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Physics of the Solid State, Vol. 46, No. 1, 2004, pp. 188191.

Translated from Fizika Tverdogo Tela, Vol. 46, No. 1, 2004, pp. 185188.
Original Russian Text Copyright 2004 by Malyshev, Peshev, Pritulov.

MAGNETISM
AND FERROELECTRICITY

Temperature Dependences of the Dielectric Properties


of LithiumTitanium Ferrite Ceramics
A. V. Malyshev, V. V. Peshev, and A. M. Pritulov
Tomsk Polytechnical University, pr. Lenina 30, Tomsk, 634034 Russia
e-mail: peshev@tpu.ru
Received December 10, 2002; in final form, May 13, 2003

AbstractTemperature dependences of the real ' and imaginary '' parts of the complex permittivity of lithiumtitanium ferrite ceramics are measured in the frequency range 102106 Hz at different test-signal amplitudes and dc bias voltages. It is found that the dielectric characteristics of the ceramic samples drastically
change in narrow temperature ranges. The assumption is made that relaxators whose reorientation is due to tunneling transitions of electrons inside bivalent iron iontrivalent metal ion pairs are involved in polarization
processes. Under certain conditions, the reorientation of relaxators can have collective character. 2004 MAIK
Nauka/Interperiodica.

1. INTRODUCTION
It is known that the conductivity and complex permittivity * substantially affect the propagation of electromagnetic waves in ferrite materials and, hence, can
be responsible for the functional properties of ferritebased devices. At present, there are many works concerned with the electrical properties of ferrites [110].
As a rule, dependences of the conductivity and complex permittivity * on the frequency f and temperature
T for polycrystalline ferrites are interpreted within
either the model of interlayer polarization [1] or the
model of interlayer polarization involving surface
states of grain boundaries [2]. Since interlayer polarization is caused primarily by charge transfer, the charge
transfer mechanism affects the characteristics of the
interlayer polarization. It is believed that charge transfer proceeds either through migration of charge carriers
over the impurity band [3, 4] or through hoppings of
carriers over localized energy levels due to electron
phonon interactions [5]. The hopping mechanism of
charge transfer in ferrites is associated with the presence of bivalent iron ions and electron transitions
between variable-valence ions, for example, Fe2+ +
Me3+
Fe3+ + Me2+ [6]. It has been established that
the higher the Fe2+ concentration, the higher the conductivity and the larger the real part ' of the permittivity. On this basis, it has been assumed that these transitions are responsible for charge transfer and polarization [79]. In this case, there is no need to invoke the
Koops model, because the recharging of ion pairs
Fe3+ + Me2+ can be considered as the
Fe2+ + Me3+
reorientation of dipoles in an ac electric field. Since the
components of ion pairs are crystal-forming ions, the
large value of ' can be explained by the high concentration of ion pairs. When electron transitions in these
pairs occur through phonon-assisted tunneling, it can

be expected that the characteristic time of polarization


will depend not only on the temperature but also on the
time of action of the polarizing field (or, in the case of
an ac electric field, on the frequency) and its strength.
It is known that electric dipoles at high concentrations bring about the spontaneous formation of electric
domains. Since the Fe2+ content varies over a wide
range, the concentrations of dipoles can also change
significantly. It can be assumed that the high permittivity for ferrites is caused not only by the interlayer
polarization but also by the polarization due to either
individual recharging of ion pairs, recharging of pairs
involved in spontaneously formed electric domains, or
recharging of pairs contained in domains induced by
the electric field.
The aim of this work was to elucidate the possible
mechanism of relaxation polarization in lithiumtitanium ferrite ceramics. For this purpose, we investigated
the temperature dependences of the real ' and imaginary '' parts of the complex permittivity at different
frequencies and amplitudes of the test signal in the
presence and absence of a dc bias voltage.
2. SAMPLES AND EXPERIMENTAL TECHNIQUE
In our experiments, we used ferrites of composition
Li0.649Fe1.598Ti0.5Zn0.2Mn0.051O4 doped with 0.22 wt %
Bi2O3. Samples were synthesized under working conditions according to the ceramic technique and were then
sintered in air at T = 1280 K for 120 min. After sintering, the samples were ground on both sides from the
initial thickness d = 1 mm to a thickness of 0.22 mm.
As a result, the samples had the form of pellets 13 mm
in diameter. Then, silver contacts were applied to the
sample surface through thermal evaporation under vacuum. The diameter of the measuring contact was equal

1063-7834/04/4601-0188$26.00 2004 MAIK Nauka/Interperiodica

TEMPERATURE DEPENDENCES OF THE DIELECTRIC PROPERTIES


(a)

