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Materials Science and Engineering B 181 (2014) 70–76

Contents lists available at ScienceDirect

Materials Science and Engineering B

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

Short communication

Structural, electrical and dielectric properties of

La0.7 Sr0.3 MnO3 –ErMnO3 multiferroic composites
S.K. Mandal a,∗ , P. Dey a , T.K. Nath b
a
Department of Physics, National Institute of Technology Agartala, Tripura 799055, India
b
Department of Physics and Meteorology, Indian Institute of Technology, Kharagpur 721302, India

a r t i c l e i n f o a b s t r a c t

Article history: A different kind of multiferroics with composite character has been studied. Detailed study
Received 18 June 2013 on electrical and dielectric properties of structurally characterized multiferroic composites
Received in revised form 23 October 2013 xLa0.7 Sr0.3 MnO3 –(1 − x)ErMnO3 (where, x = 0, 0.1, 0.15, 0.2, 1), prepared through chemical ‘pyrophoric
Accepted 18 November 2013
reaction’ technique, have been presented. Average particle size of the composites is found to be in nano-
Available online 4 December 2013
metric region. Both structural and magnetic studies confirm almost complete immiscibility within the
mixture of two compounds of La0.7 Sr0.3 MnO3 and ErMnO3 having nearly identical chemical formula.
Keywords:
Impedance value is found to be decreased with increasing La0.7 Sr0.3 MnO3 content in the compos-
Impedance
Dielectric constant ites that can be attributed to the improved electrical connectivity in the sample. Dielectric study
Multiferroic reveals that pure ErMnO3 , 0.1La0.7 Sr0.3 MnO3 –0.9ErMnO3 and 0.15La0.7 Sr0.3 MnO3 –0.85ErMnO3 compos-
ites exhibiting ferroelectric relaxor behavior, whereas 0.2La0.7 Sr0.3 MnO3 –0.8ErMnO3 composite is found
to be strongly diffusive ferroelectric sample. Appearance of a distinct hump in dielectric constant of
0.1La0.7 Sr0.3 MnO3 –0.9ErMnO3 composite at the vicinity of para-ferromagnetic transition temperature
may be due to some sort of magneto-electric coupling in these composites.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction optimized the weight percent of ferromagnetic LSMO and ferro-

electric EMO in the composite to attain sustained simultaneous
Discovery of ferroelectricity in BaTiO3 [1,2] has attracted the ferromagnetic and ferroelectric properties.
attention of a large number of researchers to study ferroelec- Impedance spectroscopy is a very powerful and convenient
tric properties of various oxide materials of different structural experimental tool to explore the correlation of electrical charac-
families, e.g., perovskites, pyrochlore, tungsten bronze, etc. for teristics of a material with its microstructure. This enables us to
technological device applications such as actuators, sensors, and evaluate and separate the contributions from various components,
transducers. In most of the applications, a high dielectric constant i.e., through grains, interfaces, grain boundaries, etc., to the overall
and a low dielectric loss are generally required together with a electrical properties of the polycrystalline materials in the fre-
small temperature coefficient of dielectric constant. The discov- quency domain [6–17]. In this present work, we have considered
ered lead-free (Ba, Ca)(Ti, Zr)O3 (BCTZ) ceramics [3] have attracted hexagonal manganites EMO as the ferroelectric component and
great attention due to the excellent piezoelectric properties (with LSMO as the ferromagnetic component in the composite. Since the
d33 = 500–600 pC/N). Depending on the chemical composition, difference in ionic radii of Er3+ and La3+ is appreciably large, thereby
various ferroelectric/antiferroelectric or paraelectric phases with promising almost no solubility between LSMO and EMO, having
slightly different dielectric properties and crystal structures of nearly identical chemical formula in the mixture. In this paper, we
different types are formed. Nowadays, multiferroic material [4], have discussed the structural, electrical and dielectric properties
combining ferromagnetic and ferroelectric properties is a matter of lead free LSMO–EMO mutiferroic composite, as a function of
of intense research interest. Recently, we have reported room tem- temperature and frequency. We have correlated the frequency and
perature ferroelectric and ferromagnetic properties of lead free temperature dependent dielectric properties to the microstructure
multiferroics composites xLa0.7 Sr0.3 MnO3 (LSMO)–(1 − x)ErMnO3 of the polycrystalline material from the experimentally observed
(EMO) (weight percent x = 0.1, 0.2) [5]. In this study, we have electrical response in the impedance spectrum.

