures E increases with the gradual increase of
SrO concentration. Also it is observed that activation energies at
high temperatures (I) are higher than the corresponding value at
low temperatures (II). Amano et al. [25] reported that the lower
activation energy at low temperatures may be due to the pres-
ence of another conduction mechanism with the (SPH) [mixed
conduction] that is both (SPH) and (VRH) could be applied
in this range of temperature, since the (VRH) model exhibits Fig. 3. Compositional dependence of dc conductivity at different temperatures.
lower activation energy than (SPH) model [25–28]. The grad- The solid lines are drawn as a guide to the eye.
F. Abdel-Wahab et al. / Materials Science and Engineering B 134 (2006) 1–8 5
conduction part due to the movement of some ions is stopped 0.3 eV [34]. This is due to the fact that the hopping energy EH
due to the blocking effect of Sr ions. Since Sr ions are of rela- depends on the dielectric constant (εp ) of a glass sample [35].
tively large ionic radius and high atomic weight in comparison The dielectric constant εp can be obtained from the equation.
with the usual alkali cations (Li, Na and K ions). So it is hard for
Sr+ to move throughout the network and hence it adds no part ED e2 1 1
EH ≈ E = = − (6)
to the conductivity of these glasses. 2 4εp rp R
where
3.2. Relation between the activation energy and the mean
V-ion spacing (R) ε−1 −1 −1
p = ε∞ − εs
Table 2
Parameters calculated from fitting using (CBH) model for V2 O5 –SrO–FeO
glasses
Glass sympole τ 0 (sec) N (cm-3 ) ε
S1 1 × 10−13 7 × 1021 8
S2 9 × 10−13 4 × 1021 3.8
S3 1 × 10−10 1 × 1021 1.95
S4 1 × 10−13 9 × 1020 18.5
S5 1 × 10−13 5.5 × 1020 14
S6 2 × 10−13 2 × 1020 3
S7 1 × 10−13 8 × 1019 4.5
S8 1 × 10−13 5 × 1019 8.5
S9 1 × 10−13 1 × 1019 3.6
Fig. 9. Variation of dielectric constant ε with the temperature.
8 F. Abdel-Wahab et al. / Materials Science and Engineering B 134 (2006) 1–8
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