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Effect of BaTiO3 addition on structural, multiferroic and magneto-dielectric properties of

0.3CoFe2O4−0.7BiFeO3 ceramics

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2014 Smart Mater. Struct. 23 105024

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 Smart Materials and Structures

Smart Mater. Struct. 23 (2014) 105024 (16pp) doi:10.1088/0964-1726/23/10/105024

Effect of BaTiO3 addition on structural,

multiferroic and magneto-dielectric
properties of 0.3CoFe2O4−0.7BiFeO3
ceramics
Nidhi Adhlakha1, K L Yadav1 and Ripandeep Singh2
1
Smart Material Research Laboratory, Department of Physics Indian Institute of Technology Roorkee,
Roorkee-247667, India
2
Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India

E-mail: klyadav35@yahoo.com

Received 12 April 2014, revised 17 July 2014

Accepted for publication 5 August 2014
Published 16 September 2014

Abstract
This study reports the various physical properties of (1 − x)(0.3CoFe2O4-0.7BiFeO3)-xBaTiO3
composites (equivalently denoted as 0.3CFO-0.7BFO/BT) with the compositions x = 0, 0.30,
0.35, 0.40 and 1.0. The composites are synthesized through a hybrid processing technique in
which 0.3CFO–0.7BFO is prepared through a sol-gel process, and BT is processed through a
solid state reaction method. Subsequently, the effects of the addition of BT on the structural,
dielectric, magnetic and magneto-dielectric properties of 0.3CFO–0.7BFO have been
investigated for various BT concentrations. The Rietveld refinement analysis of x-ray diffraction
patterns reveals the structural distortion in the BFO phase with the addition of BT, while no such
distortion has been observed for the CFO phase. Energy dispersive spectroscopy confirms the
presence of two types of grains that correspond to the 0.3CFO–0.7BFO and BT phases in field
emission scanning electron micrographs of the composites. Improved dielectric properties have
been observed, which are associated with the improved density of composites with the addition
of BT. Measurements of the magnetic and ferroelectric hysteresis loops at room temperature
indicate that the composites exhibit ferroelectricity and ferromagnetism simultaneously at room
temperature. An increase of the electric polarization has been observed due to structural
distortion arising with the addition of BT. The significant dependence of the dielectric constant
on the magnetic field has been observed in the prepared composites. The highest value of the
magneto-dielectric response (3.2%) has been observed for a 40 mol% addition of BT.
Keywords: composite ceramics, sol gel process, magnetodielectric effect

(Some figures may appear in colour only in the online journal)

1. Introduction single-phase multiferroics was experimentally confirmed for

Multiferroics are materials that exhibit coupled electric,
magnetic and structural order parameters that simultaneously
produce ferroelectricity, ferromagnetism and ferroelasticity
effects. This class of materials is attracting thorough investi-
gations toward their potential applications in spintronic
devices, actuators and sensors, etc [1–3]. The simultaneous
existence of ferroelectricity and ferromagnetism in the case of
the first time by Smolenskii and Churpis [4] in ferroelectric
Pb(Fe1/2Nb1/2)O3 perovskite [5] and was then discovered in
the antiferromagnetic single-phase material Cr2O3 [6]. The
existence of cross-coupling between magnetic and electric
order parameters, called magnetoelectric (ME) coupling, has
drawn great interest, as this effect opens the possibility to
manipulate electric properties magnetically, and vice versa.
Moreover, it provides an extra degree of freedom in designing

