Journal of Magnetism and Magnetic Materials 369 (2014) 155–161

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Magnetodielectric properties of CoFe2O4–BaTiO3

core–shell nanocomposite
M. Malar Selvi, P. Manimuthu, K. Saravana Kumar, C. Venkateswaran n
Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai 600025, India

art ic l e i nf o a b s t r a c t

Article history: The magneto-electric (ME) and multiferroic CoFe2O4 (CFO)/BaTiO3 (BTO) core–shell nanocomposite is
Received 23 April 2014 prepared by co-precipitation followed by citrate-gel method. The XRD patterns indicate that the
Received in revised form magnetic CFO phase is compatible with the ferroelectric BTO phase. The core–shell nature with
6 June 2014
homogeneous mixing of magnetic and dielectric phase is confirmed by microstructural analysis. The
Available online 19 June 2014
magnetic and ferroelectric phase preserves their basic individual properties in the core–shell form. The
Keywords: magnetodielectric (MD) response of the nanocomposite is attributed to magnetostriction of CFO at low
Core–shell frequencies, and at high frequencies is due to magnetostriction and the magnetoresistance effects. The
Nanocomposite Maxwell–Wagner effect combined with the magnetoresistance (MR) is dominant at the intermediate
Magnetocapacitance
frequencies. The ME coupling susceptibility of the sample was indirectly derived through the MD
Magnetoimpedance
measurements by eliminating the combined ‘Maxwell–Wagner and the magnetoresistive effects’. ME
Magnetoelectric coupling susceptibility
coupling susceptibility of 0.6 70.2 mV/cm Oe is obtained indirectly by MD measurements at room
temperature upto a maximum field of 7 kOe. The observed MD effects are attributed to the presence of
magnetostrictive and magnetoresistive behavior of core–shell nanocomposite.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction piezoelectric phase having high dielectric susceptibility. Another

Multiferroic materials attract current interest due to the pre-
sence of magnetic and electric orders in the same phase [1–6]. The
coupling between these orders, give an interesting phenomenon
known as magneto-electric (ME) effect [7]. This effect plays an
essential role in the design of multifunctional device and hence
miniaturization of electronic components including novel memory
elements, data storage devices, high sensitivity magnetic field
detectors etc. [8,9]. The ME effect on single phase materials usually
occurs at extreme conditions of very high magnetic fields and at
low temperatures [9]. From the application point of view, the room
temperature ME coupling at low applied fields is desirable which
requires attention towards the strain induced coupling in the
composite system [10]. The ME response of a composite depends
on the efficiency of strain transfer across the interface (magnetic/
elastic/electric) and requires a strong inter-phase elastic interac-
tion [11,12]. Compared to the composites of coarse grains, the
nanophase materials have the ability of enhancing the ME effect
due to the enhanced mechanical coupling between the constituent
phases [13]. Hence the special interest is towards the production
of nanocomposites consisting of the magnetostrictive phase with
high magnetic permeability and high electrical resistivity, and
n
Corresponding author.
E-mail address: cvunom@hotmail.com (C. Venkateswaran).
important aspect is that the magnetostrictive and the piezoelectric
phases are chemically inert with each other, even at high tem-
peratures. The combination of these properties yields material
with excellent magnetic and dielectric properties [14,15].
Accordingly, the strength of coupling is strongly related to the
strain fields of various geometries. Recently, there are several
reports on the ME behavior of nanocomposites with (a) dispersed
particles/particulates (0–3 type) (b) fiber/rod configurations (1–3
type) and (c) layered structures/laminates (2–2 type) [12,16,17].
Among these, the laminate composites are promising candidates
to gain better ME responses than others, but involving a multiple-
step assembly process. Thus, research emphasis is on enhancing
the ME coefficient in 0–3 type particulate composites. The chal-
lenges associated with this type of composites are (i) reducing the
diffusion across the interface, (ii) reducing elastic softening at the
interface, and (iii) reducing connectivity of the magnetostrictive
phase without compromising the contact area with piezoelectric
phase. All these challenges could be addressed by core–shell types
of magneto-electric multiferroic nanocomposites, where magne-
tostrictive core is surrounded by a piezoelectric shell. In such a
configuration, an insulating ferroelectric layer is supposed to
prevent an electrical contact between the more conducting mag-
netic phases. Finite conductivity interferes with the poling of the
composites to reach the maximal ME performance.
The core–shell structure of CFO/BTO nanocomposite shows
favorable properties like high ME and MD responses. It was

