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J Mater Sci: Mater Electron

DOI 10.1007/s10854-016-5473-6

Signature of multiferroicity and impedance analysis


of Co12xZnxFe22xLaxO4 nanoparticles
S. Shankar2,3 Manish Kumar1,2,3 P. Brijmohan1 Shiv Kumar1
O. P. Thakur3 Anup K. Ghosh1

Received: 23 April 2016 / Accepted: 1 August 2016


Springer Science+Business Media New York 2016

Abstract Effects of Zn2?/La3? co-doping on multiferroic


and impedance properties of co-precipitation derived
Co1-xZnxFe2-xLaxO4 (x = 0.0, 0.1 and 0.3) nanoparticles
have been investigated. The powder X-ray diffraction study
confirms the pure phase, cubic spinal structure and particle
size varies between 20 and 22 nm. The particle size
decreases with increase in co-substitution indicating the
short range ordering in CoFe2O4. The relaxations in
dielectric constant follow MaxwellWagner polarization
and arise out of charge transfer of Co and Fe ions in multioxidation states. The co-substitution of Zn2?/La3? in
CoFe2O4 at A and B sites respectively results in
improvement of Nquist plot and impedance of the
nanoparticle which confirms space charge polarization
caused by piling of charges at the interface of grain and
grain boundries. An unusual relaxation behavior is also
observed in co-substituted CoFe2O4 which may be useful
in enhancing the multiferroic properties at room temperature. It could be noted the GBs are more resistive as
compared to the grains, resulting in high impedance value
and non-Debye type behavior in the Co1-xZnxFe2-xLaxO4
nano particles. Low and stable coercivity (Hc) of 393.13 Oe
have been observed and a stable saturation magnetization
has been achieved at room temperature. PE loops have
& S. Shankar
sssubramaniam@arsd.du.ac.in
O. P. Thakur
opthakur@yahoo.com
1

Materials Research Lab., Department of Physics, Banaras


Hindu University, Varanasi 221005, India

Department of Physics, ARSD College, University of Delhi,


New Delhi 110021, India

Department of Physics, NSIT, New Delhi 110078, India

rounded corners which may be the due to the aggregation


of CoFe2O4 nanoparticles with each other resulting out of
their strong magnetization. Simultaneous occurrence of
saturation magnetization and weak ferroelectricity (PE
loop) with high values of impedance and dielectric constant
confirm the signature of multiferroicity in Co1-xZnxFe2-x
LaxO4 nanoparticles.

1 Introduction
Magnetic spinel nanostructured ferrites have attracted
considerable interest due to their remarkable electrical,
dielectric, optical, mechanical, thermal and magnetic
properties [1, 2]. Recently, the coexistence of any two of
the following three properties viz. ferromagnetism, ferroelectricity and ferroelasticity in the same material called
multiferroic materials. They have been paid a lot of
attention because of having very high potential for applications in the design of multifunctional devices such as
sensors, transducers, and information storage [3, 4]. There
are studies on spinel ferrite like CoFe2O4 nanoparticles [5]
and substitution in CoFe2O4 by various cations like Zn, La,
Mo, Mn etc. [48] in which the dielectric and magnetic
properties were found to be enhanced. The dielectric
behavior of ferrites is due to electric dipole moments that
are created upon the charge transfer between di- and
trivalent metal cations within the spinel structure. As a
consequence of that, spinel iron oxides exhibit high electrical resistivity, low eddy currents and large dielectric
losses, especially in the low frequency range. Thus ferrites
are very good dielectric materials and have many technological applications ranging from microwave to radio frequencies. The partial replacement of Fe3? by rare earth or
large ionic radius ion (La3?) in the spinel structure at

