Materials Research Bulletin 60 (2014) 367375

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Materials Research Bulletin

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Dielectric and magnetic properties of xCoFe2O4(1
x)

[0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3] composites
Jyoti Rani a , K.L. Yadav a, *, Satya Prakash b
a
b

Smart Materials Research Laboratory, Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667, India
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Roorkee, Roorkee 247667, India

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 15 February 2014
Received in revised form 2 September 2014
Accepted 4 September 2014
Available online 6 September 2014

xCoFe2O4(1
x)(0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3) composites with x = 0.1, 0.2, 0.3 and 0.4 have
been synthesized by solid state reaction method. X-ray diffraction analysis and eld emission secondary
electron microscopy have been used for structural and morphological analysis, respectively. The spinel
CoFe2O4 and perovskite 0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3 phase could be identied in the
composites. Two anomalies in dielectric constant have been identied: rst one is close to ferroelectric
to paraelectric phase transition of 0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3 ceramic and the other lies near
the magnetic transition temperature of CoFe2O4. There is an increase in magnetocapacitance and
saturation magnetization of the composites at room temperature with increase in CoFe2O4 content. The
magnetoelectric coupling coefcient (g ) was approximated by De  g M2 relation. The optical band gap
energy of the composites decreases with increase in CoFe2O4 content.
2014 Elsevier Ltd. All rights reserved.

Keywords:
A. Composites
B. Magnetic properties
C. X-ray diffraction
D. Dielectric properties

1. Introduction
Multifunctional materials are important members of the
materials family because of their potential applications in
advanced electronic devices. Materials in which coupled ferroelectric and ferromagnetic orders occur simultaneously are
known as magnetoelectric (ME) materials. The induction of
magnetization/polarization on the application of electrical eld/
magnetic eld is known as magnetoelectric (ME) effect which is
extremely useful phenomenon with a wide range of device
applications such as spintronics, multiple-stage memories,
magnetoelectric transducer, sensor and actuators, etc. [1]. The
ME materials are either single phase or composites. There are few
single phase ME materials like BiFeO3 and some rare earth
manganates. But the low critical temperatures (below room
temperature) and/or weak ME coupling of the single phase ME
materials restrict their applications in devices [2,3]. Therefore,
the ME composites containing piezoelectric and magnetrostrictive phases as constituent materials, have attracted a considerable attention of the researchers due to their higher ME effect as
compared to the single phase materials [4]. The composites are
the systems having at least two phases with different physical and
chemical properties. The properties of their nal product, i.e.

* Corresponding author. Tel.: +91 1332 285744; fax: +91 1332 273560.
E-mail address: klyadav35@yahoo.com (K.L. Yadav).
http://dx.doi.org/10.1016/j.materresbull.2014.09.013
0025-5408/ 2014 Elsevier Ltd. All rights reserved.

composites are determined by the number, type and volume ratio

of the constituent phases, as well as by the individual properties,
degree of interconnectivity and interface properties [5]. The ME
effect in composites is a product property, i.e. this effect is absent
in the individual constituent component but present in the
composites as a result of coupling between the components. The
ME effect for the composites can be written as [4]:
MEeffect

magnetic
mechanical
electrical
mechanical

or

mechanical
electrical
mechanical
magnetic

For achieving strong magnetoelectric coupling in a composite,

the ferroelectric phase with large piezoelectric response and
magnetic phase with large magnetostriction coefcient are
desirable [3]. In ME composites, lead zirconium titanate (PZT)based ceramic are widely used as a ferroelectric phase due to their
high piezoelectric properties [59]. But PZT-based ceramics suffer
the global restrictions in their use due to the toxicity of lead oxide
with respect to the environment as well as biosphere. Therefore,
there is growing demand for lead-free materials.
Among the lead-free ferroelectrics BaTiO3 (BT)-based materials,
having perovskite ABO3 structure, are becoming potential substitute for PZT-based materials as they exhibit good dielectric,
ferroelectric and piezoelectric properties [10]. Liu et al. [11]
studied a lead-free yBa(Zr0.2Ti0.8)O3(1
y)(Ba0.7Ca0.3)TiO3 [yBZT
( 1
y)BCT] ferroelectric system and reported that it shows high
piezoelectric coefcient d33620 pCN
1 (y = 0.5) which is attributed to the presence of morphotropic phase boundary (MPB)