0964-1726/14/105024+16$33.00 1 © 2014 IOP Publishing Ltd Printed in the UK

Smart Mater. Struct. 23 (2014) 105024
materials for multi-state memory elements and novel memory
devices [7]. The classification of these multiferroic materials
can be carried out on the basis of single-phase and multi-
phase materials. In the case of single-phase multiferroics, the
magnetoelectric (ME) effect is an intrinsic effect, but most of
them have a Neel and Curie temperature below room tem-
perature. Therefore, they exhibit an ME effect at low tem-
peratures—mostly at cryogenic temperatures—which limit
their applicability in practical devices [8].
Among the single-phase multiferroics, BiFeO3 (BFO)-
based ceramics [9–12] have attracted the greatest attention
due to their high antiferromagnetic transition temperature
(TN ∼ 643 K) and ferroelectric temperature (Tc ∼ 1103 K), as
well as the existence of multiferroic properties at room tem-
perature [3]. During the synthesis of BiFeO3, the kinetics of
the phase formation in a Bi2O3–Fe2O3 binary system easily
leads to the appearance of sillenite-type Bi25FeO39 and mul-
lite-type Bi2Fe4O9 impurity phases along with the BiFeO3
phase. These secondary byproducts have been interpreted as
intermediates in the formation of ferrite [13]. The BiFeO3
phase can generally be obtained with the help of leaching out
the impurities by diluted nitric acid [14]. BiFeO3 exhibits
rhombohedrally distorted perovskite structures that have the
space group R3c, and BFO-based bulk ceramics exhibit weak
macroscopic magnetic properties, which is a consequence of
intrinsic spatially modulated cycloidal spin structures with an
incommensurate long period of ∼620 Å, which is supposed to
originate from impurity phases related to Fe phase separation
[15]. A relatively enhanced magnetization has been observed
in highly constrained epitaxial films or chemically substituted
ceramics or films [16–19]; however, this enhancement is
restricted as it can only supress or destroy the spin cycloid,
but it cannot change the intrinsic antiferroelectric nature of
BFO-based single-phase materials. This gives rise to the weak
magnetoelectric effect [20]. From an application point of
view, a high ME effect is desirable; however, a low ME effect
prevents its applications [21]. In addition to this, BFO-based
ceramics remain a major challenge from an application point
of view due to their low resistivity, which is further related to
their high leakage current density. The presence of a high
leakage current is ascribed to defects and nonstoichiometry,
and it creates a major hindrance in the case of transport
measurements [15]. The weak magnetic field and high leak-
age current density are the major hindrances for practical
applications of BFO. In order to overcome these limitations,
various attempts have been made in recent years, e.g. by the
chemical substitution of BFO at different atomic sites by
forming BFO-based solid solutions and by using a multi-
component Fe-based system in different volume fractions and
connectivity was designed and fabricated [5].
Moreover, the multiferroic composites, which exhibit
better properties and a high magnetoelectric effect compared
to single-phase ones, are currently attracting a great deal of
attention. In these composites, the ME effect appears based on
the concept of product property [22], according to which a
suitable combination of piezomagnetic or magnetostrictive
and piezoelectric phases is required to yield a desirable ME
effect. The combination of these phases exhibits the
2
N Adhlakha et al
properties of its parent compounds, and the interaction
between the electric and magnetic orders make these materials
suitable for potential applications in multifunctional devices,
waveguides, ME memory devices and energy harvesters [23].
Followed by the aforementioned properties of the ME com-
posites, various ferrite-ferroelectric composites have been
prepared with different configurations, such as NiFe2O4-
BaTiO3 [24], Co0.5Zn0.5Fe2O4-PLZT [25],
Ni0.75Zn0.25Fe2O4–Ba(Ti0.85Zr0.15)O3 [26] and multilayer
composites of PZT/Terfenol-D [27] and BiFeO3-Pb(ZrTi)O3
[28], and they have shown profound improvement in their
ME coefficients; hence, they are promising candidates for
multifunctional applications. Moreover, various three-phase
particulate composites, such as 0.7BiFeO3-0.3BaTiO3-
Y3Fe5O12 [29], BaTiO3–BiFeO3–BiYbO3 [30], 0.9
(0.7BiFeO3–0.3BaTiO3)–0.1CoFe2O4 [31] and three-phase
laminate composites of 0.948Na0.5K0.5NbO3–0.052LiSbO3
and Ni0.8Zn0.2Fe2O4 [32] ceramics, have recently been
reported to have a significant increase in the ME effect along
with improved ferroelectric and ferromagnetic properties.
In this paper, we have presented a class of three-phase
ceramic composites of (1 − x)(0.3CoFe2O4-0.7BiFeO3)
−xBaTiO3 with x = 0, 0.30, 0.35, 0.40 and 1.0. Since BFO
exhibits weak ferromagnetism, the introduction of CoFe2O4
(CFO) into BFO by forming its nanocomposite is an effective
way to improve the magnetism. CFO is a hard magnetic
material with a large saturation magnetization (about
80 emu g−1) and a high coercivity (5400 Oe); Also, it is
known for its large magnetostrictive coefficient; so, it is
widely used as a piezomagnetic constituent [23]. There is a
wide study on nanostructured epitaxial thin films of BFO-
CFO, and there are a few reports on bulk CFO-BFO. The
nanocomposite xCoFe2O4-(1 − x)BiFeO3 with x = 0.30 repor-
ted by Liu et al [33] has been found to exhibit the largest
coercivity and optimal squareness (Mr/Ms). One of the che-
mical solution methods, i.e. the sol-gel method, is used to
prepare the 0.3CFO-0.7BFO ceramic. The magnetization of
the BFO system would be improved with the introduction of
the CFO; however, due to the low resistivity of the CFO, the
electrical properties deteriorated. Hence, BaTiO3 (BT) was
introduced into the 0.3CFO-0.7BFO system in order to
acquire improvements in the electrical as well as the magnetic
properties. The ceramics based on the BT are known for their
better dielectric properties, which have a higher polarization,
low losses and good chemical/mechanical stability in a large
frequency range [34].
Therefore, we have made an attempt to solve the inherent
problems of BFO by making complex composites of CFO-
BFO-BT. After a detailed literature survey, It was found that
this system had not yet been reported. The aim of the present
work is to study the structural, dielectric, magnetic and
magneto-dielectric properties of (1 − x)(0.3CoFe2O4-
0.7BiFeO3)−xBaTiO3 with x = 0, 0.30, 0.35, 0.40 and 1.0
composites. Apart from these, we have performed a detailed
Rietveld refinement analysis of the x-ray diffraction patterns
in order to study the structural transitions in composites.
Smart Mater. Struct. 23 (2014) 105024
2. Experimental
A spinel-perovskite xCoFe2O4-(1 − x)BiFeO3 (x = 0.30)
composite was synthesized through a sol-gel process. The
chemical reagents used in the experiment were of analy-
tical grade. The reagents bismuth nitrate Bi(NO3)3.5H2O,
ferric nitrate Fe(NO3)3.9H2O, cobalt nitrate (Co
(NO3)2.6H2O, ethylene glycol and citric acid were used as
starting materials. The appropriate molar proportions of
metal nitrates were fixed at Bi: Fe: Co in the ratio of 7: 13:
3. An aqueous solution of citric acid was prepared in dis-
tilled water. Bismuth nitrate, ferric nitrate and cobalt
nitrate were added in turn with constant stirring at
60–70 °C to obtain a homogeneous solution and to avoid
precipitation. After mixing the salts to their total dissolu-
tion, ethylene glycol was subsequently added into the
solution with a proportion (in mass) of citric acid/ethylene
glycol in the ratio of 70:30. The solution was then turned
into xerogel, which started to swell and filled the beaker,
generating a foamy precursor that consisted of very light
nanosized flakes. The resulting gel was then dried over-
night at 100 °C in a hot air oven to remove the excess
water; the powder obtained after drying was calcined at
800 °C for 2 h. The obtained calcined powder was then
leached in diluted HNO3 to eliminate unreacted impurity
phases of BFO.
BaTiO3 ceramics were prepared through the solid state
reaction method. The stoichiometry amounts of the high-
purity powders of BaO and TiO2 were weighed and grounded
thoroughly in an acetone media using agate mortar for 5–6 h
to obtain a homogeneous mixture. The well-mixed powder
