ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 320 (2008) 270–275

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Electrical and magnetic characterization of nanocrystalline Ni–Zn

ferrite synthesis by co-precipitation route
I.H. Gul, W. Ahmed, A. Maqsood
Thermal Physics Laboratory, Department of Physics, Quaid-i-Azam University, Islamabad 45320, Pakistan
Received 11 April 2007; received in revised form 24 May 2007
Available online 6 June 2007

Abstract

Nickel zinc ferrite nanoparticles Ni1xZnxFe2O4 (x ¼ 0.25, 0.5, 0.75, 1) have been prepared by the chemical co-precipitation route.
The samples were characterized by X-ray diffraction (XRD), DC electrical resistivity, dielectric constant and low field AC magnetic
susceptibility. The powder XRD patterns confirm the single phase spinel structure for the synthesized materials. The crystallite size was
calculated from the most intense peak (3 1 1) using the Scherrer formula. The crystallite size was found within the range 7–15 nm. The
crystallite size decreases with increasing zinc concentration. DC electrical resistivity decreases as the temperature increases indicating that
the samples have semiconductor like behavior. DC electrical resistivity of the samples at room temperature was found to vary from
1.67  109 to 4  109 O cm with zinc concentration. The activation energy and drift mobility were calculated from DC electrical resistivity
measurements. The dielectric constant for all the compositions has been studied as a function of frequency in the range from 500 Hz to
1 MHz at room temperature. The dielectric constant follows the Maxwell–Wagner interfacial polarization. AC magnetic susceptibility
measurements were carried out as a function of temperature to measure the transition temperature, which was found to decrease with
zinc concentration. The decrease of transition temperature has been explained by the distribution of cations on A and B sites.
r 2007 Elsevier B.V. All rights reserved.

PACS: 75.30.Cr; 82.80.Jp; 84.37.+q; 78.20.Ci; 75.50.Gg; 61.46.Df; 61.10.Nz

Keywords: AC magnetic susceptibility; Activation energy; Electrical resistivity; Dielectric constant; Ferrite; Nanoparticle: X-ray diffraction

1. Introduction properties of the Ni–Zn ferrite are very sensitive to the

method of preparation, the amount and the type of
Polycrystalline spinel ferrites are widely used in many substitutions [5]. This type of ferrite belongs to the group
electronic devices. These are preferred because of their high of so-called hopping semiconductors. The basic conduction
electrical resistivity, chemical stability, mechanical hard- process for Ni–Zn ferrite is due to thermally activated
ness and reasonable cost [1–4]. These are also useful to hopping of electron from one cation to another [6] and not
prevent and eliminate radio frequency interference to audio due to thermal creation of charge carriers. Ni–Zn ferrite is
systems. The systems made up of nanoparticles are generally used at high frequency due to its low losses; the
intensively studied both theoretically and practically due losses in these materials are also influenced by the grain
to their electric, dielectric and magnetic properties that are size. Zinc is known to play a decisive role in determining
sensibly different from those of the bulk materials and their the ferrite properties [7]; hence, compositional variation in
possible applications in various fields. Ni–Zn ferrites are the ferrites has been brought about by varying the zinc
well-known technological magnetic materials finding their concentration. The redistribution of metal ions over the
applications in various electronic devices. The physical tetrahedral and octahedral sites in the spinel lattice on
incorporation of zinc is responsible for the modification of
Corresponding author. ferrite properties. Nickel and zinc are known to have very
E-mail addresses: [email protected], [email protected] strong preference for the tetrahedral and octahedral sites,
(A. Maqsood). respectively, making Ni-ferrite a model inverse ferrite and

0304-8853/$ - see front matter r 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2007.05.032
 ARTICLE IN PRESS
I.H. Gul et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 270–275 271