2. Background
∗ Corresponding author. Tel.: +91 3812348530.
E-mail addresses: [email protected] (S.K. Mandal), AC impedance is a non-destructive experimental technique for
[email protected] (P. Dey). the characterization of microstructural and electrical properties of

0921-5107/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
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S.K. Mandal et al. / Materials Science and Engineering B 181 (2014) 70–76 71

various electronic materials [18]. The technique is based on ana- 4000

(112)
lyzing AC response of a system to a sinusoidal perturbation and ErMnO3
subsequent calculation of impedance as a function of frequency of
(a)

Intensity (cps)
the perturbation. The analysis of the electrical properties (dielectric 3000
constant, conductivity, dielectric loss, etc.), carried out using relax-

(110)
ation frequency (ωmax ) values, gives unambiguous results when
compared with those obtained at arbitrarily selected fixed frequen- 2000

(004)

(114)

(300)
cies. The frequency dependent impedance properties of a material

(220) (221)
can be described as complex permittivity (ε*), complex impedance

(116)

(222)
(102)
(Z*), complex admittance (Y*), complex electrical modulus (M*) and

(104)

(115)
(302)

(224)
(108)
(212) (204)
(202)
1000
dielectric loss or dissipation factor (tan ı) [19]. The real (ε , Z , Y , M )
and imaginary (ε , Z , Y , M ) parts of the complex parameters are

(111)

(214)
in turn related to one another as follows: Z* = Z − jZ = Rs − 1/jωCs ,
ε* = ε − j␧ , M* = Mel + jM = jωε0 Z*, tan(ı) = ε /ε , where ω is the 0
√
angular frequency, ε0 is the permittivity in free space, j = −1 is 20 30 40 50 60 70 80
the imaginary factor. Rs and Cs are the series resistance and capac- 2θ (in degree)
itance, respectively. The complex impedance of the system can be
demonstrated as †
x = 0.5
 (b) 2400 EMO
y(, t)d() 5000
Z ∗ (t) = Z0 (t) (1) † *
1 + jω
1600