1
2
102

PHYSICS OF THE SOLID STATE

Vol. 46

No. 1

2004

3
4
TC

101
300

'', rel. units

106

3. RESULTS AND DISCUSSION


The temperature dependences of the real ' and
imaginary '' parts of the complex permittivity measured at a test-signal amplitude Utest = 56 mV are
depicted in Fig. 1. It can be seen from Fig. 1a that the
polarization involves no less than two stages and the
permittivity ' = F(T) at saturation ( sf' ) for the lowtemperature stage depends on the frequency and
decreases with an increase in the frequency. Below, we
will consider only the most pronounced low-temperature stage. The absence of relaxation peaks in the
dependences '' = F(T) (Fig. 1b) suggests that the conduction current substantially exceeds the active component of the relaxation current. The temperature dependences of the conductance G(T) used for calculating the
values of '' are virtually independent of the frequency.
The measurements were performed during heating and
cooling of the samples. The curves '' = F(T) measured
in the course of heating and cooling coincide with each
other. The dependences ' = F(T) are characterized by
an insignificant hysteresis at a frequency of 100 Hz,
which decreases with an increase in the frequency.
Note that the temperature dependences of the permittivity ' can be well approximated within the model
of interlayer polarization. In this case, the conduction
current is dominant; therefore, the activation energy of
relaxation Ea should be equal to the activation energy of
charge transfer Ea. The activation energy Ea , which is
determined from the dependences '(T) in the framework of this model, is equal to 0.360.38 eV. However,
the dependences ''(T) can be described only at activation energies E = (0.70.74) eV > Ea . Since Ea Ea
and the temperature dependences of the conductance
G(T) for the studied samples are almost identical at different frequencies, the experimental temperature
dependences of the real ' and imaginary '' parts of the
permittivity and also the large values of ' have defied
explanation in terms of interlayer polarization.

1'

103

', rel. units

to 5 mm. The pellets with contacts were subjected to


normalizing annealing at T = 570 K for t = 1 h. The
magnetic Curie temperature TC for the ferrite ceramics
thus prepared was equal to 575 K. We measured the
capacitance C and conductance G, i.e., the conductivity
governed by both conduction current and the polarization current component coinciding in phase with the
electric field. The measurements were carried out in the
temperature range 300600 K. In the course of measurements, the samples were heated and cooled at a rate
of 2 K/min. The experiments were performed at testsignal frequencies f = 100, 103, 104 (an E7-14 bridge),
and 106 Hz (an E7-12 bridge). The real ' and imaginary
'' parts of the permittivity were calculated from the
standard formulas: ' = Cd/(S0), tan = G/(C), and
'' = 'tan , where 0 is the permittivity of free space,
is the circular frequency of the polarizing field, and
tan is the dielectric loss tangent.

189

400

104

5
6
7

102

(b)

500

600

500

600

100

102
300

400
T, K

Fig. 1. Temperature dependences of (a) real ' and (b) imaginary '' parts of the complex permittivity measured at the
test-signal amplitude Utest = 56 mV in the course of (18)
heating and (1') cooling. Frequency: (1, 1', 5) 102, (2, 6) 103,
(3, 7) 104, and (4, 8) 106 Hz.

The data presented in Fig. 1a cannot be explained in


the framework of the Debye model, because the value
of sf' depends on the frequency. Recall that, within the
Debye model, the relaxation time (T) does not depend
on the duration of the polarizing voltage pulse and,
hence, on the test-signal frequency. Consequently, the
value of sf' is equal to the static permittivity s and does
not depend on the frequency f, even though there are
distributions of the activation energy Ea and preexponential factor 0. Therefore, for (T) = const( f ), at any
test-signal frequency, there always (theoretically) exists
a temperature range in which virtually all relaxators are
involved in the reorientation and the permittivity '
reaches the same value s.
In the case when the polarization is caused by either
the reorientation of electric domains in ferroelectrics
[11] or the reorientation of relaxators due to tunneling
of charge carriers [5] between centers of localization,
the number of dipoles involved in this process is limited
by the duration of polarizing-field action. Under these

MALYSHEV et al.

190
103

(a)

(a)

1'
1

104

2'

', rel. units

', rel. units

103

102

1
2
3
1', 2', 3'
4, 4'

102
4

400

TC

101
300

400

500

(b)
'', rel. units

'', rel. units

5
6
7

(b)

104

104

102

103

5
6
7
8, 5'8'

400

100
102
300

400

500

600

600
105

106

500

600

T, K
Fig. 2. Temperature dependences of (a) real ' and (b) imaginary '' parts of the complex permittivity measured at the
test-signal amplitude Utest = 2800 mV in the course of (1
8) heating and (1', 2') cooling. Frequency: (1, 1', 5) 102, (2,
2', 6) 103, (3, 7) 104, and (4, 8) 106 Hz.