http://dx.doi.org/10.1016/j.jmmm.2014.06.039
0304-8853/& 2014 Elsevier B.V. All rights reserved.
156 M.M. Selvi et al. / Journal of Magnetism and Magnetic Materials 369 (2014) 155–161

reported that the change in magnetocapacitance value of 1.7 per-
centage for the core–shell nanoparticles in 2 T field at 134 K and
the nanotubes report 4.1 percentage at room temperature (RT) in
the 2.1 T field [18]. Duong et al. measured the direct magneto-
electric response in CFO/BTO composites using an experimental
setup consisting of a lock-in amplifier [19], and using the magnetic
pulse method [20]. Shvartsman et al. [21] and Etier et al. [22]
measured the converse magneto-electric effect for CFO/BTO
ceramic composites using a modified SQUID ac susceptometer.
Finely microstructured nanocomposites with ferrite-core and
piezoelectric-shell have not yet been ideally obtained or reported
due to the difficulty in preparation of good core–shell structured
particles. Hence, the aim of this work is to prepare finely micro-
structured core–shell magneto-electric multiferroic nanocompo-
site and determine its magneto-electric coupling indirectly from
the impedance spectroscopy study in the presence of magnetic
field [23,24].
2. Synthesis
The preparation involves three steps: (1) the core material CFO
was prepared by coprecipitation method, (2) the precursor solu-
tion of BTO for the shell was obtained through citrate-gel process
[18], and (3) finally, the core material was dispersed into BTO
precursor solution to obtain the core–shell nanocomposite.
Solution of nitrate precursors, Co(NO3)2
6H2O and Fe(NO3)3

9H2O with a molar ratio of 1:2, was used as the starting materials.
The precipitating agent (NaOH) was slowly added to the precursor
solution of CFO to maintain a pH value of 12 and was mixed
thoroughly by heating at 80 1C with constant stirring. The pre-
cipitated particles were thoroughly washed and dried at 100 1C
was used as the core material for the core–shell synthesis.
The as-prepared CFO nanoparticles were then covered with a
BTO precursor solution using citrate-gel process. The titanium
citrate solution was prepared by dissolving titanium (IV) isoprop-
oxide and citric acid in ethanol with constant stirring and heated
at 90 1C for 20 min. Similarly, the barium citrate solution was
prepared from barium carbonate. Both the citrate solutions were
thoroughly mixed and heated at 120 1C to form a gel. The as-
prepared CFO nanoparticles were dispersed in this BTO precursor
solution with continuous heating and stirring, resulting in the
gelation of BTO (shell) on the surface of the CFO (core) nanopar-
ticles. The mixture was then centrifuged for 15 min at 2500 rpm,
the supernatant liquid was decanted for getting a thick black
precipitate. The dried gel was calcined at 780 1C for 5 h to obtain a
core–shell nanocomposite powder.
measurement was carried out in an impedance analyzer (SI-1260)
by applying an ac field of 1000 mV and varying the magnetic field
from 1 kOe to 7 kOe.
4. Results and discussion
4.1. Structural and phase characterization
The room temperature XRD patterns of the core–shell (CFO/
BTO) nanocomposite, CFO and BTO samples, optimized under
similar conditions, are given in Fig. 1. The single phase nature of
CFO and BTO is evident without any trace of impurity phases. The
core–shell XRD pattern reveals the presence of both the CFO
(JCPDS: 22-1086) and BTO (JCPDS: 05-0626) phases. The absence
of impurity and intermediate phases confirm the successful for-
mation of composite materials in the core–shell form showing the
compatibility of magnetic CFO and ferroelectric BTO. By the direct
comparison method [25], the integrated intensity of the strongest
peaks of CFO and BTO is considered for calculating the approx-
imate amount of the constituent phases present in the core–shell
nanocomposite. The calculated weight percentage of CFO is 65%
and that of BTO is 35%.
The microstructure of the samples was investigated from the
HR-SEM micrographs, shown in Fig. 2. CFO [Fig. 2(a)] and core–
shell (CFO/BTO) [Fig. 2(c)] show the agglomeration of spherical
particles in the range of 20–60 nm. The nanoporous structure of
BTO is apparently observed in Fig. 2(b) which may be due to the
aggregation of the agglomerated particles with a particle diameter
of 30–100 nm resulting from the formation of compact aperture.
The large surface area of nanoporous structure plays the crucial
role in the preparation of core–shell nanocomposite.
The EDX mapping related to the SEM image of Fig. 3
(a) confirms the presence of elemental Ba, Ti, Co, Fe and O in the