* *

Intensity (cps)
800
The real and imaginary parts of the above expression are †
4000 * †
 * ***
†
* *
32 33 34
† † †
y(, t)d() * * † †
Z(ω, t) = Z0 (t) (2)
1 + ω2  2 3000 * EMO x = 0.5
† LSMO
and
 2000
 y(, t)(ω) ∗ d()
Z (ω, t) = Z0 (t) , (3) x = 0.15
1 + ω2  2
1000
respectively, where t is the time period,  the relaxation time and x = 0.1
y(, t) the distribution of relaxation time. These relations offer
wide scope for a graphical analysis of the various parameters 20 30 40 50 60 70 80
under different conditions of temperature and frequency. From the 2θ (in degree)
microstructural point of view, a ceramic sample is composed of
grains and grain boundaries, which has different resistivity () and Fig. 1. XRD pattern for (a) pure EMO sample with indexing of all peaks, (b)
0.1LSMO–0.9EMO, 0.15LSMO–0.85EMO and 0.5LSMO–0.5EMO composites. Inset in
dielectric permittivity (ε) [20]. The real part (Z ) and imaginary part (b) shows the XRD data of x = 0.5 composite and pure EMO sample, at narrow range
(Z ) of the complex impedance are given below [21]: of 2 between 31◦ and 35◦ .
Rg Rgb
Z = 2
+ (4)
1 + (ωRg Cg ) 1 + (ωRgb Cgb )2 powders with the desired metal ions embedded in its matrix. The
dried carbonaceous fine powder has been calcined (in air 5 h) at a
ωRg2 Cg
2 C
ωRgb temperature of 900 ◦ C to obtain the required composite phase.
gb
Z  = + (5) Structural characterizations have been carried out using x-ray
1 + (ωRg Cg )2 1 + (ωRgb Cgb )2 diffractometer (XRD) (Philips, PW–1729) with monochromatic Cu-
where Rg /Cg and Rgb /Cgb , are the resistance/capacitance of the K␣ radiation, and high resolution field emission scanning electron
grain and grain boundary, respectively. microscope (FE-SEM) (Carl Zeiss, SUPPRATM 40). To measure the
electrical properties of the compounds, air-drying silver paints was
3. Experimental details used on both flat surfaces of the pellets to serve as electrodes. Elec-
trical impedance (Z), capacitance (C) and dielectric loss (D) were
Multiferroic composites xLSMO–(1 − x)EMO with different measured as a function of different temperatures (300–773 K) in a
weight percent (x = 0, 0.1, 0.15, 0.2, 1) were prepared by wide range of frequencies 10 kHz–1 MHz, using precision LCR meter
chemical “pyrophoric reaction process”. The LSMO phase were (Agilent 4284A, 20 Hz–1 MHz) in conjunction with a laboratory-
prepared from high-purity La2 O3 (99.99%), Sr(NO3 )2 (99.0%) and made sample holder and heating arrangement. A chromel–alumel
Mn(CH3 COO)2 (99.0%) and EMO phase from Er(NO3 )2 (99.9%) and thermocouple and digital multimeter were used to measure the
Mn(CH3 COO)2 (99.0%). We have employed aqueous solution of the temperature. We have used high temperature silver paste for the
requisite amount of compounds in stoichiometric proportions with electrical contacts. We have taken data for both warming and cool-
triethanolamine (TEA) being added with these solutions at 1:1: 4 ing cycle, but have presented the data only those taken at cooling
(La, Sr/Er: Mn: TEA = 1: 1: 4) ratio to make viscous solution sep- cycle.
arately for LSMO and EMO. The clear solutions of TEA complexed
metal nitrates of those individual compounds of LSMO and EMO 4. Results and discussions
then are mixed properly in a single container and are evaporated
on a hot plate at 180 ◦ C with constant stirring. The continuous heat- 4.1. Structural characterizations
ing of these solutions causes foaming and puffing. When complete
dehydration occurs, the nitrate themselves are decomposed with In order to gain knowledge about the phase of this series
the evolution of brown fumes of NO2 leaving behind a voluminous, of xLSMO–(1 − x) EMO composites with different weight percent
carbonaceous, organic based, black, fluffy powders, i.e. precursor (1 ≤ x ≤ 0), we have carried out XRD at room temperature. Fig. 1(a)
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72 S.K. Mandal et al. / Materials Science and Engineering B 181 (2014) 70–76

Fig. 2. FE-SEM images for (a) LSMO, (b) EMO, (c) 0.1LSMO–0.9EMO composite and (d) 0.5LSMO–0.5EMO composite.

6
2.0x10
7
30 kHz 30 kHz
1.5x10 60 kHz 60 kHz
100 kHz 100 kHz 6
7 400 kHz 400 kHz 1.5x10
1.2x10

Z (Ohm)
1 MHz 1 MHz
Z (Ohm)

6
9.0x10 0.1LSMO-0.9EMO 1.0x106
EMO
6 (b)
6.0x10 (a)
5
5.0x10
6
3.0x10

0.0
30 kHz 30 kHz
1500 60 kHz
60 kHz 800
100 kHz 100 kHz
400 kHz 400 kHz
1200
Z (Ohm)

1 MHz 1 MHz
600
Z (Ohm)

900 0.15LSMO-0.85EMO 0.2LSMO-0.8EMO

400
600
(c) (d)