was then dried and calcined in a closed alumina crucible at
1200 °C for 2 h in an air atmosphere. The calcined powder
was again crushed and sieved in order to obtain uniform-sized
particles and was then utilized for the synthesis of the
composites.
The composites with the specific formula (1 − x)
(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 where x = 0, 0.30, 0.35,
0.40 and 1.0 were prepared by mixing 0.3CFO-0.7BFO and
BT in an acetone medium with the proportion mentioned in
the formula. These mixed powders were then pressed into
8 mm diameter discs of 1–2 mm thickness via a steel die and
hydraulic press with a uniaxial pressure of about
6 × 107 kg m−2. The obtained discs were finally sintered at
950 °C for 2 h.
The phase identification of the sintered pellets was car-
ried out using an x-ray diffractometer (Bruker D8 Advance) at
a scanning rate of 1 min at room temperature using CuKα
radiation (λ = 1.5418 Å). The distribution of grains on the
surface of the sintered pellets was analysed by taking field
emission scanning electron microscopy (FESEM) images
with the help of an FEI Quanta 200FEG electron microscope
operated at an accelerating voltage of 20 kV. Moreover, the
grain size was calculated from the micrographs of FESEM
using the linear intercept method. In order to take the elec-
trical measurements, the flat surfaces of the pellets were
polished with high-purity silver paste and then dried at 150 °C
for 2 h. The measurements of dielectric constant (ε) and
3
N Adhlakha et al
dielectric loss (tanδ) were carried out using an automated
HIOKI 3532-50 Hi-Tester LCR meter connected to a desktop
computer and a capacitance measuring assembly in the tem-
perature range of 30–500 °C at different frequencies
(1 kHz,10 kHz, 50 kHz, 100 kHz, 500 kHz and 1MHz). The
magnetic measurements on the composites were taken using a
vibrating sample magnetometer (VSM) at room temperature
in the range of −10 kOe ⩽ H ⩽ 10 kOe. The measurement of
the dielectric polarization versus the electric field (P-E hys-
teresis loops) was accomplished using a modified Sawyer-
Tower circuit (Automatic P-E loop tracer system, Marine
India Electrical Pvt. Ltd). The magnetocapacitance study was
performed using a Wayne Kerr 6500 high frequency LCR
meter along with a magnet of up to 8 kOe with an accuracy of
10 Oe (provided by Marine India Electrical Pvt. Ltd).
3. Results and discussions
3.1. Structural analysis
The x-ray diffraction patterns of (1 − x)(0.3CoFe2O4-
0.7BiFeO3)−xBaTiO3 (x = 0.30, 0.35 and 0.40) composites
along with the individual phases of 0.3CFO-0.7BFO and BT
are presented in figure 1(a). The 0.3CFO-0.7BFO prepared
through the sol-gel process exhibits a mixed spinel-perovskite
structure without any traces of impurities. All of the peaks of
0.3CFO-0.7BFO can be identified for the separate perovskite
(BFO) and spinel (CFO) phases, and they comply with the
reported values [21]. No intermediate phase was found to be
formed during the formation of the 0.3CFO-0.7BFO com-
posite. The BFO crystallizes in a rhombohedrally distorted
perovskite structure with space group R3c, and the CFO has a
cubic spinel structure with space group Fd-3m. The splitting
of the peak at 2θ = 45° in the XRD pattern of the BT reveals
that it possesses a tetragonal structure with space group
P4 mm, and a proper coincidence has been found with the
International Centre for Diffraction Data (ICDD) with the
pattern powder diffraction format (PDF) No.79-2263 [35]. It
is clear from the enlarged XRD pattern in the 2θ range of
30°–35° in figure 1(b) that there is a shift of the maximum
intense peaks with the addition of the BT that corresponds to
the BFO phase toward lower angles; however, the position of
the peaks that correspond to the CFO phase remains the same
in the composites.
This means that the addition of the BT content has led to
a structural distortion in the BFO phase. This can be
explained on the basis of a substitution model in which Ba2+
substitutes the Bi3+ ion at the A site, and Fe3+ at the B site is
substituted by Ti4+. The ionic radius of the Ba2+ ion (1.35 Å)
is larger compared to the Bi3+ ion (1.03 Å) on the A site of the
perovskite structure; also, the ionic radii of Ti4+ (0.68 Å) is
larger than Fe3+ (0.64 Å) [36]. These A/B site co-substitutions
lead to the expansion of a perovskite unit cell of the BFO;
hence, the left shifting of the peaks that correspond to the
BFO phase takes place. However, no reaction takes place
between the CFO and BT, as CFO exhibits a spinel structure,
and BT has a perovskite structure; so, these compounds have
Smart Mater. Struct. 23 (2014) 105024
Figure 1. (a) The x-ray diffraction patterns of (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites with x = 0.30, 0.35 and 0.40 along with
the individual phases, namely 0.3CFO-0.7BFO and the BT (b) enlargement of the region between 30° to 35°.
very little solid solubility with each other [37]. Hence, no
peak shifts that correspond to the CFO phase have been
observed.
In order to study the structural transitions within the
composites, we performed a detailed Rietveld refinement
analysis of the x-ray diffraction patterns using the FullProf
program. The Rietveld refinement analysis of the BFO,
CFO and BT phases in the (1 − x)(0.3CoFe2O4-0.7BiFeO3)
−xBaTiO3 composites was carried out using R3c, Fd-3m
and P4 mm space groups. Figures 2(a)–(e) show the
observed, calculated and difference patterns obtained using
the Rietveld refinement analysis. A good agreement is
observed (red closed circles) and calculated (black solid
lines). XRD patterns have been observed, which are further
confirmed by the difference pattern (blue bottom line). The
allowed Bragg positions for the space groups R3c, Fd-3m
and P4 mm are shown as vertical lines (pink). The detailed
structural parameters obtained from the Rietveld refinement
analysis along with the profile R-factors are listed in
table 1.
The lattice parameter a and the volume of the R3c unit
cell of the BFO phase are found to increase with the increased
BT concentration. The expansion of the lattice parameters
with the increased BT content in the (1 − x)BiFeO3−xBaTiO3
systems has also been previously reported [38, 39]. The lattice
parameters that correspond to the CFO phase in the compo-
sites with x = 0.30, 0.35 and 0.40 are almost the same as that
of its lattice parameters, which correspond to the pure
0.3CFO-0.7BFO phase (x = 0); this clearly indicates that no
structural change has been observed for the CFO phase in the
composites.
4
N Adhlakha et al
3.2. Microstructural analysis
The FESEM images of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)
−xBaTiO3 (x = 0, 0.30, 0.35, 0.40 and 1.0) composites are
shown in figures 3(a)–(e). All of the composites show dense
(with fewer voids) and heterogeneous microstructures with
closely packed grains, whereas the 0.3CFO-0.7BFO and BT
phases are crystallized into separate phases. The presence of
different phases in the composites is ascribed to the fact that
the grains of one of the phases has a higher possibility of
growing and therefore grows at the cost of the smaller
grains [40].
In the case of the composites, it is difficult to obtain a
homogenous microstructure due to the huge difference in the
sintering behavior and the thermal expansion coefficients of
the different phases. Figure 4 shows the EDX analysis of
different regions of the 0.6(0.3CoFe2O4-0.7BiFeO3)-
0.4BaTiO3 composite. The larger grains show strong Bi, Fe
and Co peaks along with the appearance of weak Ba and Ti
peaks. This indicates that the larger grains represent the
0.3CFO-0.7BFO phase. The EDX spectrum of the smaller
grains exhibit strong Ba and Ti peaks and weak Bi, Fe and Co
peaks in comparison. Hence, the smaller grains represent the
BT phase.
It is clearly revealed from the FESEM micrographs that
the smaller grains of the BT are dispersed distinctly in larger
grains of 0.3CFO-0.7BFO. The average grain size was cal-
culated using a linear intercept method and is shown in
table 1. The average grain size of the 0.3CFO-0.7BFO phase
synthesized using the sol-gel process is found to be higher
compared to the BT phase prepared by the solid state reaction
method, which is further ascribed to the liquid-phase sintering
mechanism. The melting point of Bi oxide is relatively low
Smart Mater. Struct. 23 (2014) 105024 N Adhlakha et al