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J. Rani et al. / Materials Research Bulletin 60 (2014) 367375

starting from a tetragonalcubicrhombohedral triple point

resulting in a very low energy barrier for polarization rotation
and lattice distortion. In magnetic materials, CoFe2O4 [CFO] is a
ferrite material with inverse spinel structure which has moderate
saturation magnetization, good chemical stability and large
magnetostriction coefcient [12]. Due to large magnetostriction
coefcient of CoFe2O4 and high piezoelectric coefcient of 0.5Ba
(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3, these materials are selected here
as constituent materials for preparing ME composites. In the
present work, xCoFe2O4(1
x)(0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)
TiO3) spinelperovskite composites have been synthesized by
solid state reaction method. The constituent CoFe2O4 phase,
having small particle size as it is obtained from solgel process, is
mixed with large size particles of 0.5Ba(Zr0.2Ti0.8)O30.5
(Ba0.7Ca0.3)TiO3 ceramic synthesized by solid state reaction
method. This mixing may provide a composite with dense
microstructure which may improve functional properties. To the
best of our knowledge, there are no reports on the optical studies
of xCoFe2O4(1
x)(0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3) composites. In the present paper structural, dielectric, ferroelectric,
magnetic and magnetodielectric properties of xCoFe2O4(1
x)
(0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3) composites have been
studied along with their optical properties.
2. Experimental
xCoFe2O4(1
x)(0.5Ba(Zr0.2Ti0.8)O30.5(Ba0.7Ca0.3)TiO3)
[xCFO(1
x)(0.5BZT0.5BCT)] spinelperovskite composites with
x = 0.1, 0.2, 0.3, and 0.4 were synthesized by solid state reaction
method. All chemicals used for the synthesis were of analytical
grade. The starting chemicals BaCO3, ZrO2, TiO2 and CaCO3 were
taken in stoichiometric proportion for the synthesis of (05BZT
05BCT) ceramic. The mixtures of oxides were mixed in acetone
media for 68 h using agate mortar. This mixture was calcined at
1100  C for 2 h in a furnace with heating rate 5  C/min. CoFe2O4 was
synthesized by solgel method using Co(NO3)26H2O and Fe
(NO3)29H2O as a starting materials. Fe(NO3)29H2O and Co
(NO3)26H2O in molar ratio 2:1 were dissolved in doubled distilled
water under a constant stirring by magnetic stirrer. Then citric acid
and ethylene glycol (in molar ratio of 1:4) were added in the above
solution. The solgel reaction was continued for 1 h and then the
temperature was increased to 80  C with continuous stirring until
the gel got dried. The powder so obtained was dried at 100  C
overnight and then this sample was ground using mortar and
pestle. Finally, the above prepared sample was calcined at 800  C
for 3 h. To obtain the nal composites, synthesized and CFO were
mixed thoroughly in agate mortar for 45 h in the molar ratio of
90:10, 80:20, 70:30 and 60:40. These mixtures were pressed to
obtain cylindrical pellet of nearly 10 mm diameter and 1 mm
thickness by applying uniaxial pressure of about 6  107 kg/m2
using hydraulic press. These pellets so obtained were sintered at
1150  C for 2 h. The phases formed in the composites were
conrmed by X-ray diffraction technique (XRD) using Bruker AXS
D8 diffractometer operating with Cu-Ka radiation (l = 1.5406 )
with a scanning rate of 1 /min. Field emission scanning electron
microscope (FESEM) (FEI Quanta 200F) operating at 20 kV, coupled
with an energy dispersive X-ray analyser (EDX), was used for the
microstructural analysis of the sintered samples. Average grain size
of the sample was calculated from FESEM micrographs with the
help of linear intercept method. Dielectric measurements as a
function of temperature and frequency were carried out with the
help of HIOKI 3532-50 LCR meter. The polarization versus electric
eld (PE) hysteresis loops measurement of the samples were
carried out by using computer controlled modied Sawyer Tower
circuit (Automatic PE loop tracer system, Marine India Electr. Pvt.,
Ltd.). For the magnetic hysteresis loops measurement, vibrating