200
300

0 0
300 350 400 450 500 550 300 350 400 450 500 550
T (K) T (K)
Fig. 3. Impedance as a function of temperature at a frequency range of 30 kHz–1 MHz for (a) pure EMO sample, (b) 0.1LSMO–0.9EMO composite, (c) 0.15LSMO–0.85EMO
composite and (d) 0.2LSMO–0.8EMO composite.
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S.K. Mandal et al. / Materials Science and Engineering B 181 (2014) 70–76 73

T (K) T (K)
300 350 400 450 500 550 350 400 450 500 550

30 kHz 330 (b)

3
2.4x10 3
60 kHz 275 1.8x10
100 kHz
400 kHz 220
3
1.8x10 1 MHz 430 473 516
30 kHz 3
1.2x10
EMO 60 kHz
ε

3
1.2x10 100 kHz

ε
(a) 400 kHz
800 kHz 6.0x10
2
2 1MHz
6.0x10

0.1LSMO-0.9EMO
0.0 0.0
30 kHz 30 kHz
60 kHz (d)
3
1.65x10 100 kHz 1000
50 kHz
400 kHz 400 kHz
1 MHz
100 kHz
800
3
1.10x10 900 kHz
0.15LSMO-0.85EMO
800 kHz 600

ε
ε

1 MHz
2
(c) 700 kHz
5.50x10 400

0.2LSMO-0.8EMO
200
0.00
360 400 440 480 520 560 300 350 400 450 500
T (K) T (K)
Fig. 4. ε as a function of temperature at a frequency range of 30 kHz–1 MHz for (a) pure EMO sample, (b) 0.1LSMO–0.9EMO composite, inset shows the expanded view of ε
at high temperature region, (c) 0.15LSMO–0.85EMO composite and (d) 0.2LSMO–0.8EMO composite.

shows XRD pattern for pure EMO sample, where the peaks were composition, i.e., with change in x, are reminiscent with the fea-
indexed on the basis of hexagonal phase following JCPDS card no tures of that of an alloy of two immiscible elements. This in turn
14-0689. Fig. 1(b) shows XRD pattern for x = 0.1, 0.15 and 0.5 com- indicates an almost complete immiscibility within the mixture of
posites. For x = 0.5 composite, we can observe from Fig. 1(b) and its those two compounds of LSMO and EMO in these multiferroic com-
inset the appearance of both LSMO and EMO peaks [5] as pointed posites.
out by ‘†’ and ‘*’ symbols, respectively. This in turn indicates chem- We have carried out FE-SEM studies on composite samples. The
ical phase separation between two components of this composite measurement was performed on the pellet of the sample. From
(x = 0.5). Since XRD is a volume fraction sensitive measurement, the individual FESEM micrograph for LSMO (Fig. 2(a)) and EMO
in case of x = 0.5 composite, i.e., for 50% LSMO–50% EMO sample (Fig. 2(b)) taken at same magnification (50 K), we could identify
the coexistence of two phases of LSMO and EMO in XRD pattern that that LSMO and EMO samples exhibit distinctively different
are distinct and comprehensible compared to that of x = 0.1 and microstructures or morphologies of grains, where LSMO grains
0.15 composite. From XRD pattern, we have estimated the average are found to be nearly spherical and EMO grains have no regular
crystallite size (˚) for both LSMO and EMO phases of the com- shape. Moreover, the sizes of the LSMO grains are estimated within
posites using Scherrer formula: ˚ = k/ˇeff cos , where ˚ is the 70–100 nm, whereas sizes of EMO particles are estimated within a
average diameter of the nanocrystals in Å, k the shape factor (gen- few hundred of nanometers. Fig. 2(c) and (d) shows typical FE-SEM
erally taken as 0.89),  the wavelength of CuK␣ radiation (1.542 Å), cross-section micrographs for x = 0.1 and 0.5 composites, respec-
 the diffraction angle and ˇeff defined as ˇeff 2 = ˇm 2 + ˇs 2 , where tively. It is evident from this figure that two different sets of phases,
ˇm and ˇs are the experimental FWHM of the present sample and corresponding to LSMO and EMO, can clearly be distinguished from
that of a standard silicon sample, respectively. The standard sili- each other. Following the individual SEM image of LSMO and EMO
con sample is used to calibrate the intrinsic width associated with (as presented and discussed above), larger particles are identified
the equipment. It is found that average crystallite size for EMO as EMO, which are embedded into LSMO matrices having smaller
phase (˚ ∼ 50 nm) is reasonably larger than that of LSMO phase particle sizes. Quite expectedly, at the frame of FE-SEM image of
( ∼ 36 nm) in the composite. x = 0.1 composite there is abundance of larger size grains or chunk of
Room temperature XRD profiles of our series of multiferroic grains (believed as EMO grains) since the weight percentage of EMO
composites xLSMO–(1 − x)EMO (1 ≤ x ≤ 0) confirm the formation of is sufficiently large compared to that of LSMO in x = 0.1 composite
pure single phase of ErMnO3 (x = 0). More significant point is that than x = 0.5 composite. From XRD, using Debye Scherrer formula,
our XRD results confirm the coexistence of two phases of LSMO we have estimated crystallite size (discussed above). From SEM
and EMO in the composites. Furthermore, two important features, what we are observing the surface morphology of the sample in
such as, negligible shift in diffraction peak positions and the sys- the respective pellet. Thus, what we are observing from SEM pic-
tematic variation of relative intensities of the peaks with varying ture is most probably the agglomeration of several crystallites in
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74 S.K. Mandal et al. / Materials Science and Engineering B 181 (2014) 70–76

