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Article history:
Received 21 February 2011
Received in revised form 22 April 2011
Accepted 23 May 2011
Available online 31 May 2011
Keywords:
Ferrite
DC resistivity
Dielectric properties
AC conductivity
a b s t r a c t
A series of polycrystalline spinel ferrites with the composition NiInxFe2-xO4 (0 x 0.3) were prepared by the
solid state reaction to study the effect of In 3+ ions substitution on their dc electrical resistivity and dielectric
properties. The dc resistivity has been investigated as a function of temperature and composition. The indium
ion increases the dc resistivity and activation energy of the system. A study of the dielectric properties of these
mixed ferrites, as a function of composition, frequency and temperature, has been undertaken. The dielectric
constant (), dielectric loss () and dielectric loss tangent (tan) all decreases with frequency as well as with
the composition. The dielectric constant () and dielectric loss tangent (tan) were increases with increasing
temperature. AC conductivity increases with increase in applied frequency. The dielectric behavior of the
present samples is attributed to the MaxwellWagner type interfacial polarization. The conduction
mechanism in these ferrites is due to electron hopping between Fe 2+ and Fe 3+ ions on adjacent octahedral
sites.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Nickel and substituted nickel ferrite is one of the versatile and
technologically important soft ferrite materials because of their
typical ferromagnetic properties, low conductivity and thus lower
eddy current losses, high electrochemical stability, catalytic behavior
etc. [13]. The polycrystalline soft ferrites having high dc resistivity
are used in making the core of the transformers and chokes, ferrites
having extremely low dielectric loss and therefore very useful for
microwave communication [4]. The dielectric properties of the
polycrystalline soft ferrites are sensitive to the applied electric eld
frequency, preparative methods and preparation conditions, chemical
compositions and doping of additives.
Study of the effect of temperature, composition and frequency on
the dielectric behavior and dc resistivity offers much valuable
information on the behavior of the localized electric charge carriers
which can lead to a good explanation and understanding of the
mechanism of electric conduction and dielectric polarization in ferrite
systems [5]. Electrical properties for substituted NiFe2O4 have been
studied by various researchers [68]. Our previous report deals with
219
(440)
(511)
(422)
(222)
(400)
(220)
(311)
0.30
0.25
0.20
0.15
0.10
0.05
5m
0.00
20
30
40
50
60
70
80
2 (degree)
Fig. 1. X-ray diffraction patterns of NiInxFe2-xO4.
5m
Fig. 2. Typical SEM for (a) x = 0.1 and (b) x = 0.2 of NiInxFe2-xO4.
Ni
3 +
+ Fe
Ni
= 0
Eg
kB T
1
0.00
0.05
0.10
0.15
0.20
0.25
0.30
4.50x106
3.75x106
(cm)
2 +
+ Fe
3.2. DC resistivity
Fig. 3 shows the variations in dc resistivity with temperature. It is
observed from Fig. 3 that for all the samples resistivity decreases with
increasing temperature, indicating the semiconducting nature of the
samples. The temperature dependence of resistivity found to follow
the Arrhenius equation [10].
3 +
3.00x106
2.25x106
1.50x106
7.50x105
1.2
1.3
1.4
1.5
1.6
1.7
1000/T (K-1)
Fig. 3. Variations in dc resistivity with temperature.
1.8
linear regions are observed in the log vs. 1000/T plot from room
temperature to well above Curie temperature (Tc). The change in slope
indicates change in conduction mechanism. The rst low-temperature
region is attributed to the conduction due to impurities, voids, defects, etc.
The second temperature region (up to Curie temperature) is attributed to
ferrimagnetic region. Third temperature region (above Curie temperature) is attributed to paramagnetic region [16]. In the present case we
observed only two regions separated at a particular temperature
(675860 K) which may corresponds to Curie temperature of the
samples. The temperature region above 860 K again follows linearity.
The Curie temperature determined from resistivity plots shows decreasing trend with increase in In3+ content, as shown in Table 1. This effect
can be explained on the basis of the number of magnetic ions present in
the two sublattices and their mutual interactions. As the concentration of
In3+ ions increases at the octahedral site, they replaced Fe3+ ions. This
leads to a decrease in the AB interaction of the type Fe3+(A)O2Fe3+(B).
