ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 279 (2004) 325330

Electrical conductivity of MnZn ferrite single crystals

with a small number of Fe2+ ions
Y. Fukudaa,*, S. Nagatab, K. Echizenyaa
a

Steel Research Laboratory, JFE Steel Corporation, 1 Kawasaki-cho, chuo-ku, Chiba 260-0835, Japan
b
Research Laboratory, Kawatetsu Mining Co., Ltd., Chiba, Japan
Received 2 December 2003; received in revised form 16 January 2004

Abstract
2
2
3 2
(0:52pap0:72; 0:20pbp0:43; 0:0023pcp0:14)
The electrical conductivity of Mn2
a Znb Fec Fe2 O4
single crystals was measured in the temperature range of 80300 K. Electrical conductivity increases monotonously
with the concentration of Fe2+ ions. The activation energy for hopping conduction is 0.0240.27 eV and shows
its minimum value in the vicinity of c 0:06: Due to low carrier mobility, a small polaron effect is expected
to be important at co0:06: In contrast, the high carrier mobility at c > 0:06 suggests that the Coulomb
interaction between carriers increases with the Fe2+ ion concentration. Polaron binding energy and Coulmb
interaction are considered to result in additional activation energy for hopping conduction. Thus, the electrical
conduction mechanism of ferrite is understood as the result of competition between the polaron effect and electron
electron interactions.
r 2004 Elsevier B.V. All rights reserved.

PACS: 72.20.I; 72.80.Ga; 75.50.Dd

Keywords: Electrical conductivity; Ferrite; Single crystal; Polaron; Hopping conduction

1. Introduction
Ferrites possess a spinel structure which consists
of unit cells containing 24 positive ions and 32
negative ions (O2 ion) and is expressed by the
general formula MeFe2O4, where Me is a divalent
metal ion such as Fe2+, Ni2+, Mn2+, or Zn2+.
The metal ions are located at two crystallographically different sites, the A site, comprising 8

*Corresponding author. Tel.: +43-262-2486; fax: +43-2622467.

E-mail address: y-fukuda@jfe-steel.co.jp (Y. Fukuda).

tetrahedrally coordinated metal ions, and the B

site, comprising 16 octahedrally coordinated metal
ions. The Zn2+ ion preferentially occupies the A
site, whereas it is known that 80% of Mn2+
occupies the A site and 20% may go to the B site
(inverse spinel) [1]. The Fe2+ ion may occupy the
B site together with Fe3+. Electrical conduction
originates between Fe2+ and Fe3+ in the B site.
The conduction mechanism of ferrites has been
discussed as that of a derivative compound of
magnetite (Fe3O4). This parent compound shows a
metalinsulator transition (Verway transition) at
120 K, which is believed to be associated with
electron charge ordering and electronelectron

0304-8853/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2004.01.090

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Y. Fukuda et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 325330

interactions [2]. Therefore, slight impurities introduce a disordered structure, causing the transition
temperature to fall abruptly or disappear [3]. As
the concentration of ions substituted in magnetite
increases, thermally activated Fe2+ valency states
result in electrical conduction by a hopping
mechanism [4]. Phillips et al. [5] have proposed
the formation of a Coulomb gap due to electron
interactions caused by the large number of excess
charges in Fe2+ ions at the B site. On the other
hand, with small Fe2+ concentrations, electrical
conductivity has been interpreted as depending on
nearest-neighbor hopping at high temperatures
and on variable range hopping at low temperatures [5].
Because of their extraordinarily small electrical
conductivity compared with metals, ferrites are
well known as outstanding core materials for
magnetic devices driven at high frequency, such as
magnetic heads of video tape recorders and
inductor/transformers used in power electronics.
In practical compositions, NiZn-type ferrite
is an insulator, and MnZn-type ferrite without
a grain boundary phase is a semiconductor of
sA10 O1 m1 because it contains a small number
of Fe2+ ions. From the practical viewpoint, a
deeper understanding of the electrical conduction
mechanism with small Fe2+ concentrations is
important. However, since conventional interest
is from the viewpoint of substances, which
considers Fe3O4 as a parent material, as mentioned
above, there have been very few reports on
electrical conductivity in ferrite with a small
number of Fe2+ ions, especially concerning single
crystals. The aim of this article is to elucidate
systematically the electrical conductivity of exactly
dened ferrite single crystals, with particular
emphasis on a small Fe2+ ion concentration
region which includes the composition of a
standard material for video recording heads.
We will discuss an electrical conduction me2
2
3 2
chanism for Mn2
(0:52pap
a Znb Fec Fe2 O4
0:72; 0:20pbp0:43; 0:0023pcp0:14) single crystals
with attention only to Fe2+ concentration.
In other words, we will disregard the effect of
Mn2+ and Zn2+ and discuss the electrical
conduction mechanism only on the basis of Fe2+
concentration.