the pellet form. That is the reason the crystallite size (estimated 30 kHz
9
from XRD) may not match with the SEM data. 60 kHz
100 kHz
400 kHz
4.2. Electrical properties
1 MHz
The electrical properties of the composites have been inves- 6
tigated by impedance spectroscopy. Fig. 3 shows the impedance (a)

tan(δ)
as a function of temperature at different frequencies ranging
from 30 kHz to 1 MHz, for (a) pure EMO, (b) 0.1LSMO-0.9EMO, (c)
0.15LSMO-0.85EMO and (d) 0.2LSMO-0.8EMO composites, respec-
tively. The value of impedance is found to be of the order of 107 3
(Fig. 3(a)) for EMO sample at lower temperature range, where
with the increase in temperature impedance value decreases.
0.1LSMO–0.9EMO composite shows the impedance in the order of EMO
106 (Fig. 3(b)), which is less than that of the pure EMO sample. The
0
abrupt change in impedance is observed for 0.15LSMO–0.85EMO 400 500 600 700
and 0.2LSMO–0.8EMO composites, where the impedance value is
found to be of the order of 103 –102 at lower temperature range T (K)
(Fig. 3(c) and (d)). This abrupt change in impedance may be due to 9 0.1LSMO-0.9EMO
the improved electrical connectivity in the composite that in turn
leads to continuous change path way. This could be attributed to 30 kHz
enhanced metallic LSMO content in the sample. 60 kHz
100 kHz
400 kHz
4.3. Dielectric properties 6
1 MHz
tan(δ)

Dielectric constant (ε) as a function of temperature curves are (b)

shown in Fig. 4, where a distinct peak is clearly observed for (a)
pure EMO, (b) 0.1LSMO–0.9EMO and (c) 0.15LSMO–0.85EMO com-
3
posites. For (d) 0.2LSMO–0.8EMO composite, the peak position is
absent. It is well known that EMO forms in a hexagonal structure
with P63 cm space group and is found to undergo phase transition
from paraelectric to ferroelectric phase at a temperature of ∼560 K
in case of single crystal. In this present case, for pure EMO we have 0
obtained para-ferroelectric transition temperature (TC *) at 510 K, 350 400 450 500 550
which is within the predicted regime for any hexagonal manganites
[22–25]. This peak is found to appear at almost same temper-
T (K)
ature for pure EMO, 0.1LSMO–0.9EMO and 0.15LSMO–0.85EMO
100 kHz
composites. Appearance of TC * at almost same temperature in
400 kHz
these two composites with that of pure EMO sample, in turn
8 1 MHz
confirms almost chemical immiscibility between LSMO and EMO
in the composites. Moreover, ε versus T curves are found to be
strongly frequency dependent for pure EMO, 0.1LSMO–0.9EMO
(c)
and 0.15LSMO–0.85EMO composites, as can be clearly seen from
6
tan(δ)