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J Mater Sci: Mater Electron

octahedral site has been reported to lead to structural distortion, which induces strain and significantly modifies the
electrical properties [9]. It has been also reported that the
Curie temperature and magnetostriction of substituted
CoFe2O4 are tunable by adjusting the suitable substitution
level. The substitution of Co2? by transition metal ions
(Zn2?, Mn2?) in the tetrahedral site [10] has modified
lattice parameter [11], dielectric properties because of the
formation of excess Fe2? ions which leads to increase in
hopping of electrons between Fe2? and Fe3? [12, 13] and
has improved the magnetoelectric coefficient and sensitivity [14].
Impedance spectroscopy is a well-developed tool to
separate out the grain (bulk) and grain boundary contribution to the total conductivity and is usually represented
as imaginary component of impedance (Z00 ) versus real
component of impedance (Z0 ). For this, the sample is
represented by an equivalent circuit containing three parallel RC elements connected in series. Each RC element of
the equivalent circuit gives rise to a semicircle with centre
of the real axis if there is a single value of relaxation time,
s given by s = 1/x, where x is the angular frequency
corresponding to maxima in Z00 versus Z0 plot [15]. The
colecole plots composed of three semicircles and confirmed the grain (bulk), GB and electrode effects respectively. The distinct process is represented by each
semicircle whose time constant is sufficiently separated
from the others over the range of measurement frequencies
[16]. The magnetic properties of spinel CoFe2O4 are sensitive to the types of cation and their distribution amongst
the two interstitial sites of spinel lattice. This feature of
CoFe2O4 has been extensively used in modern electronic
technologies, especially on magnetic and magneto-optical
recording media and is due to its significant properties
such as strong anisotropy, high saturation magnetization
and coercivity along with good mechanical hardness and
chemical stability [17]. CoFe2O4 exhibits ferromagnetism
where cobalt ions occupy the octahedral sites and Fe3?
ions are equally distributed in tetrahedral and octahedral
sites. The presence of large magnetocrystalline anisotropy
(390 kJ/m3) with a reasonable magnetization value makes
CoFe2O4 as a promising hard magnetic and recording
material [18].
The ability to prepare nanostructures with defined
morphologies and sizes in large scale is essential due to
their important physical and chemical properties and
potential for various technological applications since the
properties of nanomaterials are remarkably different from
that of their bulk counterpart. So that, in the present
investigation, we have prepared Zn2?/La3? co-substituted
CoFe2O4 nanoparticles through chemical co-precipitation
route and focused to investigate its multiferroic (electric
and magnetic) properties and impedance analysis.

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2 Experimental
Polycrystalline samples of Zn2?/La3? co-substituted cobalt
ferrite Co1-xZnxFe2-xLaxO4 (with x = 0.0, 0.1 and 0.3)
were prepared by co-precipitation route using high purity
salts of CoCl2, Fe(NO3)39H2O, anhydrous ZnCl2 and
La(NO3)36H2O. 1 M aqueous solutions were prepared and
mixed in respective stoichiometry composition. The solution mixture was kept for heating at 60 C to make it
homogenous. The ammonia solution was added drop by
drop to precipitate the metal salt solution in the form of
nanoparticles. The precipitates were washed several times
with de-ionized water to remove unwanted salts residual.
The precipitated nano-particles were dried at 100 C for
12 h. The samples obtained were rapid sintered at 700 C
for 4 h.
The structural parameters of the samples were studied
using X-ray Diffractometer employing Cu-Ka radiations.
The room temperature magnetic measurements were done
using Vibrating Sample Magnetometer. The powders were
then pressed into 1.0 cm-diameter pellets and dielectric
measurements were made using Nova Control (Alpha-A)
high performance frequency analyzer at a few selected
frequencies of 1 Hz1 MHz and in the temperature range
of 300800 K.

