Grain size effect on activation energy in spinel CoFe2O4 ceramic

Sweety Supriya, Sunil Kumar, and Manoranjan Kar

Citation: AIP Conference Proceedings 1731, 110025 (2016); doi: 10.1063/1.4948046

View online: http://dx.doi.org/10.1063/1.4948046
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 Grain Size Effect on Activation Energy in Spinel CoFe2O4
Ceramic
Sweety Supriya*, Sunil Kumar and Manoranjan Kar
Department of Physics, Indian Institute of Technology Patna, Patna-800013, India. Email: sweety@iitp.ac.in

Abstract. Cobalt ferrite of different average crystallites (from nanocrystallite to micro crystallites) has been
prepared by the Sol-Gel Method. The X-ray diffraction (XRD) analysis confirms the cubic spinel phase with no
trace of impurity phases. The effect of annealing temperature on micro structure and electric transport properties as
a function of frequency and temperature has been studied. It is observed that the electric impedance and
conductivity are strongly dependent on grain size. The impedance spectroscopic study is employed to understand
the electrical transport properties of cobalt ferrite.
Keywords: Impedance, Electrical conductivity, XRD, Grain size
PACS: 61.05C; 72.15.Lh; 72.15.Eb; 2.20Ee

INTRODUCTION
MATERIAL AND METHODS
Ferrites are the extensively used nanomaterial in
The starting materials used for the synthesis are
today’s scenario of its application like sensors,
cobalt nitrate Co(NO3)3. 6H2O procured from (Merck),
actuators, microwave absorber, micro-radiowave-
Iron nitrate Fe(NO3)3.9H2O procured from Alfa Aesar
frequency range electronic devices etc. [1,2]. Spinel
and Citric Acid procured from Merck.
ferrites are preferred intensively due to their unique
CoFe2O4 was prepared using all the above
electrical property in the range from low to high
mentioned precursor materials by the sol-gel method
frequencies. Amongst all the spinel ferrite, cobalt
[2]. The one fourth part of synthesized samples were
ferrite is of great importance because of its high
annealed at 400 oC, 600 oC, 800 oC and 1000 oC
dielectric constant in wide frequency range along with
temperature separately in air atmosphere. The sample
very good magnetic properties, i.e., high saturation
is heated at different temperatures to obtain various
magnetization, magneto-crystalline anisotropy etc.
grain sizes. The X-ray Diffraction pattern has been
Moreover these materials exhibit excellent chemical
recorded using Rigaku TTRX III diffractometer. The
stability, mechanical hardness [2]. .CoFe2O4 belongs
FESEM micrographs of all the samples have been
to an inverse spinel structure having common formula
recorded. Electroding were done on the edges of each
AB2O4. This formula consists of two sites: A and B. In
pellet using silver paint to have electrical connections
this structure, half of the trivalent cation (Fe3+)
for electrical measurement. The ac impedance
completely occupied by A site and half of the
measurement has been carried out by using an
trivalent cation (Fe3+) and divalent cation (Co2+) are
impedance analyzer (N4L PSM LCR, Model: 1735,
fully occupied by B site. In inverse spinel structure,
UK).
the 32 divalent oxygen ions are incorporated to form
closed pack FCC through 64 tetrahedral interstitial A 2. RESULTS AND DISCUSSIONS
sites. The electrical and magnetic properties of
CoFe2O4 highly depend on the site (A and B) The X-ray diffraction (XRD) pattern of CoFe2O4
occupancy of Co and Fe. Also the electrical response with temperature variation is shown in the figure 1.
of cobalt ferrite depends upon grain size, grain XRD pattern confirms the phase formation without
boundary and porosity which depend upon the method any impurity and indexed to Fd 3m space group
of preparation, final sintering temperature and duration with cubic crystal symmetry. The average crystallite
[3]. Hence different grain size (nano to micrometer) size was calculated using a full width half maximum
cobalt ferrite has been prepared by the sol-gel method of the (311) peak by employing Debye-Scherrer’s
and post annealing at different temperatures to explore formula [4] and values are listed in the table I. Typical
the grain size effect on electrical transport properties. field emission scanning electron microscopy (FE-
In this regard impedance and ac conductivity SEM) micrograph for CoFe2O4 is shown in the figure
properties of cobalt ferrite have been discussed. 2. The average particle size found to be 40 nm which

DAE Solid State Physics Symposium 2015

AIP Conf. Proc. 1731, 110025-1–110025-3; doi: 10.1063/1.4948046
Published by AIP Publishing. 978-0-7354-1378-8/$30.00

110025-1
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 is close to the crystallite size (38.9 nm) obtained from
the XRD. Similarly, it is observed that the crystallite CoFe2O4 400 oC 600 oC
size for the samples annealed d 800 oC are same with 800 oC 1000 oC
the particle size obtained from FE-SEM. This is
because the particle size can be calculated from XRD

Intensity (A.U.)
pattern correctly if size is ¢ 50 nm [4]. However the
sample annealed at 1000 oC is in larger grains. Hence
the particle size calculated from the XRD analysis is
different than FE-SEM. The particle size for this

(311)
sample found to be 120 nm from FE-SEM micrograph.