Zn-ferrite a model normal ferrite [8]. However, nano-sized The relationship between resistivity and temperature
Ni- and Zn-ferrite are known to exist as mixed spinel may be expressed as
structures [9,10].
However, the synthesis route also plays a crucial role, so r ¼ r0 eDE=kB T , (1)
that samples of comparable crystallite size prepared by where r is the DC electrical resistivity at temperature T, kB
different processes show different electrical and magnetic is the Boltzmann constant and DE is the activation energy
properties. Large-scale applications of ferrites with nano- corresponding to the electrical process.
particles and the tailoring of magnetic properties have Drift mobility, md of all the samples was calculated using
prompted the development of several widely used methods, the following relation [12,22]:
including sonochemical reactions, sol–gel techniques,
1
reverse micelles, host template, chemical co-precipitation, md ¼ , (2)
microemulsion procedures, precursor techniques, micro- ner
wave plasma and mechanical milling for the fabrication of where e is the charge of electron, r is defined above and n is
stoichiometric and chemically pure ferrite nanoparticles the concentration of charge carriers and can be calculated
[11–20]. from the well known equation
Of all these techniques, chemical co-precipitation seems Nrm PFe
to be the most convenient for the synthesis of nanoparticles n¼ , (3)
M
because of its simplicity and better control over crystallite
size and other properties of the materials. where N is the Avogadro’s number, M is the molecular
The results of our systematic investigation of crystal weight of the compound, PFe is the number of iron atoms
structure, DC electrical resistivity, dielectric constant, loss in the chemical formula of the ferrites and rm is defined
factor and magnetic transition temperature of Ni–Zn above.
0

ferrite nanoparticles are reported in this paper. The dielectric constant (e ) measurements were carried
out in the frequency range from 500 to 1 MHz at room
2. Experimental temperature using LCR meter bridge (WK LCR 4275).
The dielectric constant was determined from the formula
Ferrite nanoparticles Ni1xZnxFe2O4 (x ¼ 0.25, 0.50, Cd
0.75, 1) were prepared by chemical co-precipitation route. 0 ¼ , (4)
0 A
In order to obtain the desired compositions, stoichiometric
amounts of NiCl2  6H2O, ZnCl2 and FeCl3  6H2O were where C is capacitance of the pellet in farads, d the
dissolved in ultra-pure water. The solutions of thickness of the pellet in meters, A the cross-sectional area
NiCl2  6H2O, ZnCl2 and FeCl3  6H2O in their stoichiome- of the flat surface of the pellet and e0 is the permittivity
try (100 ml of 0.05 M NiCl2  6H2O, 100 ml of 0.2 M constant of free space.
FeCl3  6H2O, 100 ml of 0.05 M ZnCl2, in the case of To measure the Curie temperature, high-temperature AC
Ni0.5Zn0.5Fe2O4 and similarly for the other values of x) magnetic susceptibility apparatus was used. The existing
were dissolved in distilled water with a constant stirring. AC magnetic susceptibility apparatus in the research
The neutralization was carried out with 1.5 M sodium laboratory was modified for high-temperature measure-
hydroxide solution. The reaction temperature was kept at ments. The modified apparatus was calibrated with pure
85 1C for 45 min. The pH of the reaction was kept at 12. All nickel prior to measurement on the samples.
the chemicals were of analytical grade. The precipitates
were thoroughly washed with distilled water until the 3. Results and discussions
washings were free from sodium and chloride ions. The
product was dried in an electric oven at a temperature of The XRD pattern for the samples Ni1xZnxFe2O4 (for
100 1C for overnight to remove water contents. The dried x ¼ 0.25, 0.50, 0.75, 1) are shown in Fig. 1. Analysis of the
powder was mixed homogeneously in a cleaned agate diffraction pattern of all the samples confirmed the
mortar and pestle. The ground powder was then palletized formation of spinel cubic structure. Crystallite size for
using hydraulic press. A load of 50 kN for 3 min was each sample was calculated using the Scherrer formula [22]
applied on each pellet. The pellets were sintered at 600 1C considering the most intense peak (3 1 1). The crystallite
for 2 h, then the furnace was switched off. The samples size decreases from 15 to 7 nm with Zn2+ concentration.
were cooled by slow cooling to room temperature. The values of crystallite size are also tabulated in Table 1.
The structure and crystallite size were determined The above observation tells us that presence of zinc
from the X-ray diffraction (XRD) data. XRD data were obstructs the crystal growth. The surface temperature
taken at room temperature using Cu Ka (l ¼ 1.5406 Å) effects the molecular concentration at the surface of the
radiation. The particle size, t311; lattice constant, a; crystal, and hence, the crystal growth [23]. The formation
measured density, rm; X-ray density, rx; specific surface of Zn-ferrite is more exothermic as compared to the
area, S; and porosity P, were calculated using the standard formation of Ni-ferrite [24]. Thus, the crystal surface
relations [21,22]. temperature increases with addition of zinc, decreasing the
 ARTICLE IN PRESS
272 I.H. Gul et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 270–275