sample magnetometer (VSM) was used with the magnetic eld in

the range
10 kOe  H  10 kOe. Magnetocapacitance (magnetodielectric) measurement was carried out using Wayne Kerr
6500High frequency LCR meter interfaced with a magnet. The
UVvis diffuse reectance spectrophotometer (Shimadzu UV2450) was used in the wavelength range 200800 nm using BaSO4
as the reference to determine optical band gap energy of the
composites.
3. Results and discussion
3.1. Phase identication and microstructural analysis
Fig. 1 shows the XRD pattern of [xCFO(1
x)(0.5BZT0.5BCT)];
x = 0.1, 0.2, 0.3 and 0.4 composites along with that of pure (0.5BZT
0.5BCT) and CFO ceramics. XRD pattern of pure (0.5BZT0.5BCT)
and CFO exhibit perovskite and spinel (cubic) structures,
respectively. The peaks corresponding to CFO and (0.5BZT
0.5BCT) phases are observed in the XRD of all composites. The
intensity of the major peak (3 11) of CFO varies in accordance to its
mole fraction in the composites. It can be observed that with the
incorporation of CFO in (0.5BZT0.5BCT), the XRD peaks of the
ferroelectric phase show splitting. This indicates a change in
structure of the ferroelectric phase. Similar type of behaviour has
been observed by Ciomaga et al. [5] in NiFe2O4Pb(Zr0.47Ti0.53)O3
composites.
The FESEM micrographs (Fig. 2) of the sintered [xCFO-(1-x)
(0.5BZT0.5BCT)] composites indicate the dense microstructure.
The average grain size of the samples, calculated by linear
intercept method, was found to decrease with increase in CFO
concentration. The calculated values of the average grains size are
0.62, 0.44, 0.39 and 0.34 mm for x = 0.1, 0.2, 0.3 and 0.4,
respectively. The homogeneous distribution of the constituent
elements in a sample was conrmed by the line scan (shown
below of the respective microstructure in Fig. 2), taken across the
grain boundary. It can be clearly observed that there is no rise and
fall in the signal corresponding to each element along the line
which indicates the homogeneous nature of the samples. The inset
of Fig. 2(a) shows the TEM image of calcined CFO ceramic which
has been synthesized by solgel method. This image indicates that
the average particle size of synthesized CFO is 200240 nm
having nearly cuboidal shape.

Fig. 1. X-ray diffraction pattern of [xCFO(1
x)(0.5BZT0.5BCT)] composites.

J. Rani et al. / Materials Research Bulletin 60 (2014) 367375

369

Fig. 2. (a)(d) FESEM micrographs of sintered [xCFO(1
x)(0.5BZT0.5BCT)] composites for (x = 0.1, 0.2, 0.3 and 0.4) along with their line scan micrographs (shown below the
respective compositions). Inset of Fig. 2(a) shows the TEM image of calcined CFO.

3.2. Dielectric properties

Fig. 3(a) and (b) shows the variation of the dielectric constant
(e) and dielectric loss (tan d) for [xCFO(1
x)(0.5BZT0.5BCT)]
spinelperovskite composites with frequency in the range
0.1 kHz1 MHz at room temperature. It is found that e of all
synthesized composites decreases with increase in frequency and
becomes constant above 1 kHz frequency. This is because at lower
frequency, different types of polarizations such as electronic, ionic,
dipolar and space charge contribute to the dielectric constant but
some of them can not follow up the fast variation of the electric
eld at high frequency and hence the e; decreases [7]. On the other
hand, dielectric behaviour of the spinelperovskite composites
may also depend on the electron hopping between Fe2+ $ Fe3+ and
Co2+ $ Co3+ resulting in orientational polarization in ferrite phase
of the composites. The hopping of electron between these ions
does not follow the applied electric eld at higher frequency and
hence does not contribute in dielectric constant [13]. The