3 Results and discussion


The X-ray diffraction patterns for Co1-xZnxFe2-xLaxO4
(x = 0.0, 0.1 and 0.3) nanoparticles samples are presented
in Fig. 1. The well resolved peaks observed in the X-ray
diffraction patterns indicate that all the samples possess the
single phase with face-centered cubic structure. All peaks

Fig. 1 Room temperature powder X-ray diffraction patterns of


Co1-xZnxFe2-xLaxO4 (x = 0.0, 0.1 and 0.3) nanoparticles

J Mater Sci: Mater Electron

have been indexed using the standard JCPDS file for


CoFe2O4 (JCPDS #08-0234). The average crystallite size,
D, of the samples are estimated using the DebyeScherrers
equation [19]
D

0:9k
Bcosh

where D is the particle size, k is the wavelength of radia ), h is the Bragg angle and B is the
tion used (k = 1.5406 A
full width at half maxima (FWHM). Based on Debye
Scherrer equation, the average crystallite size is found to
decrease from 22 to 20 nm as co-substitution of Zn2?/La3?
ions is increased in cobalt ferrite. This suggests that Zn2?/
La3? ions co-substitution does not favour the long range
ordering of the atoms in the spinel structure.
Figure 2 shows the increase in the dielectric constant for
the Co1-xZnxFe2-xLaxO4 (for x = 0.0, 0.1 and 0.3) at
room temperature. This variation in relative permittivity
plot determines the dependency of dielectric constant on
polarization processes. Two weak relaxations appear at
room temperature, one at intermediate frequency and other
at higher frequency side for x = 0.3 composition, whereas
only one peak is observed for pure cobalt ferrite (x = 0.0)
on high frequency side. These peaks indicate different
regions of dominating polarization effect. Though
replacement of Co2? ions with non-magnetic Zn2? ions
should result in increase in dielectric constant, but the
increase is relatively higher due to the co-substitution of
rare earth La ions. The dielectric constant ranged between
411 and 25,189 at 10 kHz for x = 0.0 and x = 0.30
composition respectively. This dielectric dispersion could
be modeled by the MaxwellWagner theory of space
charge polarization. The space charge originates predominantly from the electron hopping between Fe2? and Fe3?
[20]. Higher the Fe2? concentration higher will be the
dielectric constant as per expectation due to the charge
transfer between the Fe2?Fe3?. The electron (Fe2?Fe3?)
or hole (Co3?Co2?) exchange in multi oxidation states
elements at A sites and B cationic sites (Table 2) present in
Co1-xZnxFe2-xLaxO4 system contributes dominantly
towards polarization. The contribution due to the holes is,
however, less compared to the electrons because of their
low mobility.
The colecole plots for Zn2?/La3? co-substituted cobalt
ferrite Co1-xZnxFe2-xLaxO4 (x = 0.0, 0.1 and 0.3)
nanoparticles were recorded at room (25 C) and high
(300 C) temperatures and are shown in Fig. 3a, b. The
size of the semicircle changes with grain size and the
number of grains. The plots of Fig. 3a, b confirm a single
and double semicircles starting from the origin, making an
intercept on the real axis with a large radius at low frequencies corresponding to the low-frequency side grain
boundary conduction and the high frequency side grain