Figure 2. Rietveld refined XRD patterns of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites; (a) x = 0, (b) x = 0.30, (c) x = 0.35, (d)
x = 0.40 and (e) x = 1.0 along with the observed (obs.), calculated (cal.) and difference patterns.

5
Smart Mater. Struct. 23 (2014) 105024 N Adhlakha et al

Table 1. Rietveld refined XRD parameters, grain size and bulk density of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composite ceramics.

Compositions x=0 x = 0.30 x = 0.35 x = 0.40 x = 1.0

Space group R3c R3c R3c R3c R3c
Fd-3m Fd-3m Fd-3m Fd-3m Fd-3m
P4mm P4mm P4mm P4mm
Lattice parameters (Å)
BFO phase a = 5.572 a = 5.594 a = 5.664 a = 5.915
c = 13.781 c = 13.873 c = 13.592 c = 13.981 —
Volume = 370.560 Volume = 375.964 Volume = 377.579 Volume = 423.601
CFO phase
a = 8.382 a = 8.387 a = 8.379 a = 8.389 —
Volume = 588.793 Volume = 590.016 Volume = 588.182 Volume = 590.406
BT phase
— A = 3.977 a = 3.977 A = 3.980 a = 3.998
c = 4.000 c = 3.985 c = 4.006 c = 4.031
Volume = 63.287 Volume = 63.035 Volume = 63.466 Volume = 64.461
RBragg
BFO 11.3 11.5 13.8 2.45 —
CFO 18.2 14.1 16.4 18.3 —
BT — 11.2 15.3 9.94 18.9
RF
BFO 8.18 10.2 14.4 19.3 —
CFO 16.1 16.5 17.2 17.2 —
BT — 7.74 8.92 5.86 13
χ2 1.13 1.26 1.34 1.37 1.42
Grain size (nm) 1162 736 585 436 671
Bulk density (g cm−3) 5.27 5.75 5.92 6.33 4.36