Since Curie temperature is determined by an overall strength of the AB
exchange interaction, the weakening of the Fe3+(A)O 2Fe 3+(B)
interaction results in a decrease of the Curie temperature, when the
concentration of the In3+ ions increases successively in the nickel ferrite.
The resistivity plots (Figs. 3 and 4) clearly indicates that resistivity
also varies with the substitution of In3+ ions. It is observed from Fig. 4
that, as substitution of In3+ ions increase in NiFe2O4 the resistivity
founds to increase. Though the variation is less rapid for lower indium
concentrations, the substitutions have resulted in higher DC resistivities
with the increase in x. As is evident from the compositions all the
samples in the system contain a xed quantity of nickel. Since all the Ni2
+
ions invariably reside on octahedral sites [10], they are expected to
lock up with the Fe2+ ions that developed in the course of preparation,
which is inevitable, to maintain the charge balance [17]. This locking
process reduces hopping between iron ions such as Fe 2+Fe3+ in
octahedral sites and contributes to increase the resistivity slightly for all
the compositions in the system. Since indium ions are known to have
initial preference for A-sites [11], the substitution at rst is considered to
replace Fe3+ ions at tetrahedral sites only and this replacement of Fe3+
ions (0.67 ) by In3+ ions (0.91 ) obviously pushes the tetrahedron of
4 oxygen ions around it, thus, reducing the distance between two metal
ions in B-sublattice, which increases the hopping probability. This
process contributes to decrease slightly the resistivity as long as the
indium ions substitute iron ions at the A-sites. The observed resistivity
behavior for smaller concentrations of indium is in accordance with the
above two processes and suggests that the former process is slightly
dominant over the latter and the resistivity is slightly increased up to
x b 0.10 indium concentration. However, for higher concentrations of
indium, the resistivity is increased signicantly. This can be explained
with the supposition that the indium ions at higher concentrations
occupy B-sites as well [11]. It may also be due to the indium ions in
B-sites do not participate in the conduction processes, but limit the
degree of conduction by acting as scattering centers in the sense that
they reduce the number of Fe3+ ions [18]. The total number of iron ions
present at B-sites decreases with every step of indium concentration and
also the available Fe 2+ ions for hopping at these sites decrease in
number; thus, under these situation, it may lead to balance the
quantities of Fe2+ and Ni2+ ions to lock-up effectively and result in
Table 1
Activation energy in paramagnetic (Ep), ferrimagnetic (Ef) region, Ep Ef (Eg) and Curie
temperature (TC) of NiInxFe2-xO4.
Comp. x
Ep (eV)
Ef (eV)
Eg (eV)
TC (K)
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.421
0.445
0.467
0.49
0.547
0.616
0.707
0.052
0.066
0.077
0.088
0.121
0.132
0.165
0.369
0.379
0.390
0.402
0.426
0.484
0.542
840
795
771
745
730
695
675
2.4
0
at 600 C
220
2.0
1.6
1.2
0.8
0.00
0.05
0.10
0.15
0.20
0.25
0.30
In content x
Fig. 4. Variations in dc resistivity with In3+ content x.
higher resistivity. The observed higher resistivity for higher indiumconcentrated samples is in agreement with these considerations. The
activation energies for conduction are computed from log verses 1000/
T plots for all the samples and the data is given in Table 1. In the table Ef
is the activation energy corresponding to ferrimagnetic region and Ep
that corresponding to paramagnetic region. It is noted from the table
that the activation energies in paramagnetic region is higher than those
in ferrimagnetic region. This could be attributed to the disordered states
of the paramagnetic region and the ordered states of the ferrimagnetic
region [19]. This also suggests that the process of conduction is affected
by the change in magnetic ordering [20]. It can also be noted from the
table that as In3+ content increases, the resultant activation energies
(Ep Ef = Eg) of electric conduction also increase. Higher values of
activation energy have been found to correspond to low conductivity
values of samples. It may also be due to the probability of electron
hopping responsible for electrical conduction in ferrites depends upon
the activation energy, which is associated with the electrical energy
barrier experienced by the electrons during hopping [21,22]. Hence
higher activation energy implies the higher electrical resistivity. The
magnitude of activation energy for all the compositions with In3+
content suggests that the conduction process in the present ferrites is
due to hopping of polarons.