dispersion of e observed at low frequency region for all composites

can be explained by Koops phenomenological model [14] and
MaxwellWagner polarization theory [15,16]. The application of
electric eld on the composites causes the accumulation of space
charge, provided by the ferrite phase, at the interface of the two
phases due to different permittivities and conductivities [17]. As
the system becomes more heterogeneous, the space charge
polarization increases leading to increase in dispersion behaviour
of e. The value of e of the composites decreases on increasing CFO
concentration because the incorporation of CFO dilutes the
dielectric properties of ferroelectric phase as suggested for
Ba0.8Sr0.2TiO3CoFe2O4 system [18]. The decrease in value of tan d
becomes steeper with increase in CFO concentration in low
frequency region indicating the heterogeneous conduction in
composites [19].
The dielectric constant (e) and dielectric loss (tan d) of [xCFO
(1
x)(0.5BZT0.5BCT)] spinelperovskite composites (x = 0.1, 0.2,
0.3 and 0.4) were determined as a function of temperature at

Fig. 3. (a) Dielectric constant (e) and (b) dielectric loss (tan d) of [xCFO(1
x)(0.5BZT0.5BCT)]; x = 0.1, 0.2, 0.3 and 0.4 composites as a function of frequency at room
temperature.

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J. Rani et al. / Materials Research Bulletin 60 (2014) 367375

Fig. 4. (a)(d) Dielectric constant (e) (e) and (f) dielectric loss (tan d) of [xCFO(1
x)(0.5BZT0.5BCT)]; x = 0.1, 0.2, 0.3, and 0.4 composites as a function of temperature at 5,
10, 50, 100, 500 kHz and 1 MHz frequencies.

J. Rani et al. / Materials Research Bulletin 60 (2014) 367375

different frequencies and these plots are shown in Fig. 4. Two

dielectric anomalies are observed for all composites in Fig. 4. The
initial dielectric anomaly at low temperature was observed close to
the ferroelectric to paraelectric transition temperature of 0.5BZT
0.5BCT ceramic and may be taken as the signature of ferroelectricity in the composites. This anomaly shifts towards higher
temperature with the increase in frequency indicating the relaxor
behaviour of [xCFO(1
x)(0.5BZT0.5BCT)] composites. The
relaxor behaviour originates from the disordered distribution of
the different ions on the equivalent lattice sites (i.e. compositional,
disorder, also called chemical, ionic or substitutional disorder).
These materials have short-range polarization ordering and have
high frequency dependent dielectric properties [20]. The shifting
of dielectric anomaly towards higher temperature with the
increase in frequency indicates the decrease in relaxation time
with increase in temperature [21]. The second dielectric anomaly
at high temperature region may correspond to the magnetic
transition temperature (500  C) of CFO [22]. Fig. 4(e)(h) shows
tan d of [xCFO(1
x)(0.5BZT0.5BCT)] composites. The broad
peak in tan d, which shifts towards higher temperature with
increasing frequency, can be clearly observed (inset of Fig. 4(e)
(h)). This behaviour of the tan d also conrms the relaxor behaviour
of the composites. The value of tan d increases signicantly at
higher temperature due to the increase in space charge conduction
which may be associated with transportation of defects such as
oxygen vacancies to the electrodedielectric interface [23].
Fig. 5(a) and (b) shows the temperature dependence of
dielectric constant (e) and dielectric loss (tan d) for [xCFO
(1
x)(0.5BZT0.5BCT)] composites for x = 0.1, 0.2, 0.3 and 0.4 at
frequency 5 kHz. It is observed that the value e of composites
decreases at room temperature and increases at high temperature
with increasing CFO content. This decrease in e at room
temperature may be due to the low resistivity of ferrite while at
high temperature the hopping conduction between Fe3+ $ Fe2+and
Co2+ $ Co3+ in the ferrite phase dominates [24]. As the CFO content
increases, the Fe and Co ions increases resulting in the increase in
hopping. Hence, value of e and tan d increases at high temperature
with increase in CFO content in the composites.
3.3. Polarizationelectric eld hysteresis loop
Fig. 6 illustrates the polarizationelectric eld (PE) hysteresis
loops for [xCFO(1
x)(0.5BZT0.5BCT)] composites at room
temperature. All composites exhibit the PE hysteresis loop
thereby indicating the ferroelectric nature. The spontaneous
polarization (2Ps), remnant polarizations (2Pr) and the coercive