3. Experimental

The phase composition of the samples was determined by

X-ray diffraction (XRD) (GE XRD 3003 TT) using Cu Kα (λ ¼
1.54056 Å) radiation with two theta in the range of 20–701 with
a step size of 0.04 steps/s. The core–shell morphology of the
samples was determined by high resolution scanning electron
microscopy (HR-SEM) (FEI Quanta FEG 200) and high resolution
transmission electron microscopy (HR-TEM) (JEOL-TEM 2010). The
room temperature magnetic properties were determined using a
vibrating sample magnetometer (VSM) (Lakeshore VSM 7410) at a
field of 15 kOe. The dielectric measurements were performed
using a Solartron impedance analyzer (SI-1260) in the frequency
range of 1–1 MHz. For the magnetoimpedance (MI) measure-
ments, a specially designed sample holder was used to place the
sample in the form of pellet (1.29 mm thickness and 8 mm Fig. 1. XRD patterns of (a) CFO, (b) CFO-BTO core–shell nanocomposite, (c) BTO. ‘*’
diameter) between magnetic poles. The magnetodielectric (MD) BTO phase and ‘#’ CFO phase.
 M.M. Selvi et al. / Journal of Magnetism and Magnetic Materials 369 (2014) 155–161
Fig. 2. HR-SEM image of (a) CFO, (b) nanoporous BaTiO3 and (c) CFO-BTO core–
shell nanocomposite,
CFO/BTO core–shell nanocomposite. The area-mapping of EDX
(Fig. 3(b)–(i)) indicates that the elements Co, Fe and O are
uniformly distributed in the BTO matrix.
The HR-TEM micrograph of the core–shell nanocomposite is
shown in Fig. 4, where the higher magnification image in the inset
confirms the core–shell nature. The presence of two phases is
clearly seen due to the difference in transmission intensities of
CFO and BTO phases. The brighter BTO shell was present at the
grain boundary of the darker CFO core. In the core–shell image,
the magnetic CFO particles form agglomerates in the BTO matrix.
157
The diameter of this core–shell nanoparticle was  87 nm with an
average thickness of the core and shell being 70 nm and 15 nm.
4.2. Functional properties
The room temperature magnetization measurement of CFO and
core–shell nanocomposite at a maximum applied field of 15 kOe is
shown in Fig. 5(a), showing almost a similar behavior. The
observed saturation magnetization (Ms), remanent magnetization
(Mr) and coercivity (Hc) are 49 emu/g, 14 emu/g and 885 Oe,
respectively, for CFO nanoparticles. The BTO coated nanocompo-
site shows reduced Ms (24 emu/g) and Mr (9.4 emu/g) values. The
magnetic moment of the composite comes only from CFO, since
BTO is diamagnetic. The weight percentage of CFO in core–shell
nanocomposite is almost 65% and hence, the magnetization of the
composite should be 49  0.65 ¼ 32 emu/g. This value is higher
than the experimentally obtained value of 24 emu/g, which is
mainly due to the nonmagnetic BTO. A magnetic dead layer
created by BTO existing due to surface/interface defects clearly