(825 °C); so, it can form a liquid phase in a multiple oxide
system during sintering at 950 °C. During this stage, a rear-
rangement of particles occurs, which is followed by enhanced
material transport. Given that the sintering temperature is
maintained above the liquid formation temperature of Bi
oxide and is therefore in a second stage, the smaller particles
are further dissolved, which results in an increase of density
via the reprecipitation of the particles on relatively larger
grains. In the final stage of sintering, grain coursing occurs,
which results in the enhancement of the grain size in the
end [41].
The grain size is found to decrease with the increased BT
content, as the addition of the BT content shows an inhibiting
effect on the grain growth process. The Ti4+ ions play the role
of donor, as it possesses a higher valence than Fe3+; hence,
the charge compensation can be achieved by filling the oxy-
gen vacancies. Consequently, the suppression of oxygen
vacancies results in slower oxygen ion motion and hence less
grain growth [42]. The average grain size of the composites
with x = 0.30, 0.35 and 0.40 is found to be less than 1 μm. The
bulk density of the present samples was measured using
Archimedes’s method, and the density data shown in table 1
illustrates that the addition of the BT leads to the densification
of the ceramic composites. This denser microstructure will in
turn make a contribution to induce the enhancement in the
electrical properties of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)
−xBaTiO3 composites.
3.3. Dielectric properties
3.3.1. Temperature dependent variation. The temperature
dependence of dielectric constant (ε) and the corresponding
dielectric loss tangent (tan δ) at different frequencies (1 kHz,
10 kHz, 50 kHz, 100 kHz, 500 kHz and 1 MHz) are shown in
figures 5(a)–(e). It has been found that for each composite, the
value of the dielectric constant increases with the increasing
temperature up to a certain transition temperature and then
decreases at higher temperatures. The increase of the mobility
of the space charge carriers with the increasing temperature
gives rise to an increase of the space charge polarization and
the conductivity, which leads to an increase of the dielectric
constant and the after-transition temperature; due to the
disappearance of the domains, the dielectric constant
decreases [26]. There are many factors that influence the
frequency dependence of a dielectric constant such as
microscopic compositional fluctuation, interfacial polarization
and macrodomain and microdomain switching [43]. The
dielectric constant at low frequencies is mainly determined
by the contribution of dipolar and interfacial polarizations;
however, at higher frequencies, the electronic polarization
contributes to the value of the dielectric constant. This is the
reason that the dielectric constant increases at a higher rate for a
1 kHz frequency as compared to the other frequencies [44].
Moreover, the peaks of the dielectric constant shift to
higher temperature as the frequency increases. This is a
typical characteristic of the relaxor behavior of the

6
Smart Mater. Struct. 23 (2014) 105024
Figure 3. FESEM images of the fractured surfaces of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites with (a) x = 0, (b) x = 0.30, (c)
x = 0.35, (d) x = 0.40 and (e) x = 1.0.
composites. The composite with a 30 mol% addition of BT
[figure 5(b)] exhibits prominent diffuseness in the dielectric
peaks and an apparent dependence on the frequency, which is
ascribed to the presence of a large number of ions at the A and
B sites of the ABO3 perovskite. The diffused maximum
appears to be due to the difference in polarizations that
correspond to each ion, which would give rise to different
relaxation times [38]. The presence of the diffused behavior in
the composite with x = 0.30 is attributed to the randomly
distributed strain field in the microstructure, which may have
7
N Adhlakha et al
originated due to lattice distortion induced by the addition of
BT content or due to the increase of the grain boundaries with
the decrease of the grain size.
An anomaly in the dielectric constant has been observed
for all of the given compositions in the vicinity of the
magnetic transition temperature, i.e. the Neel temperature of
the BFO. This kind of anomaly has been reported by several
groups in the bulk and thin film form of BFO, and these
studies predicted the possibility of magnetoelectric coupling
in the system [45, 46].
Smart Mater. Struct. 23 (2014) 105024
Figure 4. EDX spectrum of different regions of the 0.6(0.3CoFe2O4-0.7BiFeO3)-0.4BaTiO3 composites where Spectrum 1 corresponds to
spot 1, and Spectrum 2 corresponds to spot 2.
BT is well known for its normal ferroelectric behavior;
however, the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 com-
posites exhibit a mixture of relaxor and normal character-
istics, as 0.3CFO-0.7BFO shows the relaxor behavior. It has
been found that with an increase of the concentration of BT
beyond 30 mol%, the diffuseness of the peaks is reduced.
Moreover, there is a shift of the transition temperature toward
a higher temperature with the addition of BT content in the
0.3CFO-0.7BFO. This increase of the transition temperature
may be ascribed to the structural distortion, i.e. the increase of
the unit cell volume of BFO caused by the BT addition, as
given in table 1. BT exhibits a larger dielectric constant and a
smaller tanδ compared to 0.3CFO-0.7BFO. This indicates that
the dielectric properties of 0.3CFO-0.7BFO can be improved
by introducing BT content. The increase of the dielectric
constant with the addition of BT content is believed to be
caused by improved densification (given in table 1) in the
ceramic composites with the increase of BT content [47]. The
value of the average dielectric loss is slightly decreased with
the addition of BT, which is also ascribed to the denser
microstructure obtained due to the addition of BT [48].
Moreover, this can also be ascribed to the reduction of grain
size with the addition of BT, as the dielectric loss is less for
grains of smaller size due to the fact that the grain boundary
acts as a pining site for the domain wall movement. At higher
temperatures, the dielectric constant increases rapidly, which
indicates the increased space charge conduction that relates to
the movement of defects such as oxygen vacancies toward the
dielectric-electrode interface [49].
8
N Adhlakha et al
3.3.2. Frequency dependent variation. Figure 6(a) shows the
variation of the dielectric constant with the frequency at room
temperature in the frequency range of 100 Hz to 1 MHz. The
dielectric constants of all of the composites exhibit a general
behavior to decrease with the increased frequency. It shows
dispersion in the low-frequency region and attains a saturation
value at a higher frequency region. The decrease of the
dielectric constant in the low-frequency range is attributed to
the space charge polarization due to the presence of A site
vacancies, oxygen vacancies and the coexistence of Fe3+/Fe2+
in the ferrite phase [50]. The rapid decrease of the dielectric
constant with the increase of frequency can be explained on
the basis of the dipolar relaxation phenomenon due to
Maxwell–Wagner type interfacial polarization, in which the
dipoles are able to follow the applied field at low frequencies;
hence, this leads to the high value of the dielectric constant.
At higher frequencies, due to the lack of the ability of dipoles
to follow the fast alternation of an applied field, the dielectric
constant remains constant [51]. Moreover, at low frequencies,
different types of polarizations contribute to the dielectric
constant such as electronic, ionic, atomic and interfacial
polarizations, etc However, the constant arises due to the
electronic polarization at higher frequencies. With an
increase of the frequency, the ionic and orientation
polarizabilities descend, and their contribution finally
becomes insignificant. The existence of the space charge
polarization due to the inhomogeneous dielectric structure is
responsible for the high value of the dielectric constant at
low frequencies [44]. It is noted that the value of the
Smart Mater. Struct. 23 (2014) 105024 N Adhlakha et al