Fig. 4(a)–(c). Thus we can assign a typical relaxor ferroelectric char-

acteristic with these three samples. These dielectric peaks are found
to be broadened markedly with increase in LSMO content in the
composite. For x = 0.2 composite, as shown in Fig. 4(d), the rather
broad transition in ε versus T curve along with strong frequency 4
dependence, mimics the characteristics of strongly diffusive fer-
roelectric relaxor [26] material. This observation of enhanced
0.15LSMO-0.85EMO
diffusive dielectric characteristics of the composites with increase
in LSMO, seems to be originated from the increased conductance 2
of the samples [27]. This enhanced conductivity of the composites 320 360 400 440 480
with increase in LSMO is also evidenced from electrical study, as T (K)
discussed in previous section.
Fig. 5(a)–(c) shows the variation of dielectric loss [tan(ı)] as a Fig. 5. Tan(ı) (dielectric loss) as a function of temperature at a frequency range of
30 kHz–1 MHz for (a) pure EMO sample, (b) 0.1LSMO–0.9EMO composite and (c)
function of temperature in the frequency range of 30 kHz–1 MHz 0.15LSMO–0.85EMO composite.
for pure EMO, 0.1LSMO–0.9EMO and 0.15LSMO–0.85EMO samples,
respectively. The loss pattern has typical features characterized by;
(a) a gradual increase in dielectric loss with temperature and (b) an to the combined effect of the reorientation of thermally activated
asymmetry in pattern. The gradual increase in the dielectric loss at polar flips and loss of polarization with rise in temperature [14].
high temperature region is indicative of transition from one type Furthermore, ε as a function of temperature curves at our
of process to another. It may be related to some thermal process lowest frequency of f = 30 kHz and at our highest frequency of
occurring in the material signifying maximum possible energy loss. f = 1 MHz, for pure EMO and 0.1LSMO–0.9EMO composite are
The broadened peak at lower temperature region may be attributed shown in Fig. 6(a)–(d) (extracted from Fig. 4). For 0.1LSMO–0.9EMO
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S.K. Mandal et al. / Materials Science and Engineering B 181 (2014) 70–76 75

600
30 kHz 1 MHz
275
EMO EMO

400 (a) (b)

ε 220

ε
200
165
260
30 kHz 1 MHz
800

0.1LSMO-0.9EMO 0.1LSMO-0.9EMO
(d) 250
(c)
600

ε
ε

240
400

350 400 450 350 400 450

T (K) T (K)

Fig. 6. Dielectric constant (ε) as a function of temperature at 1 MHz frequency for (a) pure EMO and (b) 0.1LSMO–0.9EMO composite. For 0.1LSMO–0.9EMO composite, a
hump near its ferromagnetic TC is clearly observed, whereas for pure EMO the hump is absent.

composite, in spite of consistent transition temperature (TC *) and ε

value with that of pure EMO, a distinct hump (Fig. 6 (b)) appeared in
the vicinity of para-ferromagnetic Currie temperature (TC ) (Fig. 7)
of the composite, which is absent in case of pure EMO (Fig. 6(a)). We 0.000 0.0000
have also incorporated the error bars in the figures. However, given
the accuracy of our measurement is 0.1%, the dimension of the error
-0.002 (a) -0.0002
bar is within the size of the symbol. Hence it confirms the real phys-
dχ /dT [(a. u.)/K]