demonstrates the dilution effect of the non-magnetic phase [26].
The presence of non-magnetic BTO and interface effects are
expected to influence the magnetic moment of the core–shell
nanocomposite by changing the distribution of magnetic ions and
their spin orientation, there by affecting the magnetic properties
[27]. The coercive field increases to 1119 Oe in the core–shell
nanocomposite, due to the higher field for spin reversal in the
presence of non-magnetic shell [28]. Similar results have been
observed for the core–shell structure of BaTiO3–Ni0.5Zn0.5Fe2O4
nanocomposite [27].
The pyroelectric measurement on the core–shell nanocompo-
site shows anomaly at 313 K for all the frequencies (Fig. 6(a))
consistent with that of the pure BTO (Fig. 6(b)). The anomaly
around 313 K is attributed to the ferroelectric to paraelectric phase
transition of BTO. The Curie temperature (TC) of BTO is  390 K.
The strong decrease in TC observed for the core–shell nanocom-
posite is attributed to the combination of the intrinsic size effect
and the size dependent dilution effect of a grain boundary dead
layer. Below the critical grain size ( 100 nm), the piezoelectric
BTO induces a stress on the inner portion of the grain leading to
the pinning points inside the grain, and hence the domain wall
motion is inhibited. The competition between the surface bond
contraction and the domain wall pinning affects the ferroelectric
to paraelectric phase transition (TC) of BTO (due to the decrease in
the c/a value) [26]. Incidentally, the pyromagnetic measurement
also shows an anomaly at the same temperature (Fig. 5(b)),
indicating the intrinsic magneto-electric coupling of the CFO/BTO
core–shell nanocomposites. This is due to the sharp increase in the
compressive strain and the increase in the magnetization value.
4.3. Magnetoimpedance analysis
To confirm the possible coupling between CFO (core) and BTO
(shell), a systematic investigation is carried out on the basis
of magnetodielectric (MD) data. Fig. 7 reveals the magnetoimpe-
dance (MI ¼(Z0 (H)  Z0 (0))/Z0 (0)) values for the core–shell nano-
composite at different frequencies. Two facts to be considered for
the possible origin of MD effect in composite material are
(1) magnetostriction (MS) effect through strain mediated interface
coupling and (2) magnetoresistance (MR) effect combined with
the Maxwell–Wagner (MW) effect.
At low frequencies, the MR effect does not contribute to MD
response and hence the MS of CFO with BTO matrix gives rise to
MD response. Above some higher frequency, the MR effect will
emerge along with the MW effect. There exists an intermediate
frequency region where these two effects cancel each other.
Above the intermediate frequency region, the MD effect has the
158 M.M. Selvi et al. / Journal of Magnetism and Magnetic Materials 369 (2014) 155–161