2. Experimental procedure
Electrical conductivity was measured in
2
2
3 2
(0:52pap0:72; 0:20p
Mn2
a Znb Fec Fe2 O4
bp0:43; 0:0023pcp0:14) single crystals produced
by the modied Bridgman method [6]. In preparing specimens, raw materials were introduced into
a platinum crucible as liquid drops and, by moving
the crucible downward, the crystal was growing
from the melting zone kept at a xed width.
The compositions of crystals were determined
by uorescence X-ray analysis. Since the carrier
number is strongly associated with the number of
Fe2+ ions, the correct value of the Fe2+ concentration is very important. Quantitative analysis of
Fe2+ was performed by the potassium dichromate
titration method (JIS M8213).
Specimens for electrical conductivity measurement were cut to a size of 1 mm  2 mm  15 mm
L. Gold electrodes were formed by sputtering and
joined to a lead with indium solder. DC conductivity was measured in the temperature range
of 80300 K by the four terminal technique. AC
conductivity was measured by the two-probe
method, applying an impedance analyzer
(HP4192A), over the frequency range 50500 kHz
in the same temperature range as for DC
conductivity. Curie temperatures were obtained
by measurement in a vibrating sample magnetometer (Toei Industry, VSM-3).

3. Experimental results
3.1. Composition
An example of the appearance and composition
change of a single crystal is shown in Fig. 1 [7].
The size of the grown crystal was 580 mm in length
and 110 mm in diameter. Composition change was
suppressed to within 1 mol% over a length of
500 mm. Specimens for measurements were obtained by cutting grown ingots. The compositions
and Curie temperatures Tc of the specimens are
summarized in Fig. 2. Since Tc of all the specimens
is above room temperature, all specimens are
ferromagnetic in the range of measurement temperatures used here. The relationship of Fe2+ to

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Y. Fukuda et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 325330

327

Fig. 3. Relation between Fe2+ and total Fe.

Fig. 1. Appearance and composition change of growth crystal.

Fig. 2. Compositions and Curie temperatures of MaZnbFe(2+c)O4.

total iron concentration is shown in Fig. 3 with the

2
2
2
3
calculated values of Mn2
a Znb Fec2g Fe22g O4g :
Although the oxygen content of the single crystals
was slightly excessive, the deviation from the
stoichiometric composition g was not more than
4.5  103. The discussion in this article is based
on analytic values of the Fe2+ concentration.
3.2. DC conductivity
DC conductivity sDC is plotted against 1000=T
over the temperature range of 80300 K in Fig. 4.
At elevated temperatures, ferrite exhibits semicon-

Fig. 4. Temperature dependence of the DC conductivity sDC :

ductive behavior with thermally activated conductivity. The slope of electrical conductivity at
high temperatures is steeper than in the lowtemperature region. Ferrites with smaller Fe2+ ion
concentrations show a larger slope. In Fig. 5,
electrical conductivity at 298 K is plotted against
Fe2+ ion concentration and increases monotonously with Fe2+. In particular, conductivities in
the range of c 0:003420:02 shows abrupt
changes. Electrical conductivity for the hopping
mechanism can be expressed by the following
formula:
sDC AT 1 expW =kB T;

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Y. Fukuda et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 325330

3.3. AC conductivity
The frequency dependence of AC conductivity
sAC is expressed by

Fig. 5. Fe2+ concentration dependence of DC conductivity

sDC (K, J) and carrier mobility mD (m,n) at 298 K. (J and n
for MnxFe3xO4 by Ref. [5]).

Fig. 6. Fe2+ concentration dependence of activation energy W

(m, n) and pre-exponential factor A(K, J) in s
AT 1 expW =kT: (n and J for MnxFe3xO4 by Ref. [4]).

where W is activation energy, A is a preexponential temperature-independent factor, and

kB is the Bortzmann constant. Activation energy
W and the pre-exponential factor A for 140300 K
are shown in Fig. 6. It should be noted that
activation energy shows its minimum value in the
vicinity of c 0:06: At co0:06; activation energy
decreases abruptly, but conversely, increases gradually at c > 0:06: A similar tendency is observed
with the pre-exponential factor A: However, the
minimum value of A shifts to c 0:1; in contrast
to that of activation energy. It is also characteristic
of A that the slope at high c values is large
compared with that of activation energy.

sAC o s  sDC ;

sAC opos ;

where s is the real part of complex conductivity, o

is angular frequency (o 2pf ), and s is an
exponent. The value of s at co0:03 is larger
than sDC ; while s is substantially the same in both
cases at c > 0:03: Figs. 7 and 8 show the relationships between AC conductivity and 1000=T for

Fig. 7. Temperature dependence of the AC conductivity sAC

for c 0:0063:

Fig. 8. Temperature dependence of the AC conductivity sAC

for c 0:011:

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Y. Fukuda et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 325330

Fig. 9. Temperature dependence of the c value for c 0:0023;

0.0063 and 0.011.

specimens with c 0:0063 and c 0:011; respectively. The slope of AC conductivity at c 0:0063
is larger than the slope at c 0:011: The values of
s determined by least-mean-square analyses for
c 0:0023; 0.0063, and 0.011 are plotted as a
function of temperature in Fig. 9. At c 0:0023
and 0.0063, a linear relationship exists between s
and T: There are three temperature regions for
c 0:011; i.e., the high-temperature region where
sA0; the low-temperature region in which a linear
relationship exists between s and T; and an
intermediate region where s decreases rapidly with
increasing temperature.