ical origin of the hump. We suppose this appearance of hump in ε

versus T curve near TC to some sort of magneto-electric coupling -0.004 x=1 -0.0004
effect in the composite. This, in fact implies a finite probability of x = 0.5
tuning electrical properties of ferroelectric phase of composites by -0.006 x = 0.2
its ferromagnetic counterpart. However, for proper understanding -0.0006
of the physics behind this appearance of hump, further rigorous
x = 0.1
-0.008
experimental study is essential. -0.0008
-0.010 x LSMO - (1-x) EMO LSMO
4.4. Magnetic property
-0.0010
300 320 340 360
For basic magnetic characterization and to examine the exis-
tence of room temperature ferromagnetism, we have carried
out ac magnetic susceptibility ( ) as a function of temperature. 50 x = 0.1 T (K)
Fig. 7(a) shows differentiated in arbitrary unit as a function of HC= 69 Gauss
temperature for pure LSMO (calcined at 900 ◦ C) and for the series of (b)
M (emu/gm)

multiferroic composites xLSMO–(1 − x) EMO, where x = 0.1, 0.2 and 25

0.5. We have estimated their corresponding para-ferromagnetic
Curie temperatures, i.e., TC , from the minimum points of the 0 12
differentiated versus T curves (Fig. 7(a)). These TC values of
8
our series of multiferroic composites xLSMO–(1 − x) EMO, where 4
x = 0.1, 0.2, 0.5 and 1, confirm the existence of room temperature -25 0
ferromagnetism in this series of samples. We found that while -4
TC initially decreased from 364 K for x = 1 optimally doped LSMO -8
(prepared under identical condition) to 348 K for x = 0.9 composite,
-50 -12
-300-200-100 0 100 200 300
there was no significant shift for all lower x composites as can
be clearly seen from Fig. 7(a). This observation mimics with the -4000-2000 0 2000 4000
observation as obtained by Park et al. [28] for LSMO: LuMnO3 H (Oe)
composites and thus following them, based upon this observation
(Fig. 7(a)), we can also assign only about 1% solubility of EMO Fig. 7. (a) Derivative plot of for xLSMO–(1 − x) EMO composites, the lowest point
into LSMO in our composite. Thus the estimation of TC of this corresponding to TC . (b) M–H curve at T = 300 K for x = 0.1 composite. Inset shows
series of composites further establishes chemical phase separation the expanded view of the coercive field.
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76 S.K. Mandal et al. / Materials Science and Engineering B 181 (2014) 70–76