molecular concentration at the crystal surface and hence, from this table that the lattice parameter increases from
obstructing the grain growth. 8.359 to 8.438 Å with Zn2+ concentration. The addition of
The lattice parameter, measured density, X-ray density Zn2+ in Ni-ferrite causes the Fe3+ ions to migrate from A
and crystallite size are also tabulated in Table 1. It is seen site to B site. Zn2+ ions being larger (0.82 Å) than Fe3+
ions (0.67 Å) make the A sites and thus the lattice expands,
increasing the lattice parameter. From Table 1, it is seen
that the measured density and X-ray densities increase
from 2.81 to 2.91 g cm3 and 5.30 to 5.39 g cm3 with Zn2+
concentration, respectively. This may be due to the fact
that Zn2+ has greater atomic weight (65.39 amu) than the
Ni2+ (58.69 amu) ions.
The resistivity of the ferrites, in general, depends on the
density, porosity, grain size and chemical composition of
the sample [25]. Conductivity in these ferrites is reported to
occur as a result of electron hopping between ions of the
same element (Fe) existing in different valence states (Fe2+
and Fe3+) on equivalent lattice sites [26,27]. The DC
electrical resistivity for all the samples was measured by
two probes method in a temperature range from 400 to
600 K. The measured DC resistivity of the samples at room
temperature was found to vary from 1.67  109 to
4  109 O cm with zinc concentration as given in Table 1.
From Fig. 2 it is seen that the DC electrical resistivity
shows a linear decrease with temperature for all the
samples. The variation of resistivity is explained on the
basis of actual location of cation in the spinel structure.
Occurrence of ions in more than one valence states is
caused by the preparation conditions, especially, the
sintering temperature: Fe2+ ions in the lattice are created
due to zinc loss during the sintering process. Loss of Zn
results in cation vacancies and unsaturated oxygen ions.
The excess electrons on oxygen then bond with the
neighboring Fe3+ ions in the spinel lattice due to
electrostatic interaction giving rise to Fe2+ ions. The
overall charge balance is restored by oxygen loss from the
sample. Formation of Fe2+ ions leads to deviations from
ferrite stoichiometry. The number of Fe2+ ions depends on
the amount of zinc lost from the sample on volatilization,
which in turn is dependent on the sintering temperature of
the ferrite. Higher the sintering temperature, greater is the
Fig. 1. Indexed X-ray diffraction patterns of Ni1xZnxFe2O4 ferrite possibility of Fe2+ formation. Creation of Fe2+ ions gives
nanoparticles. rise to electron hopping between the Fe ions in +2 and +3

Table 1
Crystallite size(t311), lattice constant (a), volume (V), measured density(rm), X-ray density(rx), resistivity(r), activation energy(DE), correlation coefficient
(R), drift mobility (md) and transition temperature(Tt)

Parameter x ¼ 0.25 x ¼ 0.5 x ¼ 0.75 x ¼ 1.00

t311 (nm) 15 12 9 7
A (Å) 8.359 8.396 8.403 8.438
V (Å3) 584 591 593 600
rm (g cm3) 2.81 2.83 2.91 2.96
rx (g cm3) 5.30 5.34 5.36 5.39
r (  108 O cm) at 300 K 16.7 19.83 8.76 17.3
DE (eV) 0.507 0.51 0.597 0.705
R 0.998 0.999 0.999 0.999
md (cm2 V1 s1) at 300 K 0.261  1012 0.220  1012 0.488  1012 0.245  1012
Tt (75 K) 477 337 140 –
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I.H. Gul et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 270–275 273

15 x=0.25
x=0.25 2.0x10-9
x=0.50 x=0.50
14
x=0.75
x=0.75
1.5x10-9 x=1.00
13 x=1.00

μd (cm2.v-1.s-1)
12
lnρ (Ω-cm)

1.0x10-9

11
5.0x10-10
10

9 0.0

8
20 22 24 26 28 30
7 1/kBT (eV)-1
20 22 24 26 28 30
Fig. 3. Drift mobility as a function of inverse temperature (1/kBT) for
1/kBT (eV)-1
Ni1xZnxFe2O4 ferrite nanoparticles.
Fig. 2. Variation of DC electrical resistivity (ln r) with inverse tempera-
ture (1/kBT) for Ni1xZnxFe2O4 ferrites nanoparticles.