(220)

(440)
(400)
(111)

(511)
(222)

(533)
(422)
ELECTRICAL CHARACTERIZATION
10 20 30 40 50 60 70 80
The effect of the frequency on the real part of 2T (Degree)
impedance (Zˈ) with different grain sizes due to
different annealing temperature is illustrated in the FIGURE 1. XRD pattern of CoFe2O4 of particular
figure 3. The decrease in Zˈ with increase in frequency annealing temperatures.
is the normal behavior of the ferrite [5]. Small grain
size results in increase in number of grain boundaries.
Therefore the greater number of energy barriers
becomes an obstacle in the conduction of charge
carriers and results in high impedance. But it is not
valid for the samples where the bulk dielectrics are
highly dominated over the grain boundary. In this case,
if the particle size increases the bulk dielectric
contribution increases more compared to decrease due
to decrease of grain boundaries. Hence the above
discussion concludes that the dielectric constant can be
increased or decreased with the grain size which
entirely depends upon the material characteristics. In
the present case cobalt ferrite’s dielectric constant FIGURE 2. SEM micrograph of CoFe2O4 annealed at
increases with the increase of grain size. The grain can 800 oC.
be considered as a core-shell model, the dipole in
surface (shell wall) behaves differently compared to 500 (11.9 nm)
(15.5 nm)
the core (natural dielectric behavior of cobalt ferrite
400 (38.9 nm)
i.e., bulk dielectric). The increase in annealing (70.4 nm)
temperature, grain size increases, surface to volume 300
Z' (K:)

ratio decreases, the effect of surface charge

polarization decreases due to high crystallization. But 200
the contribution from dipole polarization is higher for
100
the higher grain size samples. The samples with very
large grains (annealed at 1000 oC) show an abrupt 0
change in dielectric constant, hence in impedance as 0
10
1
10 10
2
10
3
10
4
10
5 6
10
shown in figure 3. It could be due to a reduction of the Frequency (Hz)
Fe3+ cations into Fe2+ cations, which causes an
increase in the number of electrons hoppings and FIGURE 3. Variation of the real part of impedance
hence an improvement in dielectric polarization and with respect to frequency of CoFe2O4 annealed at
impedance [3, 6]. However, it needs further different temperatures.
investigation to confirm the reduction of Fe3+ to Fe2+.
The frequency variation of the imaginary part of The appearance of peak at certain frequencies
the cobalt ferrite with different particle size is shown indicates the appearance of relaxation times. If the
in the figure 4. The magnitude of Zˈˈ is found to be frequency of applied external field is less than natural
lower than the magnitude of Zˈ, which indicates that ac frequency, results in positive relaxation. When the
loss is lower than the charge storage. The ac loss is a frequency of applied external field is greater than the
maximum when the applied external frequency equals internal field natural frequency results in negative
the flipping frequency of cations. relaxation. The magnitude of Zˈˈ increases with the

110025-2
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 increase in grain size. The reason for this is same as conductivity decreases with the increase particle size,
explained earlier for Zˈ. The activation energy is which supports the earlier observation found
obtained by analyzing the ac loss data (frequency corresponding to impedance. The nature of electrical
variation of Zˈˈ) where the data were plotted log (fmax) transport in the sample could be studied in terms of ac
verses 1000/T [3]. The activation energy is found to conductivity. The conductivity is observed to decrease
be 0.00029 eV , 0.00025 eV, 0.00027, 0.0.00057 eV with the increasing frequency corresponding to
for CoFe2O4 annealed at temperatures 400 oC, 600 oC, annealing temperature, which validate well with the
800 oC and 1000 oC respectively. Therefore the large results of impedance spectra of figure 4 and figure 5.
particle size sample requires high activation energy for The ac conductivity increases with frequency which is
the hopping of charge carriers. the normal behavior of the ferrite [5].

TABLE 1. Crystallite size and particle size for CoFe2O4 CONCLUSION

annealed at different temperatures. Cobalt ferrite with different average grain size has
been synthesized by the sol-gel method. Samples are
Temperature Full Width Crystallite size
(oC) Half maxima (XRD) crystallize to simple cubic with Fd 3m space group
nm which is consigned from the XRD analysis. Crystallite
400 0.73168 11.9 size (calculated from XRD) and particle size
600 0.7538 15.5 (calculated from FESEM) are almost equal at the range
800 0.22379 38.9 of nano size. The grain size variation in CoFe2O4
1000 0.12385 70.4 causes significant changes in the electrical properties.
Electrical transport property studies reveal the abrupt
change in impedance while increasing the particle size
(11.9 nm) from nano to micrometer and validated the result of
250 (15.5 nm) impedance and ac conductivity to each other. The
(38.9 nm)
200 (70.4 nm)
activation energy for hopping of charge carriers
increases monotonously with the increase in particle
150 size.
Z'' (K:)

100
ACKNOWLEDGMENTS
50
Authors are thankful to CSIR, DST and DAE, India
0 vide sanction number 03/1183/10/EMR-II,
1 2 3 4 5 6
10 10 10 10 10 10 SR/FTP/PS-103/2009 and 2011/20/37P/03/BRNS/007
Frequency (Hz) respectively for financial assistance and also UGC-ref.
No.: 4050/ (NET-JUNE 2013) for JRF.
FIGURE 4. Variation of the imaginary part of impedance
(Zˈˈ) with respect to frequency of CoFe2O4 annealed at
different temperature.
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and Ch. Leroux, Materials Research Bulletin 59, 49–58
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-1
lnVa.c(Z) (:m)

2. Lawrence kumar, Pawan kumar and Manoranjan Kar,

-10 Appl Nanosci 3, 75–82 (2013).
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(11.9 nm) Govindaraj, Journal of Applied Physics 101, 084111-
-12 (15.5 nm) 084116-6 (2007).
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(70.4 nm)
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Diffraction, Boston: Addison-Wesley, 1978, pp. 388-390.
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084321-084321-8 (2012).
FIGURE 5. Variation ac conductivity with respect to
6. Anjali Verma and Dinesh C. Dube, J. Am. Ceram. Soc.
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A variation of ac conductivity of CoFe2O4 as a
function of frequency with varying particle size is
shown in the figure 5. It is observed that the ac

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