Fig. 2 Variation of dielectric constant with frequency for Co1-xZnx


Fe2-xLaxO4 (x = 0.0, 0.1 and 0.3) nanoparticles

conduction respectively. The centres of the semicircle lie


on a line below the real axis indicating non-Debye behavior
[21]. If we consider the semicircle to be made up of a
parallel combination of RC elements, using equation f = 1/
2pRC, we can calculate the relaxation time (s), which is the
reciprocal of peak frequency [22]. The diameter of the
semicircle corresponds to the resistance of the grain [23].
Evolution of the impedance spectra with temperature is
interesting in co-substituted cobalt ferrites as shown in
Fig. 3b. The presence of new semicircular arc in all
Co1-xZnxFe2-xLaxO4 (x = 0.0, 0.1 and 0.3) nanoparticles
in the ColeCole plots with increasing temperature (at
300 C) is an indication of another type of conduction
process. This second semicircle confirms the GB effect in
the sample at high temperature. Few of the ColeCole plots
are not complete semicircle which is due to the presence of
only grain boundary resistance and suggesting that conduction is predominantly through the grain boundary volume for Co1-xZnxFe2-xLaxO4 (x = 0.0, 0.1 and 0.3)
nanoparticles. The reason for evolution from distinct to
overlapped semicircular arcs can be attributed due to the
disordering in atomic arrangement at the grain and grainboundary which results in enhanced electron scattering.
Moreover in polycrystalline materials, low frequency arc is
attributed to the grain boundary contribution and the high
frequency arc corresponds to the grain contribution [8].
The increase in Zn2?/La3? content in CoFe2O4 results in
the increase of diameter of the semicircle, indicating a rise
in grain interior resistance [23]. Thus, the total impedance
(Z = Z0 - jZ00 , where Z0 is the real part and Z00 is the
imaginary part of the impedance) of all samples is
increasing with increase in Zn2?/La3? content. Furthermore, with increasing temperature, the systematic changes
in the diameter of these semicircular arcs are clear. These
changes indicate the relative contributions from grain
resistance and grain boundary resistance which can also be

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J Mater Sci: Mater Electron


Fig. 3 a Nyquist (Colecole)
plots for Co1-xZnxFe2-xLaxO4
(x = 0.0, 0.1 and 0.3)
nanoparticles at room
temperature (25 C). b Nyquist
(Colecole) plots for
Co1-xZnxFe2-xLaxO4 (x = 0.0,
0.1 and 0.3) nanoparticles at
high temperature (300 C)

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J Mater Sci: Mater Electron


Table 1 Grain and Grain
boundary resistances in
Co1-xZnxFe2-xLaxO4 system

High Temp (300 C)

Room Temp
Rg

Rgb

Cg

Cgb

Rg

Rgb

Cg

Cgb

0.0

3.5E5

1.4E-7

220

600

2.662E-7

9.759E-9

0.1

2.04E6

2.67E6

4.09E-12

3.12E-12

1.05E5

1.7E5

1.058E-9

6.536E-10

0.3

1.12E6

1.16E-9

2.2E5

4.8E5

3.803E-9

1.743E-9

understood by the diameter of semicircular arcs. The corresponding resistances are tabulated in Table 1.
The distribution of grain size, grain boundaries, and the
ions that substitute Fe3?/Fe2? ions decide the structure,
electrical, and impedance properties of CoFe2O4. In Co1-x
ZnxFe2-xLaxO4 system, the effect of Zn2?/La3? incorporation is remarkable in terms of increasing impedance. The
enhanced electrical resistivity of Co1-xZnxFe2-xLaxO4 (0.1
and 0.3) compared to CoFe2O4 can be attributed to the
following important factors. The first most significant one is
the reduction of active Fe3? ions (at the B site) by La and
Co2? by Zn2? (at A site) substitution. Electron hopping
between Fe3? and Fe2? ions (Fe3? $ Fe2?) is the primary
mechanism by which electrical conduction occurs in ferrites. The hopping mechanism involves [24]: Fe3? ? e- $
Fe2? and La3? ? e- $ La2?; similarly p-type charge
transfer occurs between Co and Zn ions. Low concentration
of La ions induces reduction in Fe3? ions which decreases
the rate of hopping and hence conductivity, i.e., increases
resistivity of the compound. Apart from these microstructure variations with increasing Zn2?/La3? content contributes toward impedance enhancement. Distinctively,
increasing Zn2?/La3? content induces grain size reduction
and formation of insulating secondary phase at the GBs.
Figure 4 shows a step like decrease of Z0 with an
increase of both frequency and temperature for Co0.7
Zn0.3Fe1.3La0.3O7 nanoparticles. The coincidence of Z0
values at higher frequencies at all temperatures indicates a
possible release of space charge [25]. The inset of Fig. 4
shows frequency dependency of Z00 at different measuring
temperatures (150, 200, 250 and 300 C) for Co0.7Zn0.3
Fe1.3La0.3O7 nanoparticles. It shows that Z00 values attain a
maximum peak whose magnitude decreases with temperature indicating an increasing respective loss of the Co0.7
Zn0.3Fe1.3La0.3O7 nanoparticles. The peak shifts to higher
frequencies with increasing temperature indicating the
occurrence of relaxation in the Co0.7Zn0.3Fe1.3La0.3O7
system [26]. The peak broadening with increase in temperature confirms the presence of temperature dependent
electrical relaxation phenomenon in the material. The
relaxation process is due to the presence of immobile
species at low temperature and defects/vacancies at higher
temperatures [2628]. The relaxation behavior in the
material is also confirmed from the peak frequency around
100 Hz, which is in the middle point of the step-like