1.6x104 x=0.25
valence states. The hopping probability depends upon the x=0.50
activation energy, which is associated with the electrical x=0.75
Dielectric constant (ε′)

energy barrier experienced by the electrons during hopping. 1.2x104 x=1.00

The activation energy calculated from the slope of
inverse temperature vs. ln r plot, lies within the range
8.0x103
0.507–0.705 eV. It is seen from Table 1 that values of
activation energy increase with zinc concentration. This
increase in activation energy can be related with the 4.0x103
increase in lattice constant ‘a’ with zinc concentration. The
increase in the value of ‘a’ manifests itself as increase in
inter-ionic distances in the ferrite and consequently, in an 0.0
increase in the barrier height encountered by the hopping
6 7 8 9 10 11 12 13 14
electrons [28].
ln f(Hz)
The drift mobility (md) of all the samples was calculated
using Eqs. (2) and (3) and is plotted as a function of the Fig. 4. Frequency dependence of dielectric constant (e0 ) for Ni1xZnx
inverse temperature in Fig. 3. It is seen from the figure that Fe2O4 ferrite nanoparticles.
the drift mobility increases with increase in temperature.
This is due to the fact that with increase in temperature
more carriers find energy to overcome the activation energy and ferric ions cannot follow the alternating field, which
barrier, which results in an increase in their mobility. causes a decrease in the contribution of interfacial
The dielectric properties of Ni–Zn ferrites were studied polarization in dielectric constant, and thus, we see a
in a frequency range from 500 to 1 MHz at room decrease in the dielectric constant.
temperature. The dielectric constant was calculated using The temperature dependence of AC susceptibility
Eq. (4). The dielectric constant decreases with increase in measurements for all the samples was carried out using a
frequency for all the samples as shown in Fig. 4. The low field of 0.6 Oe from 77 to 650 K. The AC magnetic
decrease is rapid at lower frequencies and slower at higher susceptibility data as a function of temperature for the
frequencies. The decrease in dielectric constant with system Ni1xZnxFe2O4 are shown in Fig. 5. It is observed
increase in frequency is a normal dielectric behavior. This from the plots that AC magnetic susceptibility falls sharply
normal dielectric behavior is also observed by several other when the magnetic state of the samples changes from
investigations [29–31]. The dielectric structure was sup- ferrimagnetic to paramagnetic except for x ¼ 1 sample.
posed to be composed of two layers. The highly conducting For this sample, the magnetic transition temperature is
grains, which are separated by relatively poor conducting low, around 10 K [32]. The magnetic properties of
substances called the grain boundaries [30]. This causes the Ni1xZnxFe2O4 ferrites strongly depend on the Zn2+
localized accumulation of charges under the influence of concentration. The change in transition temperature is
electric field, which results in interfacial polarization. At due to the influence of cations stoichiometry and their
higher frequencies the electron exchange between ferrous occupancy in the specific sites. In addition, formation of
 ARTICLE IN PRESS
274 I.H. Gul et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 270–275

of the samples at room temperature was found to vary

2.8x10-3 x=0.25
from 1.67  109 to 4  109 O cm with Zn2+ concentration.
x=0.50
Inverse susceptibility (arb. units)

Activation energy calculated from the DC electrical

x=0.75
2.4x10-3 resistivity vs. temperature for all the samples ranges from
x=1.00
0.507 to 0.705 eV. The activation energy increases with Zn
2.0x10-3 concentration. The drift mobility was also determined from
the resistivity measurement. It has been observed that drift
1.6x10-3
mobility increases by increasing temperature. The dielectric
constant of all the samples decreases with increase in
frequency.
1.2x10-3

Acknowledgments
8.0x10-4
100 200 300 400 500 600 The authors would like to acknowledge Higher Educa-
Temperature (K) tion Commission (HEC) Islamabad, Pakistan and Quaid-i-
Azam University Research fund (URF) for providing
Fig. 5. Temperature dependence of inverse AC magnetic susceptibility (1/
w) for Ni1xZnxFe2O4 ferrite nanoparticles. Transition temperatures are financial support for this work.
indicated by the straight lines.
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