371

eld (2Ec) of the samples are given in Table 1. The decreasing value
of remnant polarization for these spinelperovskite composites
may be attributed to the dilution of ferroelectric properties of
(0.5BZT0.5BCT) with increasing CFO phase. Similar observation
was reported by Wang et al. [18]. The increase in coercive
eld value of the composites with increase in CFO concentration
may be due to the pinning and hindering of the domain wall
motion of the ferroelectric region due to the existence of magnetic
CFO phase [25].
3.4. Magnetic properties
The magnetizationmagnetic eld (MH) hysteresis loops for
[xCFO(1
x)(0.5BZT0.5BCT)] composites are shown in Fig. 7(a).
All composites exhibit typical ferromagnetic hysteresis loops,
indicating the presence of ordered magnetic structure in the
composites. The magnetic moment of the composites in terms of
Bohr magneton was determined by using following relation [13].
 0 
ss
mB M 
(1)
5585
0

where mB is Bohr magneton, M and s s represent the molecular

weight and magnetization per gram mol of the sample, respectively, and 5585 is the magnetic factor. The variation of coercive
eld (2Hc), saturation magnetization (2Ms) and magnetic moment
(mB) of the composites with CFO content are shown in Fig. 7(b), and
their values are given in Table 1. The value of saturation
magnetization for synthesized [04CFO06(05BZT05BCT)] composite is higher than the previously reported values for 0.9
(0.7BiFeO30.3BaTiO3)0.1CoFe2O4 [26] and 0.5BiFe0.5Cr0.5O3
0.5NiFe2O4 [27] composites. The saturation magnetization and
magnetic moment increase with increasing concentration of CFO
because each grain of CFO acts as a centre of magnetization and the
saturation magnetization of composites is the vector sum of all
these individual contributions. Thus the magnetic ordering
increases with the increase in ferrite content which results in
the increase of net magnetization [7]. The value of coercive eld of
the composites is much lower than pure CFO ceramic (1500 Oe)
[28], indicating the easy magnetization characteristic of ferromagnetic phase in ferroelectric matrix. The coercive eld of the
composites was found to decrease with increasing CFO concentration which means that magnetization can be realized more easily
with increasing CFO content [9]. It is suggested that the
ferroelectric grains in ferrite phase act as pores in the presence
of applied magnetic eld and break the magnetic circuit. As the
concentration of CFO increases, these pores decrease and

Fig. 5. (a) Dielectric constant (e) (b) dielectric loss (tan d) of [xCFO(1
x)(0.5BZT0.5BCT)]; x = 0.1, 0.2, 0.3, and 0.4 composites as a function of temperature at frequency
5 kHz.

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J. Rani et al. / Materials Research Bulletin 60 (2014) 367375

Fig. 6. PE hysteresis loop of [xCFO(1
x)(0.5BZT0.5BCT)] composites; x = 0.1, 0.2, 0.3, and 0.4 at room temperature.

interaction between CFO grains increases with reduction in

domain wall pinning by nonmagnetic phase leading to improved
coercivity [7,29].
3.5. Magnetodielectric study
The magnetodielectric study of the composites is an indirect
way to investigate the coupling between ferroelectricity and
magnetism of the composite materials. Fig. 8(a) shows the
percentage change in dielectric constant of the composites as a
function of magnetic eld at room temperature at frequency
1 kHz. In magnetoelectric materials, an applied magnetic eld
affects the magnetic order as well as the dielectric constant of the
system. The change in dielectric constant (or capacitance) on the
application of external magnetic eld is called magnetodielectric
(or magnetocapacitance) effect. The magnetocapacitance (MC) is
dened as [30]:
MC