decreasing curve in Z0 . The relaxation phenomena, to the


best of our knowledge, has not been reported in the literature of CoFe2O4 but recent studies on multiferroic BiFeO3
based materials show a similar kind of behavior at 375, 400
and 425 C for BiFeO310 % BaTiO3 solid solution [21]
and 100 C for BiFeO3CoFe2O4 bilayered thin films [29].
It indicates that the CoFe2O4 is beneficial in shifting this
relaxation peak to low temperature side. But in our case we
observe the present relaxation behavior in Zn2?/La3?
co-substituted cobalt ferrite (Co0.7Zn0.3Fe1.3La0.3O7)
nanoparticles system at below 300 C and believe that it
will be helpful to achieve this phenomena at room temperature to make the suitable composites with Zn2?/La3?
co-substituted cobalt ferrite Co1-xZnxFe2-xLaxO4 which is
under investigation. Additionally, above 10 kHz, both Z0
and Z00 curves merge together and are independent of
temperature. It is confirmed from literature [30] that the
grain effects are attributed to the high frequency impedance
behavior, while GB effects are responsible for the low
frequency phenomena. The impedance spectroscopy of
high frequency side for the system confirms that Co0.7
Zn0.3Fe1.3La0.3O7 nanoparticles grains are insensitive to the
fast switch of applied alternate electric field. However, the
low frequency diffusion behavior confirms the GBs effect
in the Co0.7Zn0.3Fe1.3La0.3O7 nanoparticles system.
Figure 5a depicts the room temperature magnetization
(MH) of Zn2?/La3? co-substituted cobalt ferrite Co1-x
ZnxFe2-xLaxO4 (for x = 0.0, 0.1 and 0.3) samples. The
role of non-magnetic Zn2? ions substituted at tetrahedral
(A) sites of CoFe2O4 is to decrease the magnetic moment
and increase the saturation magnetization and of La3? ions
substituted at octahedral (B) site of CoFe2O4 is to decrease
saturation magnetization [6, 31]. Substitution of the low
magnetic moment of La3? ions (3.3 lB) as compared to
that of Fe3? ions (5 lB) the magnetization of B-sublattice
gets lowered which results in the decrease of saturation
magnetization [6, 32]. Since the magnetization of CoFe2O4
mainly depends on the concentration of Co2? ions at the
B-site, the contribution of Zn2?/La3? ions result in lowering the concentration of Co2? ions at the B-site
(Table 2).
Figure 5b and Table 2 show a low and stable coercivity
(Hc), slower decrease in remnant and saturation magnetization (Mr and Ms) values of Co1-xZnxFe2-xLaxO4 system.
It confirms the low loss and enhanced magnetic response of

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J Mater Sci: Mater Electron

Fig. 4 Frequency dependence of real a and imaginary impedance


b of Co0.7Zn0.3Fe1.3La0.3O7 nanocomposite at 150, 200, 250 and
300 C from 10 Hz to 10 MHz

Co1-xZnxFe2-xLaxO4 system. The magnetic moment (nB)


per formula unit in Bohr magneton (lB) was calculated by
using the following relation: [33]
nB