conditions, the real part of the permittivity at saturation


sf' is a decreasing function of the frequency (see
Fig. 1a).
In order to elucidate the influence of the polarizingfield strength of the permittivity, we measured the temperature dependences of ' and '' at the same frequencies and the test-signal amplitude Utest = 2800 mV
(Fig. 2). As can be seen from Fig. 2a, the dependences
' = F(T) have a considerable hysteresis at a frequency
of 100 Hz, which decreases with an increase in the frequency. These dependences exhibit an anomalous
behavior, which manifests itself in a drastic decrease in
the values of ' with an increase in the temperature
beginning with T = 550 K (Fig. 2a, curves 1, 1').
The hysteresis observed in the dependence ' =
F(T) and a sharp decrease in the values of ' (Fig. 2a,
curves 1, 1') indicate that the ferrite possibly possess
ferroelectric-like properties. However, these features
are observed only at a high test-signal amplitude Utest =
2.8 V and a long duration of polarizing-field action ( f =
100 Hz). When an ac electric field with a high strength

500
T, K

600

Fig. 3. Temperature dependences of (a) real ' and (b) imaginary '' parts of the complex permittivity measured at the
test-signal amplitude Utest = 56 mV and frequency f =
103 Hz in the course of (18) heating and (1'8') cooling at
dc polarizing voltages Up: (1, 1', 5, 5') 0.2, (2, 2', 6, 6') 0.25,
(3, 3', 7, 7') 0.3, and (4, 4', 8, 8') 0 V.

and a low frequency is applied to the sample, the concentration of dipoles oriented along the same direction
can reach large values in certain time intervals. The
interaction between dipoles within these intervals can
lead to specific features in the behavior of polarization
(due to the collective reorientation of the dipoles) and,
possibly, to the formation of electric domains. Thus, we
believe that the features revealed in the temperature
dependences of the permittivity ' are associated with
the collective character of the dipole reorientation during part of the half-cycle of the ac electric field. To put
it differently, the electric field at regular intervals
induces a ferroelectric-like state in the dipole system.
In this respect, it is of interest to investigate the temperature dependences of the dielectric properties under
conditions where the dc polarizing voltage Up and the
ac test-signal voltage Utest = 56 mV < Up are applied to
the sample. In this case, the test signal does not change
the state of the dipole system and serves only for testing, whereas the concentration of dipoles oriented by
the dc electric field does not depend on the test-signal
frequency. It can be expected that, at a dc polarizing
voltage Up, the specific features in the temperature
dependences of the dielectric characteristics should be
observed at frequencies f > 100 Hz (unlike the depenPHYSICS OF THE SOLID STATE

Vol. 46

No. 1

2004

TEMPERATURE DEPENDENCES OF THE DIELECTRIC PROPERTIES


3

100

2'

3'

', rel. units

103

1'

460

1
2
3
4, 1'4'

480

102

400
'', rel. units

voltage Up. Similar features are observed in the temperature dependences of the dielectric characteristics measured at a frequency of 10 kHz (Fig. 4). As was
expected, the temperatures Tstart and Tend at f = 10 kHz
are equal to those at f = 1 kHz; i.e., these temperatures
depend on the dc polarizing voltage Up and are independent of the frequency f at low test-signal voltages
Utest. The inset shows the specific features in the dependences '(T) measured during cooling.

(a)

200

500

4. CONCLUSIONS
Thus, it was established that the activation energy of
relaxation polarization differs from the activation
energy of charge transfer and that the conductivity does
not depend on the frequency. This means that the interlayer polarization makes an insignificant contribution
to the high permittivity ' in the frequency and temperature ranges covered. It is found that the dielectric characteristics of the ceramic samples drastically change in
narrow temperature ranges. The features observed in
the temperature dependences of the dielectric characteristics can be associated with the collective reorientation of dipoles; in turn, the collective polarization is
most likely induced by the electric field.

600

(b)

105

5
6
7
8, 5'8'

104
103
102

400

500
T, K

600

Fig. 4. Temperature dependences of (a) real ' and (b) imaginary '' parts of the complex permittivity measured at the
test-signal amplitude Utest = 56 mV and frequency f =
104 Hz in the course of (18) heating and (1'8') cooling at
dc polarizing voltages Up: (1, 1', 5, 5') 0.2, (2, 2', 6, 6') 0.25,
(3, 3', 7, 7') 0.3, and (4, 4', 8, 8') 0 V. The inset shows the specific features in the dependences '(T) measured during (1'
3') cooling. Curve 3 in the inset is depicted for comparison.

REFERENCES

dences shown in Fig. 1, for which Utest is also equal to


56 mV).
Figure 3 shows the dependences '(T) and ''(T)
measured at a low test-signal voltage Utest and dc polarizing voltage Up = 00.3 V in the course of heating and
cooling. The measurements were performed with a
temperature step of 2 K. Actually, these dependences at
Up 0 exhibit a pronounced temperature hysteresis.
Analysis of the dependences '(T) and ''(T) measured
during heating at Up 0 shows that the values of '
jumpwise increase and the values of '' jumpwise
decrease in the same temperature range 460530 K.
The drastic changes observed in the dielectric characteristics start and end at temperatures Tstart and Tend,
respectively. Note that the temperature Tend monotonically decreases with an increase in the dc polarizing

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Translated by O. Borovik-Romanova