eH
e0
 100%
e0

(2)

where e(H) and e(0) represent the value of dielectric constant at

magnetic eld (H) and at zero magnetic eld, respectively. The
values of magnetocapacitance percentage for all synthesized
composites are given in Table 1. The value of magnetocapacitance

of these composites is found to be higher than the previously

reported value [31]. In composites, the ME coupling mainly arises
from the magneticmechanicalelectric interaction between
magnetostrictive and piezoelectric phase through the stress/strain
at interface [32]. The application of external magnetic eld on the
composites generates stress on CFO phase due to its magnetostriction effect. This stress is transferred to the ferroelectric phase
mechanically, resulting in an electric polarization of the ferroelectric phase via ME effect [33] and hence the dielectric behaviour
gets modied. The thermodynamic potential (F) for a ferroelectromagnet can be expressed as:
0

b
b
0
F F0 aP2 P4
PE a M2 M4
MH g P2 M2
2

(3)

where P and M are the order parameters for polarization and

magnetization, respectively and a,b, a0 , b0 and g are coupling
coefcients. The term g P2M2 shows the coupling between
polarization (P) and magnetization (M) known as magnetoelectric
coupling term which is valid for any ferroelectromagnets [34].
Kimura et al. [35] used thermodynamic potential (F) of the
ferroelectromagnet to calculate the effect of magnetic ordering on
the dielectric susceptibility and found that the difference of
relative dielectric constant will be proportional to the square of
magnetic-order parameter, i.e. De  g M2. The linear tting with

Table 1
Ferroelectric, magnetic, magnetocapacitance and optical properties of [xCFO(1
x)(0.5BZT0.5BCT)] composites.
x value

2Ps
(mC/cm2)

2Pr
(mC/cm2)

2Ec
(kV/cm)

2Ms
(emu/g)

2Hc
(kOe)

Magnetic moment (mB)

MC (%)

Eg
(eV)

0.1
0.2
0.3
0.4

4.923
3.305
2.999
2.212

1.819
1.328
1.285
0.933

10.678
17.309
19.21
11.454

10.899
30.179
37.770
44.897

0.507
0.475
0.339
0.204

0.219
0.609
0.766
0.915

0.33
0.67
0.76
1.07

3.17
3.14
3.06
2.87

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373

Fig. 7. (a) Magnetization versus magnetic eld (MH) curves (b) Coercivity (2Hc), saturation magnetization (2Ms) and magnetic moment (mB) variation with CFO content for
[xCFO(1
x)(0.5BZT0.5BCT)] composites; x = 0.1, 0.2, 0.3, and 0.4 at room temperature.

this formula gives the value of magnetoelectric coupling coefcient g . The fractional change of dielectric constant (De/e(0)) as a
function of M2 for [04CFO06(05BZT05BCT)] is shown in Fig. 8(b),
and the variation of M2 with magnetic eld (H) for x = 0.4 is shown
in inset of Fig. 8(b). The calculated value of g for [04CFO06
(05BZT05BCT)] composite is 
2.18  10
5 (emu/g)
2. Similarly
the values of g are
1.99  10
4,
3.03  10
5 and
2.33  10
5 for
x = 0.1, 0.2 and 0.3, respectively.
3.6. Optical band gap determination
The optical properties of [xCFO(1
x)(0.5BZT0.5BCT)] composites (x = 0.1, 0.2, 0.3 and 0.4) have been determined by taking
diffuse reectance spectra. The value of optical band gap energy
(Eg) can be evaluated with the help of fundamental absorption,
which corresponds to electron excitation from the valance band to
conduction band. The reectance values have been converted to
absorbance by application of KubelkaMunk function which is
expressed as:
FR