Figure 5. Dielectric constant as a function of temperature for the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites (a) x = 0, (b) x = 0.30,
(c) x = 0.35, (d) x = 0.40 and (e) x = 1.0, and the inset shows the corresponding variation of the dielectric loss with temperature.

dielectric constant is increased with the increase of the BT
content, and it is at a maximum (∼1600) for the composite
with x = 0.40 at a 100 Hz frequency. The increase of the
dielectric constant with the increase of the BT content is
ascribed to the large value of the dielectric constant of the
BT (∼3000) as compared to 0.3CFO-0.7BFO (∼600) for a
100 Hz frequency.
The variation of the loss tangent (tanδ) with the
frequency is shown in figure 6(b). A maximum has been
observed at around 500 Hz, and its presence can be thought of
as the frequency of an applied field becoming nearly equal to
the hopping frequency of the electrons between different ionic
sites. Similar types of maxima have also been previously
reported in other multiferroic composites [52]. The effect of

9
Smart Mater. Struct. 23 (2014) 105024 N Adhlakha et al

Figure 6. Frequency dependent variation of (a) the dielectric constant and (b) the dielectric loss for the (1 − x)(0.3CoFe2O4-0.7BiFeO3)
−xBaTiO3 composites with x = 0, 0.30, 0.35 and 0.40. The inset of figure 6(a) shows the variation of the dielectric constant with the frequency
for BaTiO3.

interfacial polarization and heterogeneous conduction

between the multiphase interfaces is ineluctable in the case
of multiferroic composites, and this effect becomes prominent
in the case of high ferrite content. Dielectric response peaks in
the dielectric loss appear at low frequencies, which is
attributed to the fact that the response time τ = 1/ωmax of
the motion of space charges that corresponds to the ferrite
phase is comparatively long compared to other mechanisms
[53]. The combined contribution of the p- and n-type charge
carriers toward the polarization may be the reason for this
abnormal behavior, which appears in the dielectric loss versus
the frequency. At lower frequencies, the contribution of the
mobility of the p-type charge carriers decreases more rapidly;
hence, the change in the number of p-type charge carriers may
be responsible for the shift of the position of the observed
peaks [54]. At higher frequencies, the dielectric losses are
reduced, as tanδ is associated with the dissipation of energy in Figure 7. M-H loops of (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3
dielectric systems. (x = 0, 0.30, 0.35 and 0.40) composites at room temperature. The
inset shows the magnified view of the hysteresis loop in the low field
range for a composite with x = 0.
3.4. Magnetic properties

Figure 7 presents the magnetic hysteresis (M-H) loops of the
(1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 (x = 0, 0.30, 0.35
and 0.40) composites obtained at room temperature using a
vibrating sample magnetometer (VSM) with an applied field
of −10 kOe ⩽ H ⩽ 10 kOe in which the magnified view of the
magnetic hysteresis loop of the composite with x = 0 is shown
in the inset of figure 7. The typical ferromagnetic behavior is
clear from the hysteresis loops, which show the presence of
an ordered magnetic structure at room temperature in mixed
spinel-perovskite systems. BFO is known to be anti-
ferromagnetic in nature with G-type spin ordering below the
Neel temperature, which has been modulated by a cycloidal
spiral with a large period λ = 620 ± 20 Å [55] and shows weak
ferro/ferrimagnetic characteristics in some temperature ranges
[56]. In addition, due to the canting of antiferromagnetic
sublattices, it exhibits a residual magnetic moment (weak
ferromagnetism) [57]. Liu et al [33] have reported that in
BFO-CFO systems, there is a significant increase in the
values of the saturation magnetization as well as the coercive
field with the addition of CFO above 20 mol%, which is
attributed to the presence of magnetoelastic coupling in the
system. The magnetism observed in the 0.3CFO-0.7BFO
composite (x = 0) can be attributed to the combined effects of
the BFO and CFO. The contribution of the magnetization in
the composite (x = 0) is dominated by CFO due to the high
value of the magnetization of CFO, as BFO possesses weak
ferromagnetic behavior. Similar types of observations are
reported earlier [58, 59]. In the case of doped- and solid-
solution BFO systems, the increased magnetic properties have
been explained by the canting of an antiferromagnetic Fe-O-
Fe spin structure that arose due to structural distortion. The
change of the spinoidal structure of a pure BiFeO3 to a
homogenous ferromagnetic state by doping BiFeO3-based