4. Discussion
The conduction carrier of a ferrite is the excess
charge of Fe2+ ions. At nite temperatures,
carriers may be thermally activated to hop to
Fe3+ sites and contribute in this way to electrical
transport. Therefore, electrical conductivity increases with Fe2+ concentration, as shown in Fig.
4. However, electronlattice interaction (polaron
effect) and electronelectron interaction (Coulomb
interaction) must be taken into account when
discussing an electrical conduction mechanism.
Due to the polarization effect of its surroundings,
it is usually assumed that an electron is not entirely
free to move. The importance of the Coulomb
interaction on hopping conduction is characterized
by the formation of a Coulomb gap at c > 0:5 at
low temperature [8].

329

The polaron effect in ferrite has been summarized by Whall et al. [9] in the following three items.
Firstly, due to the small binding energy of polarons,
the formation of polarons may be difcult in the
case of c > 0:1 [10]. Secondly, overlapping of
polarization clouds reduces polaron binding energy
[11]. Thirdly, since Fe3O4 has relatively high roomtemperature mobility (A105 m2/V s), the polaron
contribution to hopping energy is small at high
Fe2+ concentrations [12].
On the assumption that the carrier number at
room temperature is equal to the number of Fe2+
ions nFe2 ; carrier mobility mD was calculated by
mD sDC =enFe2 ; where e is the electronic charge.
The calculated results were shown in Fig. 5 with
the DC conductivity data. Mobility at co0:01 was
estimated as 109107 m2/V s. This low value
suggests small polaron formation. We note that
co0:01 is included in the range which Mott
predicted [10] and in which the formation of
polarons is possible. The polaron binding energy
results in an additional activation energy for
hopping conduction. The rapid increase in activation energy at co0:1 in Fig. 5 is considered to
originate in polaron formation.
The following discussion is based on AC
conductivities. Two theories have been advanced
for frequency-dependent polaron conduction, one
proposed by Pollak et al. [1315] and the other by
Pike [16]. Austin et al. [11] adapted Pollaks theory
to DC impurity conduction and obtained a
relationship for so due to impurity polaron
conduction, as follows:
sopofln1=ot0 g4 ;

30

where t0 is the pre-exponential factor of relaxation

time. This relationship implies that s in Eq. (2)
should be independent. We conclude that Pollaks
theory cannot explain the results in Fig. 9. Starting
from Pollaks theory, Pike constructed a new
model based on polaron hopping between randomly distributed localized states with overlapping
wave functions [16]. In this theory, s is given by
following expression:
s 1  6kB T=Wm ;

where Wm is the ground-state energy. This

relationship shows linear temperature dependence

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Y. Fukuda et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 325330

between s and T: The change in the specimens

with c 0:0023; 0.0063, and c 0:011 at low
temperatures can be explained by this theory.
This result suggests that the majority carriers for
co0:011 are small polarons. It should be noted
that this composition range is in good agreement with the low-mobility composition range
mentioned above.
Mobility was similarly estimated as 106
105 m2/V s for c > 0:01: The third item described
above suggests that the polaron effect is not
particularly important. Phillips et al. [5] have
shown that, at higher Fe2+ concentrations, Coulomb interactions between carriers are important
and result in an increase in activation energy for
hopping conduction. Therefore, the gradual increase in activation energy at c > 0:1 in Fig. 5 can
be interpreted in terms of Coulomb interactions
between carriers at the B site.

other hand, the high carrier mobility in the case of

c > 0:06 suggests that the polaron effect is not
particularly important, and the Coulomb interaction between carriers increases with Fe2+ ion
concentration at c > 0:01: Polaron binding energy
and Coulmb interaction are considered to result in
additional activation energy for hopping conduction. The mechanism of electrical conduction in
ferrite is therefore understood as the result of
competition between a polaron effect and electronelectron interactions.

References
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[2]
[3]
[4]
[5]

5. Conclusion
The electrical conductivity of exactly dened
MnZn ferrite single crystals was investigated
systematically, with particular emphasis on the
concentration of Fe2+ ions. Electrical conductivity
increases monotonously with Fe2+ concentration.
Measurements showed clearly that the activation
energy minimum is at an Fe2+ concentration of
c 0:06: Due to low carrier mobility, a smallpolaron effect is expected to be important at
co0:01: Small polaron conduction with a small
number of Fe2+ ions is also supported by the
frequency distribution of AC conductivity. On the

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[8]
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