M  Ms
5585

where M is the molecular weight of particular composition


and Ms is saturation magnetization (emu/gm).The magnetic
moment (nB) obtained for Co1-xZnxFe2-xLaxO4 system
decreases from 3.36 to 1.63 lB as Zn2?/La3? concentration
increases from 0 to 30 %. Increasing of the co-substitution
of Zn/La in CoFe2O4 system causes rapid decrease in saturation magnetization which is due to the increase in the
molecular weight.
Polarization versus Electric field PE hysteresis loops
measured at different frequencies (50, 100 and 200 Hz
respectively) are plotted in Fig. 6. The PE loops have
rounded corners and indicate weak ferroelectricity, which
may be due to the large electrical leakage. The PE loops
do not display any saturation or concave form with electric
field, which may be, because of aggregation of CoFe2O4
nanoparticles with each other due to their strong magnetization and consequently channels are created [6]. Figure 6
confirmed the signature of weak ferroelectricity from the
frequency dependence of the PE curve at 300 K. It is
found that the width of the P-E loops decrease with

Table 2 Cations distribution,


magnetic parameters in
Co1-xZnxFe2-xLaxO4 system

123

Fig. 5 a Room temperature hysteresis loops of Co1-xZnxFe2-xLaxO4


(x = 0.0, 0.1 and 0.3) nanoparticles at 5000 Oe. b Enlarged Room
temperature hysteresis loops of Co1-xZnxFe2-xLaxO4 (x = 0.0, 0.1
and 0.3) nanoparticles at 5000 Oe

increase the frequency from 50 to 200 Hz, which supports


the ferroelectric behavior of this composition [6]. So, there
is a clear evidence of possible multiferroicity in the nonmagnetic Zn/La co-doped cobalt ferrite system. The detail
study is under investigation to give the actual mechanism
of the multiferroicity in the present Zn/La-doped CoFe2O4
system.

A site

B site

Ms (emu/gm)

Mr (emu/gm)

Hc (Oe)

nB (lB)

0.0

Co0.5Fe0.5

Co0.5Fe1.5

87.63

12.33

393.13

3.36

0.1

Co0.4Zn0.1Fe0.5

Co0.5Fe1.4La0.1

58.45

8.26

393.13

2.62

0.3

Coo.4Zn0.3Fe0.3

Co0.4Fe1.3La0.3

33.81

4.99

393.13

1.63

J Mater Sci: Mater Electron

References

Fig. 6 PE loop at different frequencies for Co0.7Zn0.3Fe1.3La0.3O7 at


room temperature

4 Conclusions
Zn2?/La3? co-substituted CoFe2O4 nanoparticles have
been successfully prepared by chemical co-precipitation
method. The powder XRD patterns of Zn2?/La3? co-substituted CoFe2O4 nanoparticles showed a similar single
phasic cubic spinel structure as that of CoFe2O4 nanoparticles and the decrease in particle size with increase in
Zn2?/La3? concentration (x) indicated the short range
ordering in CoFe2O4. The dielectric study confirmed the
samples follow MaxwellWagner polarization arising out
of charge transfer of ions in multi-oxidation states. Impedance study revealed the enhanced impedance values and
non-Debye type behavior in Zn2?/La3? co-substituted
CoFe2O4 nanoparticles. Room temperature magnetization
study showed the low and stable coercivity with saturated
M-H loops. PE loop measurement confirmed the weak
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aggregation of CoFe2O4 nanoparticles with each other
resulting out of their strong magnetization. The high values
of impedance and dielectric constant with saturation
magnetization and variation of weak ferroelectricity (PE
loop) with frequency confirms the multiferroic nature of
Co1-xZnxFe2-xLaxO4 nano particles.
Acknowledgments Authors are thankful to NPL, New Delhi, India
and IIT-BHU, Varanasi, India for their characterization facilities.

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