between those two compounds and ensures negligible solubility References

between them. Fig. 7(b) shows the external field (H) dependent
magnetization (M) exhibiting prominent hysteresis loops with [1] M.E. Lines, A.M. Glass, Principles and Applications of Ferroelectrics and Related
Materials, Oxford University Press, London, 1977.
reasonably good coercive field (HC ) (inset in Fig. 7(b)). [2] B. Wul, L.M. Goldman, C. R. Acad. Sci. URSS 46 (1945) 139.
[3] W. Li, Z. Xu, R. Chu, P. Fu, G. Zang, Mater. Lett. 64 (2010) 2325.
5. Conclusions [4] J.R. Sahu, A. Ghosh, A. Sundaresan, C.N.R. Rao, Mater. Res. Bull. 44 (2009)
2123–2126, and references therein.
[5] P. Dey, T.K. Nath, M.L. Nanda Goswami, T.K. Kundu, Appl. Phys. Lett. 90 (2007)
In conclusions, we have studied a different kind of multiferroics 162510.
with composite character. In this direction, we have carried out [6] S. Lanfredi, A.C.M. Rodrigues, J. Appl. Phys. 86 (1999) 2215.
detailed study on electrical and dielectric properties of structurally [7] A. Huanosta, O. Alvarez-Fregoso, E. Amano, C. Tabares-Munoz, M.E. Mendoza-
Alvarez, J.G. Mendoza-Alvarez, J. Appl. Phys. 69 (1991) 404.
characterized multiferroic composites xLSMO–(1 − x) EMO (where, [8] A. Huanosta, A.R. West, J. Appl. Phys. 61 (1987) 5386.
x = 0, 0.1, 0.15, 0.2, 1), prepared through chemical ‘pyrophoric reac- [9] N. Hirose, A.R. West, J. Am. Ceram. Soc. 79 (1996) 1633.
tion’ technique. Average particle size of the composites is found [10] D.C. Sinclair, A.R. West, Phys. Rev. B 39 (1989) 13486.
[11] S. Sahoo, D.K. Pradhan, R.N.P. Choudhary, B.K. Mathur, Adv. Mater. Lett. 3 (2)
to be in nanometric region. Our structural and magnetic stud- (2012) 97.
ies confirm almost complete immiscibility within the mixture of [12] P.R. Das, B. Pati, B.C. Sutar, R.N.P. Choudhury, Adv. Mater. Lett. 3 (1) (2012)
two compounds of LSMO and EMO having nearly identical chem- 8–14.
[13] P.R. Das, S. Behera, R. Padhee, P. Nayak, R.N.P. Choudhary, J. Adv. Ceram. 1 (3)
ical formula. The value of impedance is found to be decreased (2012) 232.
with increasing LSMO content in the composites. This feature can [14] S. Dutta, R.N.P. Choudhary, P.K. Sinha, A.K. Thakur, J. Appl. Phys. 96 (2004)
be attributed to the improved electrical connectivity in the sam- 1607.
[15] B. Behera, P. Nayak, R.N.P. Choudhary, Mater. Lett. 59 (2005) 3489.
ple. Our dielectric study reveals that pure EMO, 0.1LSMO–0.9EMO
[16] S. Dussan, A. Kumar, J.F. Scott, R.S. Katiyar, Appl. Phys. Lett. 96 (2010) 072904.
and 0.15LSMO–0.85EMO composites exhibit ferroelectric relaxor [17] O. Raymond, R. Font, G. Alvarez, J. Portelles, G. Srinivasan, J.M. Siqueiros, MRS
behavior, whereas 0.2LSMO–0.8EMO composite is found to be Online Proceedings Library, 966, 2006, 0966-T03-05.
strongly diffusive ferroelectric sample. Appearance of a distinct [18] J.R. Macdonald, Impedance Spectroscopy, Wiley, New York, 1987.
[19] K. Srinivas, P. Sarah, S.V. Suryanaryana, Bull. Mater. Sci. 26 (2003) 247.
hump in dielectric constant of 0.1LSMO–0.9EMO composite at the [20] J.R. Dygas, G. Fafilek, M.W. Breiter, Solid State Ionics 119 (1999) 115.
vicinity of para-ferromagnetic transition temperature is indicative [21] H.T. Langhammer, D. Makovec, Y. Pu, H.-P. Abicht, M. Drofenik, J. Eur. Ceram.
of some sort of magneto-electric coupling in these composites. Fur- Soc. 26 (2006) 2899.
[22] Z.J. Huang, Y. Cao, Y.Y. Sun, Y.Y. Xue, C.W. Chu, Phys. Rev. B 56 (1997) 2623.
ther study is proposed to investigate magneto electric coupling in [23] B. Lorenz, A.P. Litvinchuk, M.M. Gospodinov, C.W. Chu, Phys. Rev. Lett. 92 (2004)
this multiferroic composite. 087204.
[24] T. Katsufuji, S. Mori, M. Masaki, Y. Moritomo, N. Yamamoto, H. Takagi, Phys.
Acknowledgment Rev. B 64 (2001) 104419.
[25] H. Sugie, N. Iwata, K. Kohn, J. Phys. Soc. Jpn. 71 (2002) 1558.
[26] L.E. Cross, Ferroelectrics 76 (1987) 241.
One of the authors S. K. Mandal acknowledges the DST Project [27] A.I. Baranov, Ferroelectrics 285 (2003) 225.
(No. SR/FTP/PS-019/2012), India. We would like to acknowledge Dr. [28] S. Park, N. Hur, S. Guha, S.-W. Cheong, Phys. Rev. Lett. 92 (2004) 167206.

T.K. Kundu for help in electrical and dielectric measurements.