3.3. Dielectric properties
3.3.1. Frequency dependent dielectric properties
The variation of the dielectric constant () and dielectric loss () as a
function of frequency for all samples at room temperature is shown in
Figs. 5 and 6 respectively. It can be seen that all the samples show strong
frequency dependence as well as composition dependence. Therefore, the
dielectric variation of present system may be separately discussed in two
aspects i.e. frequency dependence and composition dependence. It is clear
that the dielectric constant and dielectric loss decreases with increasing
frequency. The high values of dielectric parameters at lower frequency
region is due to MaxwellWagner interfacial type of polarization [23,24]
for the inhomogeneous double layer dielectric structure which is in
agreement with Koops Phenomenological theory [25].
The dielectric constant and dielectric loss decreases with increasing frequency and then reaches a constant value due to the fact that
beyond a certain frequency of external AC eld, the electron exchange
between Fe 2+ and Fe 3+ cannot follow the alternating eld. The
inhomogeneous dielectric structure was supposed to be consisted by
two layers. The rst one is the fairly well conducting large ferrite
grains which are separated by the second thin layer of the poorly
conducting grain boundaries. The grain boundaries of low
Table 2
Dielectric constant () and dielectric loss () measured at room temperature at 100 Hz
and at 1 MHz of NiInxFe2-xO4.
0.00
0.05
0.10
0.15
0.20
0.25
0.30
1800
1500
1200
221
Comp. x
0.00
0.05
0.10
0.15
0.20
0.25
0.30
900
600
Dielectric constant
Dielectric loss
100 (Hz)
1 (MHz)
100 (Hz)
1 (MHz)
1734
1213
728
436
346
218
109
65.84
46.09
27.65
16.59
13.17
8.30
65.84
1179
696
348
139
70
59
29
8.58
4.38
2.19
0.88
0.44
0.43
0.21
300
observed from Fig. 7 that the dielectric loss tangent decreases with
increase in In 3+ content x. This can be attributed to the increase in
resistivity which causes reduction in tan. Our results on variation of
dielectric loss tangent as a function of frequency suggest that the
sample having compositional formula NiIn0.3Fe1.7O4 has the lowest
dielectric loss tangent tan and highest resistivity.
0
2
log f
0.00
0.05
0.10
0.15
0.20
0.25
0.30
1000
800
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.7
1200
600
400
200
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
2
log f
Fig. 6. Variation of dielectric loss () with log f.
log f
Fig. 7. Variation of dielectric loss tangent (tan) with log f.
222
2800
2100
0.00
0.05
0.10
0.15
0.20
0.25
0.30
ac = 0 tan
1400
700
0
400
500
600
700
800
Temperature (K)
Fig. 8. Variation of dielectric constant () with temperature.
mechanism. Thus, the dielectric polarization increases, and consequently increases the dielectric constant and dielectric loss tangent.
3.3.3. AC conductivity
The electrical conductivity in ferrite is mainly due to hopping
electron between ions of the same element present in more than one
valance state, distributed randomly over crystallographicaly equivalent lattice sites. Ferrite structurally from cubic close packed oxygen
lattice with the cation at the octahedral (B) and the tetrahedral (A)
sites. The distance between two metal ions on (B) sites smaller than
the distance between two metals ions on (B) and (A) site, therefore
the hopping between (A) and (B) has very small probability compared
with that for BB hopping [32]. The hopping between AA sites does
not exist, due to that there are only Fe 3+ ions at A sites and any Fe 2+
ions formed during processing preferentially occupy B sites only [10].
The charges can migrate under the inuence of the applied eld
contributing to the electrical response of the system. Conductivity
increases with increase in applied frequency when the conduction is
due to hopping of electrons, on the other hand conductivity deceases
when the conduction is due to band conduction.
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.00
0.05
0.10
0.15
0.20
0.25
-3.5
-4.0
-4.5
log ac
-5.0
-5.5
-6.0
-6.5
0
400
500
600
700
800
Temperature (K)
Fig. 9. Variation of dielectric loss tangent (tan) with temperature.
10
12
log 2
Fig. 10. Variation of ac conductivity with frequency.
14
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