10
Smart Mater. Struct. 23 (2014) 105024 N Adhlakha et al

Table 2. Magnetic parameters of (1 − x)(0.3CoFe2O4-0.7BiFeO3) 2Ms, 2Mr and μ B , as there is a decrease of concentration of the
−xBaTiO3 composites observed at room temperature (300 K). magnetic Fe3+ with the increase of the nonmagnetic BaTiO3
Magnetic concentration [67].
2Mr 2Ms 2Hc moment
Composition (x) (emu g−1) (emu g−1) (kOe) (μB)
3.5. Ferroelectric behavior
0.00 11.536 32.908 1.545 0.853
0.30 6.894 25.349 1.317 0.725 Figures 8(a)–(e) shows the polarization-electric field (P-E)
0.35 6.527 21.284 1.375 0.618 hysteresis loops of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)
0.40 5.402 20.444 1.189 0.603 −xBaTiO3 composites with x = 0, 0.30, 0.35, 0.40 and 1.0
measured using a Sawyer–Tower circuit at a frequency of
50 Hz at room temperature. Due to a much lower resistance of
the ferrite phase, the composite ceramics are not fully polar-
compounds with nonmagnetic ions has been reported by ized. Moreover, the polarization of the composites becomes
Khomchenko et al [60]. In the case of BiFeO3-BaTiO3 solid difficult as they can withstand only low voltages [68]. The P-
solutions, it has been reported that the addition of BT content E hysteresis loop of pure 0.3CFO-0.7BFO represents the
can enhance the ferromagnetism feature in the sys- reversal of polarization, which clearly indicates that the
tem [56, 61]. leakage current is overwhelming, and under a high maximum
The possible reasons behind the observed magnetization electric field, it would be easily broken down. Such types of
in the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites P-E loops have also been reported earlier in doped BiFeO3
(x > 0) might be the following: (i) The change in the bond [69, 70] ceramics. However, the improvement in the shape of
angle of the Fe-O-Fe caused by the distortion created by the ferroelectric hysteresis loops has been observed with the
substitution of Bi and Fe by Ba and Ti, respectively, may addition of BT content, which indicates the reduction of
allow the canting of the antiferromagnetic sublattices. More- leakage current due to reduced oxygen vacancies (V2+ o ). The
over, this substitution is able to break the cycloidal spin reason may be ascribed to the substitution of Fe3+ ions with
structure of the BFO matrix, releasing the macroscopic Ti4+ ions with the addition of BT. Ti exhibits a higher valence
magnetization [62]. (ii) The addition of Ba2+ ions in BFO than Fe ions; hence, it acts as a donor, which leads to the
requires charge compensation, which might give rise to the reduction of oxygen vacancies that originate from the tran-
formation of Fe4+ or oxygen vacancies. The magnetic spin sition of Fe3+ to Fe2+ [71]; this is given by equation (3):
structure changes from antiferromagnetic to ferrimagnetic
with the incorporation of Fe4+ in the compound, which is
2TiO2 + Vo2 + → 2Ti Fe+ + 4Oo (3)
further ascribed to the difference in the magnetic moment
between Fe3+ and Fe4+ [63]. (iii) Gehring [64] and Good-
The saturation has not been achieved in the PE loops, as
enough et al [65] suggested that the statistical distribution of
they are dominated by the leakage current that originated
Fe3+ and Ti4+ ions in the octahedra or the creation of lattice
from the mixed valence of the Fe ions.
defects might lead to bulk magnetization and ferromagnetism.
Figure 8(f) shows the variation of the remnant polariza-
Inspite of the above facts, the ferromagnetic properties of the
tion (2Pr) and spontaneous polarization (2Ps) with the BT
composites are strongly dependent on the CoFe2O4 con-
content. The values of 2Pr and 2Ps are found to increase with
centration because of its high value of magnetization.
an increase of the BT content in the composites. The increase
The Bohr magnetons per atom, ion or formula unit μ B is
of the ferroelectric polarization may be attributed to the dis-
related to units of specific magnetization σs′ in emu g−1 as
tortion in the structure created by the addition of BT content,
follows (1):
evidenced by the results of the XRD. Moreover, the intro-
n × N0 × μ B duction of the electric polarization from the BT contributes to
σs′ = , (1)
M the increase of polarization. Similar behavior is also observed
in BiFeO3-Na0.5K0.5NbO3 [72] and BiFeO3-BaTiO3 solid
where M is the molecular weight, n is the number of unpaired
solutions [73]. The values of the coercive field (2Ec) for the
electron spins and No is Avogadro’s Number. The magnetic
composites with x = 0 to x = 0.40 are 15.25 kV cm−1,
moment in the Bohr magneton has been calculated for the
14.41 kV cm−1, 8.03 kV cm−1, 18.64 kV cm−1 and
samples using the simplified relation: −1
11.12 kV cm , respectively.
Mσs′
μB = , (2)
5585
3.6. Magneto-dielectric studies
where the factor 5585 is a product of the Bohr magneton ( μ B )
and Avogadro’s Number (No) [66]. The values of saturation The coupling between the electric and magnetic polarizations
magnetization (2Ms), remnant magnetization (2Mr), coercive can be investigated indirectly by recording the change in the
field (2Hc) and Bohr magneton ( μ B ) calculated from the value of the dielectric constant as a function of an applied
hysteresis loops of the composites are shown in table 2. The magnetic field (H) at 1 kHz, and it is plotted in figure 9(a).
increase of the BT content leads to a decrease in the values of The magneto-dielectric (MD) effect or magnetocapacitance is

11
Smart Mater. Struct. 23 (2014) 105024 N Adhlakha et al

Figure 8. Polarization hysteresis loops of the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites with (a) x = 0, (b) x = 0.30, (c) x = 0.35,
(d) x = 0.40 and (e) x = 1.0 (f). The variation of the remnant polarization (2Pr) and spontaneous polarization (2Ps) with BT content in the
(1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites.

Figure 9. (a) Magneto-dielectric effect of (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites at a 1 kHz frequency, (b) the variation of the
magnetocapacitance with (magnetization)2 for the composite with x = 0.40; the inset shows the variation of (magnetization)2 with an applied
magnetic field.

defined here as equation (4):
ε (H )−ε (0)
MC = × 100,
ε (0)
where ε(H) and ε(0) represent the dielectric constant in the
presence and absence of a magnetic field, respectively. The
absolute value of the magnetocapacitance experiences a
continuous increase with an increase in the applied magnetic
field, and the curve of MC gradually becomes flat at higher
fields, suggesting that MC has been saturated.
The observed magneto-dielectric effect can be positive or
negative. It has been found that in our case, Δεr decreases
(4) with the increase of the applied magnetic field, which sig-
nifies a negative coupling coefficient [74]. Katsufuji et al
[75, 76] reported that the negative or positive sign of the
magneto-dielectric effect depends on the product of the spin-
pair correlation of the neighbouring spins and the coupling
constant. The representative values of the MD response under
an applied magnetic field of 8 kOe at 1 kHz frequency for
(1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3 composites with