Fig. 3. (a) The EDS spectrum of the CFO-BTO core–shell nanocomposites. Corresponding elemental area-mappings for Ba, Ti, Co, Fe, O, BTO and CFO are shown in (b), (c), (d),
(e), (f), (g) and (h) respectively.
 M.M. Selvi et al. / Journal of Magnetism and Magnetic Materials 369 (2014) 155–161
Fig. 4. HR-TEM image and inset shows higher magnification of core–shell
nanocomposite.
Fig. 5. (a) Field dependent magnetic hysteresis loops of CFO and CFO-BTO core–
shell nanocomposites. (b) Temperature dependent magnetization, derivative of
magnetic moment with temperature is in the inset at an applied magnetic field of
1000 Oe.
contribution from MR effect combined with the MW space charge
polarization. According to literature [29], Maxwell–Wagner relaxa-
tion is related to the heterogeneous nature of the composites.
159
Fig. 6. Temperature dependent dielectric constant of (a) CFO-BTO core–shell
nanocomposites, (b) BTO nanoparticles at different frequencies.
Fig. 7. Frequency dependent MI plot of CFO-BTO core–shell nanocomposites.
In order to eliminate the contribution of MW effect, the region
above conductivity cut-off is to be calculated. The variation of
magnetocapacitance, MC ¼(ε0 (H)  ε0 (0))/ε0 (0), for the core–shell
nanocomposite with frequency shows a peak at 25 kHz, as given in
Fig. 8. At low frequencies, the charge carriers in the low resistivity
layer respond to the applied field (increasing MC). But at high
160 M.M. Selvi et al. / Journal of Magnetism and Magnetic Materials 369 (2014) 155–161
Fig. 8. Frequency dependent MC plot of CFO-BTO core–shell nanocomposites with
applied field between 1 kOe and 7 kOe.
Fig. 9. Frequency dependent dielectric loss plot for the CFO-BTO core–shell
nanocomposite having frequency larger than 25 kHz.
frequencies, charge carriers do not have time to respond to the
applied field (decreasing MC). Hence a cut-off exists in the
frequency dependent dielectric response, which leads to a max-
imum MC value around 1/RC [29]. The frequency region above
conductivity cut-off (maximum value of MC) is taken in order to
obtain the intrinsic magnetocapacitance. This suggests that the
observed MD effect below 25 kHz does not truly reflect the
intrinsic ME coupling [29] which is attributed to the MR effect
combined with MW effect. The MD response should originate
from the co-contributions of MS and MR effects in the range
of 25 kHz to 2.5 MHz. Above the frequency of 2.5 MHz, the charge
carriers have low response to the field, leading to decrease in the
value of MR.
4.4. Magneto-electric coupling susceptibility
The ME coupling susceptibility of the core–shell is evaluated at
2.5 MHz frequency. At this frequency, the MD effect is almost
independent of the applied field (Hdc) with low dielectric losses
(Fig. 9). Under this simplifying condition, Jang et al. [23] had
derived an expression to evaluate the magneto-electric coupling
susceptibility, χE ¼ (E0/Hdc)MC, where E0 is the applied electric
excitation signal (1000 mV), Hdc is the applied magnetic field in
Tesla and MC is the magnetocapacitance values. The value of χE is
in the range of 0.6 70.2 mV/cm Oe for the applied magnetic field
between 1 kOe and 7 kOe.
5. Conclusion
The combination of co-precipitation followed by citrate-gel
method were used to prepare the CFO/BTO core–shell nanocom-
posite. The weight percentage of CFO (65%) and BTO (35%) was
calculated from the XRD pattern. The homogeneous distribution of
core–shell nanocomposite was confirmed by microscopic analysis.
The magnetic properties were derived from the magnetic phase.
The electrical properties are strongly influenced by extrinsic
phenomena. The pyroelectric and pyromagnetic measurements
show an anomaly around 313 K which is assigned to the ferro-
electric phase transition of BTO indicating the intrinsic ME
coupling of the sample. The lower TC indicates that the ferro-
electric BTO becomes progressively more symmetric in nature and
hence the heat effect on the tetragonal (ferroelectric) to cubic
(paraelectric) transition is gradually reduced. The MD effects can
be attributed to the strain-mediated ME coupling and MR com-
bined with the Maxwell–Wagner effect. The room temperature
Magneto-electric coupling susceptibility of the sample was
derived from the magnetodielectric measurements by eliminating
the contribution of Maxwell–Wagner combined with the magne-
toresistance effect which was attributed due to the presence of
both magnetostriction and magnetoresistance.
Acknowledgment
MM thanks University of Madras for DKMK endowment scho-
larship and Mr. B. Soundararajan of our department for his kind
help. Authors thank SAIF, IIT Madras for VSM and HR-SEM
measurements. Authors also thank NCNSNT, University of Madras
for HR-TEM measurement.
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