1
R2
2R

(4)

where R is the diffused reectance, F(R) is KubelkaMunk function

[36]. Within the energy range having the absorption edge features,
F(R) can be assumed to be proportional to the absorption
coefcient (a) [37]. The optical band gap (Eg) for [xCFO(1
x)
(0.5BZT0.5BCT)] composites can be deduced by Taucs relation.
According to this relation, the absorption coefcient for direct band

gap materials is given by:

hna Ahn
Eg 1=2

(5)

where hv is the photon energy, a is the absorption coefcient, and A

is a constant of proportionality [38]. Fig. 9 shows the (hna)2
versus hn plot (Tauc plot) for [xCFO(1
x)(0.5BZT0.5BCT)]
composites (x = 0.1, 0.2, 0.3 and 0.4). The extrapolation of the linear
portion of (hna)2 versus hn plots upto (hna)2 = 0 gives the value of Eg
for all composition, and these values are given in Table 1. Inset of
Fig. 9(a) shows the optical band gap 3.26 eV of (0.5BZT0.5BCT)
which is a solid solution of BZT and BCT. The band gap of
(0.5BZT0.5BCT) is dominant in the synthesized composite system.
This optical band gap may be associated with intermediate energy
levels within the band gap which may be due to the presence of
structural orderdisorder in the lattice due to the symmetry
break between O


Zr


O, O

Ti


O bonds (oxygen vacancies) as
suggested by Sczancoski et al. [39]. These intermediary energy
levels may be composed of 2p states of oxygen situated near the
valence band and 3d and 4d state of titanium and zirconium,
respectively, which are positioned below conduction band (deep
and shallow holes) [40]. As the concentration of CFO increases,
the optical band gap of (0.5BZT0.5BCT) ceramic decreases. The
possible reason for this decrease in optical band gap with the
increase in CFO content may be as follows: the optical band gap of
CFO is low (1.42 eV) [41], which results in the shifting of optical
band gap of (0.5BZT0.5BCT) towards low energy side. Further,
addition of CFO results in narrowing of the band gap due to lowering
of the conduction band and an upward shift of the valence band on

Fig. 8. (a) Magnetocapacitance of [xCFO(1
x)(0.5BZT0.5BCT)]; x = 0.1, 0.2, 0.3 and 0.4 composites at room temperature. (b) Variation of magnetocapacitance with
(magnetization)2 for [04CFO06(05BZT05BCT)] composite. Inset shows variation of (magnetization)2 with magnetic eld (H) for x = 0.4.

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J. Rani et al. / Materials Research Bulletin 60 (2014) 367375

Fig. 9. (a)(d) (hna)2 versus hn plot for [xCFO(1
x)(0.5BZT0.5BCT)] composites with x = 0.1, 0.2, 0.3 and 0.4, inset of Fig. 9(a) shows the (hna)2 versus hn plot for the pure
(0.5BZT0.5BCT).

account of the potential uctuation introduced by the electron

electron and electronimpurity interactions [42]. Thus the band gap
of (0.5BZT0.5BCT) may be tuned by the addition of CFO.
4. Conclusions
Ferroelectric (0.5BZT0.5BCT) and magnetic CFO phases have
been used with molar ratio 90:10, 80:20, 70:30 and 60:40 for the
synthesis of composites using solid state reaction method. CFO
addition leads to the splitting of XRD peaks of ferroelectric
(0.5BZT0.5BCT) phase. The synthesized composites have a ne
grained homogeneous morphology. The variation of e with
frequency at room temperature reveals the decrease in e with
increasing CFO concentration of the composites. The temperature
dependency of dielectric properties indicates the relaxor behaviour for all composites with the presence of two dielectric
anomalies. Typical PE-loop conrms the ferroelectric nature of
the composites. In the prepared composites, the saturation
magnetization increases whereas the coercive eld decreases
with the increase in CFO content. Magnetocapacitance (1.07%)
was maximum for x = 0.4 composition. Increase in CFO content also
leads to decrease in optical band gap of the composites. Magnetic
and magnetocapacitance properties of these composites increase
with increasing CFO concentration which may make them useful
for applications in devices.
Acknowledgement
Authors would like to acknowledge the nancial help from
Council of Scientic and Industrial Research, New Delhi, India
under the research grant no. 03(1272)/13/EMR-II dated 12.04.2013.

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