12
Smart Mater. Struct. 23 (2014) 105024
x = 0, 0.30, 0.35 and 0.40 are 0.4%, 1.1%, 2.3% and 3.2%,
respectively.
There may be several reasons for the existence of
magnetocapacitance in multiferroics. This may be due to one
of these effects, namely the magnetostriction effect, mag-
netoresistance or magnetoelectric coupling. The magnetos-
triction effect, which is the change of the sample dimension
(δL/L) by the magnetic order, might be considered to be the
origin of the observed magnetocapacitance [77]. The (Δεr),
which is observed due to magnetostriction, was found to be
two orders of magnitude smaller than the observed (Δεr) in
the case of the BiMnO3 [78]. BiFeO3 is also of a similar
kind, so one can expect the same to be true for this system
also. So, magnetostriction may not be the cause of the
magnetocapacitance in our system. As suggested by Catalan
[79], the magnetoresistive artifacts can also give rise to the
magneto-dielectric effect; hence, the resistivity measurement
was performed to check the presence of magnetoresistance
(Mr) in the system. It has been found that there is a negli-
gible variation of magnetoresistance (0.03%) with an
applied magnetic field. This means that the magnetocapa-
citance in the system is not attributed to the
magnetoresistance.
Hence, the existence of magnetocapacitance in the
ceramics is attributed to the presence of magnetoelectric
coupling. When a magnetic field is applied to a multiferroic
material, the material gets strained under the influence of an
applied magnetic field. This strain would induce stress,
which generates an electric field on ferroelectric domains;
hence, the dielectric behavior is modified [80]. It is clear
from figure 9(a) that the relationship between Δεr and H is
approximately quadratic and in the framework of the Ginz-
burg–Landau theory for the second-order phase transition;
there exists an intrinsic quadratic magnetoelectric coupling
term, i.e. γP 2M 2 in free energy [78]. The origin of such a
behavior has been predicted as a signature of coupling
between magnetic and ferroelectric domains. The thermo-
dynamic potential [77] of a ferroelectromagnet can be
written in the form (5):
β 4
φ = φ0 + αP 2 + P addition of BT content. The variations of dielectric constant
2 (ε) and dielectric loss tangent (tan δ) with the temperature
β′ , (5)
− PE + α′P 2 + M 4
2 inclusion of BT content. The variations of the dielectric
− MH + γP 2M 2
where α, β, α′, β′ and γ are the coupling coefficients, and P
and M are the polarization and magnetization, respectively.
The term γP2M2 that represents the exchange magneto-
electric interaction is always allowed in a ferroelectro-
magnet, regardless of symmetry. This free energy expression
was used by Kimura et al [77] to calculate the effect of
magnetic ordering on dielectric susceptibility, and it has
been found that the effect of magnetic ordering on a
dielectric constant will be proportional to Δεr γM 2 .
Figure 9(b) shows the variation of Δε /ε (0) with the square
of magnetization ( )
M 2 for the (1 − x)(0.3CoFe2O4-
0.7BiFeO3)−xBaTiO3 composite with x = 0.40, and a linear
13
N Adhlakha et al
change has been observed, which means that the afore-
( )
mentioned relation Δεr ~ γM 2 is followed by the compo-
site. The observation of the linear behavior leads to the
conclusion that the magnetocapacitance observed in the
system arises from the coupling term γP 2M 2 in the ther-
modynamic potential [77]. The inset of figure 9(b) shows the
variation of M 2 with an applied magnetic field up to 8 kOe.
The absolute value of γ was calculated using linear fitting,
and it was found to be ∼4.09 × 10−2 (emu g)−2 for a com-
posite with x = 0.40. There are many reports on magneto-
electric coupling measurements via static and dynamic ME
voltage coefficient measurements [81–84], PE loop mea-
surements under the influence of magnetic poling [85, 86],
or the measurement of magnetization under electric poling
[87, 88] and the ME voltage coefficient measurement from
P-H loops [89]. Here, we have carried out the magneto-
dielectric measurement, which gives the signature of the
magnetoelectric coupling in our system.
4. Conclusions
In summary, the (1 − x)(0.3CoFe2O4-0.7BiFeO3)−xBaTiO3
composites or the composites equivalently denoted as
0.3CFO-0.7BFO/BT with x = 0, 0.30, 0.35, 0.40 and 1.0
were prepared through a hybrid processing technique in
which 0.3CFO-0.7BFO was prepared through the sol-gel
process, and the BT was prepared through the solid state
reaction method. The x-ray diffraction pattern reveals the
structural distortion in the BFO phase with the addition of
BT, while no such distortion has been observed in the CFO
phase. In order to study the structural transitions, the Riet-
veld refinement analysis has been performed for the com-
posites, and the observed refined lattice parameters confirm
the structural distortion in the BFO phase. FESEM micro-
graphs reveal the presence of the closely packed grains, and
the average grain size was found to decrease with the
shows the increase of ε and the decrease of tan δ with the
constant with the frequency show the dispersion in the low-
frequency region and attain a saturation value at a higher-
frequency region. The magnetic hysteresis loops observed at
room temperature show the presence of an ordered magnetic
structure. The P-E hysteresis loops show the improvement in
ferroelectricity with the addition of BT due to a reduction of
the leakage current. The magneto-dielectric effect has been
observed at room temperature with the highest value of
magnetocapacitance at 3.2% for a 40 mol% addition of BT.
The magnetoelectric coupling coefficient (γ ) was approxi-
mated by Δεr ~ γM 2 , and the value of γ was calculated using
linear fitting; it was found to be ∼4.09 × 10−2 (emu g)−2 for a
composite with x = 0.40.
Smart Mater. Struct. 23 (2014) 105024
Acknowledgement
We would like to thank the Council of Scientific and Indus-
trial Research (CSIR), New Delhi, India, grant No. 03(1272)/
13/EMR- II (dated 12.04.2013), for their financial support.
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